A Dissertation
Entitled
Synthesis and Characterization of Lewis Acidic Aluminum and Gallium
Complexes
By
Nicholas Bruck Kingsley
Submitted as a partial fulfillment of the requirements for
the Doctor of Philosophy Degree in Chemistry
Advisor: Mark R. Mason, Ph.D.
College of Graduate Studies
The University of Toledo
August 2009
An abstract of
Synthesis and Characterization of Lewis Acidic Aluminum and Gallium
Complexes
Nicholas Bruck Kingsley
Submitted in partial fulfillment of the requirements for
the Doctor of Philosophy Degree in Chemistry
The University of Toledo
August 2009
Di- and tri(3-methylindolyl)methanes and related pyrrolyl-based ligands have
strong electron-withdrawing ability and reduced N→M π-donation when coordinated in
the η1–N bound mode since the nitrogen lone pair is delocalized over the aromatic
system. Thus, complexes based on these frameworks are potentially ideal for generation
of tripodal monomeric electrophilic metal centers. This dissertation reports the synthesis
and characterization of Lewis acidic aluminum and gallium complexes using di- and
tri(3-methylindolyl)methanes, tris(pyrrolyl-α-methyl)amine, and isonitriles.
In chapter 2, the synthesis and characterization of the first extensive series of
isonitrile complexes of aluminum and gallium are reported. The new complexes are
R3M•C≡NtBu (M = Al: R = tBu (1a), Me (1c), iBu (1e), Et (1f); M = Ga: R = tBu (1b),
Me (1d)); R3M•C≡N(2,6-dimethylphenyl) (M = Al: R = tBu (2a), Me (2c), iBu (2e), Et
ii
(2f); M = Ga: R = tBu (2b), Me (2d)).
characterized by 1H and
All 12 of the new complexes have been
13
C NMR spectroscopy, and seven of these complexes (1a, 1b,
1d, 2a, 2b, 2c, and 2d) have been characterized by X-ray crystallography, which
confirms the structures as donor-acceptor complexes with one isonitrile bound to a metal
trialkyl.
These isonitrile complexes serve as models of unknown non-classical CO
complexes of aluminum and gallium, and are presumed to model the intermediates for
CO insertion into Al–C and Ga–C bonds. Enthalpies of formation for these complexes
were determined using Isothermal Titration Calorimetry (ITC) in collaboration with Drs.
Bob Flowers and Joe Teprovich at Lehigh University.
In chapter 3, the synthesis and characterization of group 13 complexes with 3methylindole
(L1),
di(3-methylindolyl)phenylmethane
(L2),
and
tri(3-
methylindolyl)methane (L3) are reported. Within this report are the first examples of μ2η1:η1-N-indolyl moieties bridging group 13 elements, specifically aluminum in the
complexes; [L1AlR2]2 (R = Me (7a), Et (7b), iBu (7c)), (L2Al2Me4) (8), (L3Al3R6) (R =
Me (9a), Et (9b)), (L3Al3HiBu5) (9c). These complexes have been characterized by 1H
and 13C NMR spectroscopy and elemental analysis. X-ray crystallography confirmed the
presence of the bridging 3-methylindolyl group in 7a, 8, 9a, 9b, and 9c where there is one
3-methylindolyl moiety per aluminum. Complexes 7a-7c are observed as isomers in
solution with a 60:40 ratio of anti:syn. NMR spectroscopic data suggests interconversion
between syn and anti isomers for 7a-7c in solution.
In chapter 4, the synthesis and spectroscopic characterization of four- and fivecoordinate complexes of aluminum and gallium are reported. This includes the synthesis
of
four-coordinate
anionic
aluminum
iii
and
gallium
complexes
of
tri(3-
methylindolyl)methane,
four-coordinate
neutral
aluminum
complexes
of
tri(3-
methylindolyl)imidazolylmethane (L4), and five-coordinate aluminum and gallium
complexes
of
tris(pyrrolyl-α-methyl)amine
(L5).
These
complexes
include:
[(L3MX)][Li(THF4)] (M = Al: X = Cl (3a), H (4a), D (4b), tBu (4c); M = Ga: X = Cl
(3b)); (L4AlR) (R = Me (5a), Et (5b), iBu (5c), tBu (5d); (L5M(HNMe2)) (M = Al (6a),
Ga (6b)). These complexes have been characterized by 1H and
13
C NMR spectroscopy.
X-ray crystallography confirmed the structures of 3b, 6b and 7a. These complexes serve
as precursors to potential three- or four-coordinate neutral, Lewis acidic, group 13
compounds although initial attempts to generate these were unsuccessful.
iv
This dissertation is dedicated to
My wife and daughter whose constant love
and support made this a reality
v
Acknowledgement
I would like to express my gratitude and give thanks to my advisor Dr. Mark R.
Mason for his support, encouragement and guidance. His guidance and advice have
helped me immensely in my professional development as a scientist.
I would also like to thank Drs. Joseph Schmidt, Ron Viola, and Viranga
Tillekeratne for serving on my committee and providing me valuable guidance in
professional and personal matters.
I would like to give a great acknowledgement to Dr. Kristin Kirschbaum. Her
expertise in X-ray crystallography and her immense patience has been extremely
appreciated and necessary for me to complete the structures that are included in this
thesis. She has a very busy schedule and her willingness to set aside time was of great
help to me.
Dr. Yong-Wah Kim provided me with help in NMR spectroscopy. Despite a very
busy schedule, he would help with any questions that I had for running different
experiments.
I would like to thank Steve Moder, scientific glass blower, for his help in
repairing and fabricating glassware used in my work and in my teaching lab. It is his
abilities that allowed me to do some of the experiments that I have done. Also I would
like to thank Char and Pam in the chemistry office and Tony and Steph in the Chemistry
stockroom for their support in my research and teaching.
Acknowledgement is needed for my present and past group members, Dr. Bassam
Fneich, Bingxu Song, Anirban Das, Ryan Rondo, Christopher Yeisley, Adam Keith,
vi
Emmanuel Tive, Jessica Davis, Laura Sieg, Andrew Ramos, and David Holtzapple for
their help and support.
I am grateful to The University of Toledo and the National Science Foundation
for financial support. The material in chapter 2 is based upon work supported by the
National Science Foundation under Grant No. 0407542 (awarded to Dr. Mark R. Mason).
Any opinions, findings, and conclusions or recommendations expressed in this material
are those of the author and do not necessarily reflect the views of the National Science
Foundation.
I would like to thank family and friends for the support they have given for the
past 5 years. Finally I would especially like to thank my wife Erin and daughter Meara.
Without their continued support and understanding I would not be where I am at right
now.
vii
Table of Contents
Abstract
ii
Dedication
v
Acknowledgements
vi
Table of Contents
viii
List of Appendix Contents
x
List of Figures
xi
List of Tables
xiv
List of Schemes
xv
List of Abbreviations
xvi
Chapter 1
Chapter 2
Group 13 Lewis Acids: Synthetic Routes and Applications
1.1
Introduction
1
1.2
General Structural Features and Applications of MAO
2
1.3
Group 13 Perfluoroaryl Complexes and Derivatives
5
1.4
Triamidoamine Group 13 Complexes
12
1.5
Tripodal Triamine Group 13 Complexes
16
1.6
Multidentate Lewis Acids
18
1.7
Research Statement
20
Isonitrile Complexes of Trialkylaluminum and Trialkylgallium
Reagents
2.1
Introduction
21
2.2
Experimental
26
2.3
X-ray Crystallography
33
viii
Chapter 3
2.4
Results and Discussion
37
2.4.1
Preparation of Isonitrile Complexes
37
2.4.2
IR Spectroscopy
40
2.4.3
Molecular Structures
42
2.4.4
Reactivity of Donor-Acceptor Complexes
44
2.4.5
Isothermal Titration Calorimetry
48
2.6
Conclusions
52
Confirmation of Bridging N-Indolyls in 3-Methylindole and
Di- and Tri(3-methylindolyl)methane Complexes of
Dialkylaluminum Moieties
3.1
Introduction
53
3.2
Experimental
57
3.3
X-ray Crystallography
65
3.4
Results and Discussion
66
3.4.1
Preparation of Di- and Tri(3-methylindolyl)methanes
66
3.4.2
Reactions of 3-Methylindole and R3Al (R = Me, Et, iBu)
67
3.4.3
Variable Temperature NMR of 7a and 7b
76
3.4.4
Reaction of Di(3-methylindolyl)phenylmethane and Me3Al 78
3.4.5
Reactions of Tri(3-methylindolyl)methane and R3Al
80
(R = Me, Et, iBu)
3.5
Chapter 4
Conclusions
90
Group 13 Complexes of Di- and Tri(3-methylindolyl)methanes and
Tris(pyrrolyl-α-methyl)amine
4.1
Introduction
91
ix
Chapter 5
4.2
Experimental
95
4.3
X-ray Crystallography
103
4.4
Results and Discussion
106
4.4.1
Synthesis of [{tri(3-methylindolyl)methane}MX]
106
4.4.2
Reactivity of 3a-4b
110
4.4.3
Synthesis of (1-CH3-2-C3H2N2)HC(3-CH3C8H4N)2AlR
(R = Me, Et, iBu, tBu)
112
4.4.4
Synthesis of (TPA)M(HNMe2) (M = Al, Ga)
116
4.5
Conclusions
119
Concluding Remarks
120
References
Appendix
123
CIF Files for Compounds
CIF File for tBu3Al·C≡NtBu
131
CIF File for tBu3Ga·C≡NtBu
141
CIF File for Me3Ga·C≡NtBu
150
CIF File for Me3Al·C≡N(2,6-Me2C6H3)
157
CIF File for Me3Ga·C≡N(2,6-Me2C6H3)
166
CIF File for tBu3Al·C≡N(2,6-Me2C6H3)
175
CIF File for tBu3Ga·C≡N(2,6-Me2C6H3)
183
CIF File for [3-methylindolyl(AlMe2)]2
191
CIF File for [{di(3-methylindolyl)phenylmethane}(AlMe2)2]
203
CIF File for [{tri(3-methylindolyl)methane}(AlMe2)3]
219
CIF File for [{di(3-methylindolyl)imidazolylmethane}AlEt]
231
CIF File for [(tris(pyrrolyl-α-methyl)amine)Al(HNMe2)]
245
x
List of Figures
Figure 1.1
Preorganization of trigonal monopyramidal geometry.
17
Figure 2.1
Isonitrile complexes of group 13 trialkyls reported herein.
26
Figure 2.2
ORTEP diagrams of 1a, 1b and 1d. Thermal ellipsoids are drawn 43
at the 30% probability level. Hydrogen atoms are omitted for
clarity.
Figure 2.3
ORTEP diagrams of 2a-d. Thermal ellipsoids are drawn at the
43
30% probability level. Hydrogen atoms are omitted for clarity.
Figure 2.4
ORTEP diagram of 3. Thermal ellipsoids are drawn at the 30%
46
probability level. Most hydrogen atoms are omitted for clarity.
Figure 2.5
ITC thermogram for titration of tBuN≡C with iBu3Al
50
(Top) Heat change associated with addition of 5 μL aliquots
of tBuN≡C (0.010 M) to iBu3Al (1.4 mL, 0.10 M) at 25 °C.
(Bottom) Binding isotherm.
Figure 3.1
Binding descriptions for η1 and μ2-η1:η1 coordination modes.
54
Figure 3.2
ORTEP diagram of N-sodioindole•TMEDA generated from CIF
54
file from Cambridge Crystallographic Database.
Figure 3.3
Bridging pyrrolidine and monomeric pyrrole complexes isolated
55
by Smith and Cowley.
Figure 3.4
Bridging dialkylaluminum complexes of di(3-methylindolyl)
56
methanes.
Figure 3.5
Numbering scheme for indole .
58
Figure 3.6
gCOSY spectrum of 7c in benzene-d6 from 7.0 ppm to 8.4 ppm.
71
xi
Figure 3.7
HMQC spectrum of 7c in benzene-d6 from 116 to 134 ppm.
72
Figure 3.8
ORTEP diagram of 7a. Both syn isomers of the whole molecule
73
disorder are shown. Thermal ellipsoids are drawn at the 30%
probability level. Hydrogen atoms are omitted for clarity.
Figure 3.9
Variable-temperature 1H NMR plot of 7a in CDCl3 from
77
-10 to 60 °C.
Figure 3.10
Variable-temperature 1H NMR plot of 7b in CDCl3 from
77
20 to 60 °C.
Figure 3.11
ORTEP diagram of 8. Thermal ellipsoids are drawn at the 30%
79
probability level. Hydrogen atoms are omitted for clarity.
Figure 3.12
ORTEP diagram of 9a. Thermal ellipsoids are drawn at the 30%
82
probability level. Hydrogen atoms are omitted for clarity.
Figure 3.13
ORTEP diagram of 9b. Thermal ellipsoids are drawn at the 30%
85
probability level. Hydrogen atoms are omitted for clarity.
Figure 3.14
1
H NMR spectrum of aliphatic region of 9c in benzene-d6 from
87
─2.0 ppm to 2.6 ppm.
Figure 3.15
ORTEP diagram of 9c. Thermal ellipsoids are drawn at the 30%
88
probability level. Hydrogen atoms are omitted for clarity.
Figure 4.1
1
Figure 4.2
ORTEP diagram of 3b. Thermal ellipsoids are drawn at the 30%
H NMR spectrum of 3a in chloroform-d.
107
108
probability level. Hydrogen atoms and disordered lithium cation
are omitted for clarity.
Figure 4.3
1
H NMR spectrum of 5d in chloroform-d.
xii
114
Figure 4.4
ORTEP diagram of 5b. Thermal ellipsoids are drawn at the 30% 115
probability level. Hydrogen atoms are omitted for clarity.
Figure 4.5
ORTEP diagram of 6a. Thermal ellipsoids are drawn at the 30%
probability level. Hydrogen atoms are omitted for clarity.
xiii
118
List of Tables
Table 1.1
Calculated dissociation energies (kJ mol-1) of the gas phase
11
complexes (RI-BP86/def2-TZVPP level of theory)
Table 2.1
Crystal data and structure refinement details
35
Table 2.2
C≡N stretching frequencies and coordination shifts for 1a-1f
41
and 2a-2f
Table 2.3
Select bond distances and angles for 1a, 1b, 1d, and 2a-2d
44
Table 2.4
Reactivity of complexes in C6D6
45
Table 2.5
Enthalpies of complexation for complexes of Me3Al and Et3Al
49
Table 2.6
ITC thermodynamic data summary
51
Table 3.1
Crystal data and structure refinement details
66
Table 3.2
Select bond distances and angles for C22H28Al2N2, 7a
74
Table 3.3
Select bond distances and angles for C29H32Al2N2, 8
80
Table 3.4
Select bond distances and angles for 9a
83
Table 3.5
13
89
Table 4.1
Crystal data and structure refinement details
105
Table 4.2
Chloride abstraction reactions
111
Table 4.3
Select bond distances and angles for 5b
115
Table 4.4
Select bond distances and angles for 6a
119
C and 1H NMR chemical shifts for alpha nuclei in benzene-d6
xiv
List of Schemes
Scheme 2.1
Decomposition pathways of X3M•C≡NR
(M = Al, Ga, In; R = H, CH3; X = H, CH3)
as proposed by Timoshkin and Schaefer
25
Scheme 2.2
β-Hydride elimination of tBu3Al at elevated temperatures
47
xv
LIST OF ABBREVIATIONS
2–D
Two Dimensional
CCD
Charge Couple Device
CDCl3
Chloroform-d
C6D6
Benzene-d6
CIF
Crystallographic Information File
DIBAL
Diisobutylaluminumhydride
g-COSY
Gated Correlation Spectroscopy
ES
Electrospray
g-HMBC
gated-Heteronuclear Multiple Bond Coherence
g-HMQC
gated-Heteronuclear Multiple Quantum Coherence
HRMS
High-resolution Mass Spectrometry
IR
Infrared
ITC
Isothermal Titration Calorimetry
MAO
Methylaluminoxanes
Mes*
2,4,6-tri(tert-butyl)phenyl
MOCVD
Metal Organic Chemical Vapor Deposition
NMR
Nuclear Magnetic Resonance
NOESY
Nuclear Overhauser Enhancement Spectroscopy
ORTEP
Oak-Ridge Thermal Ellipsoid Parameters
TEAL
Triethylaluminum
THF
Tetrahydrofuran
xvi
TIBAL
Triisobutylaluminum
TREN
Tris-2-aminoethylamine
TPA
Tris(pyrrolyl-α-methyl)amine
xvii
Chapter One
Group 13 Lewis Acids: Synthetic Routes and Applications
1.1 Introduction
Organoboron, -aluminum, and -gallium Lewis acids have found utility as reagents in
organic synthesis and for the polymerization of olefins and polar monomers.1-4 Strong
Lewis acids, the most common being E(C6F5)3 (E = B, Al, Ga) and methylaluminoxanes
(MAO), have been used as oxygen and moisture scavengers, catalysts, cocatalysts, and
stabilizers for various types of catalytic processes.2 The high Lewis acidity of E(C6F5)3 is
due to the inclusion of the three strong electron-withdrawing pentafluorophenyl ligands.
When aluminum compounds are used as powerful Lewis acid catalysts for organic
transformations, mechanistic studies show that trigonal bipyramidal (TBP) alumatranes
are the active intermediates.5,6 Perfluoroaryl ligands are costly and MAO is used in large
excess (up to 1000 fold) which greatly contributes to the cost of a particular catalytic
system leading to interest in the design and synthesis of new group 13 Lewis acids.
Complexes of aluminum and gallium alkyls with nitrogen-donor ligands are
widely being investigated for use in organic synthesis and catalysis. The Lewis acidic
nature of the metal atom allows these complexes to act as catalysts and cocatalysts for
reactions such as the polymerization of ethylene.7 Cationic complexes of aluminum are
1
of interest because of the enhanced Lewis acidity at the aluminum center versus their
neutral analogs.
Low-coordinate aluminum cationic species are more electrophilic,
making them better acceptors of electron donors. The stability of the complexes formed
depends on both the counter anion as well as the ligand. For example, weak Lewis bases
such as NMe2Ph can sometimes be used to stabilize the formation of cationic aluminum
alkyls.
In the following sections, group 13 Lewis acids and their uses will be discussed.
Although the uses of methylaluminoxanes have been reviewed,2,8,9 there will be a brief
discussion because of their pertinence to this review. The uses of perfluoroarylboranes
and alanes as Lewis acids along with Lewis acidic aluminum compounds that are used as
catalysts for ethylene polymerization will also be reviewed. Emphasis shall be placed on
group 13 complexes bearing triamine and tetraamine ligand frameworks and their
derivatives. These complexes have been designed to increase the Lewis acidity of the
metal center, serve as a framework and are closely related to the complexes discussed in
this dissertation.
Cationic aluminum complexes as well as Salen complexes of group 13 elements
have been extensively reviewed by Atwood.10 The complexes discussed in that review
have been excluded from this discussion.
A comprehensive review on structurally
characterized organo-aluminum compounds, including those with N-donor ligands, has
been carried out by Holloway and Melnik.11
1.2 General Structural Features and Applications of MAO
The discovery of alkylaluminoxanes, more specifically MAO, has proved very
important for metal-catalyzed olefin polymerization.
2
Alkylaluminoxanes, which are
oligomeric compounds that have –Al(R)–O–subunits, have been known since the late
1950’s and are active for the polymerization of monomers such as epoxides and
lactones.12
The most active alkylaluminoxane (when combined with group 4
metallocenes) for polymerization of ethylene and propylene is methylaluminoxane.
Metallocenes that are activated by alkylaluminum halides have poor activity for the
polymerization of propylene and higher α-olefins, limiting their use in metallocene
catalytic systems. A plethora of research was done in this field to increase the activity
and performance of these systems. The first breakthrough came when Reichert and
Meyer13 found rate enhancement for ethylene polymerization upon addition of water to
the Cp2ZrEtCl/AlEtCl2 system.
Similar results have also been reported for
Cp2ZrCl2/AlMe2Cl systems and data suggests that the formation of ClMeAl–O–AlClMe
dimer, a stronger Lewis acid than Me2AlCl, is responsible for the rate increase. The
major breakthrough came when Sinn and Kaminsky reported that the addition of water to
an inactive Cp2ZrMe2/AlMe3 system gave high activity for ethylene polymerization.14
These results led to resurgence in research on Ziegler-Natta catalysts and began the
metallocene and single-site polymerization catalysis era.15-23
MAO is prepared by controlled hydrolysis of AlMe3 and is usually assigned the
general formula [–Al(Me)–O–]n where n ≈ 5-20.16 Despite extensive research, the exact
composition and molecular structure of MAO is not well understood. There are many
proposed structures for MAO which include linear chains (1), cyclic rings (2), and twoor three-dimensional clusters (3, 4).24,25 It is believed that MAO has the general formula
[AlO0.8-0.75(CH3)1.4-1.5]n.
Work by Sinn and coworkers23 suggests that the major
component of MAO is a tetrameric species with the basic formula [Al4O3(CH3)6]4. This
3
Me
O
Me
Al
Me
Me
Al O
Me
Al
O
O
3
Me
Me
n
2
t
O
Bu
Al
O
t
Bu
O
Al
Al
O
Bu
O
Al
Al
O
t
t
Bu
Bu
4
t
Al
O
O
Bu
Al
O
Al
O
Me
t
Al
O
Al
Al
Al
Me
Me
Al
O
O
AlMe2
n
1
Me
Al
Me
tetrameric compound has a CH3:Al ratio of 1.5 and is in agreement with the accepted
general formula for MAO.
Based on NMR spectroscopic studies of MAO, it is postulated that there is cage
formation under mild conditions while the aluminum centers are mostly tetracoordinated.
Even with its synthetic usefulness and the extensive research done in this area, the
active structure of MAO is still not completely characterized because MAO undergoes
structural interconversion in solution. There are also two types of Me3Al in solutions of
MAO, free Me3Al and Me3Al that is associated in a cluster. The different types of Me3Al
undergo rapid exchange in solution.
MAO’s catalytic activity varies with storage duration and method of synthesis,
therefore many attempts to modify MAO over the years have been explored. Controlled
hydrolysis of triethylaluminum (TEAL) and triisobutylaluminum (TIBAL) in similar
fashion to the synthesis of MAO has yielded promising results. These TEAL and TIBAL
derivatives of MAO have much longer shelf life and improved solubility in aliphatic
4
solvents but they are not as active in metallocene catalyzed olefin polymerization. 26
Commercially available products prepared by including a mixture of triisobutylaluminum
and triethylaluminum during the hydrolysis process show increased shelf life and
promising activity for polymerization.
Other modifications to MAO include the
incorporation of B(C6F5)3 and Al(C6F5)3 into solid MAO. When these mixtures are
heated in solution there is B/Al and Al/Al ligand exchange and the incorporation of
pentafluorophenyl groups into MAO. The activity of these derivatives has a 4-7 fold
increase for ethylene polymerization when compared to similar runs with untreated
MAO.27
There are drawbacks to the use of MAO as an activator for metallocene catalyzed
olefin polymerization. A high ratio of MAO to catalyst (102:1 to 104:1) is needed to
achieve good activity, adding to the high cost of the cocatalysts and high ash content
(Al2O3) in the polymer that is produced. High concentrations of cocatalyst along with the
unknown and complicated structural motifs of MAO render the characterization of
catalytically active species increasingly difficult. Consequently, the activation process
and nature of the catalytically active species are not well understood.
1.3 Group 13 Perfluoroaryl Complexes and Derivatives
The imperfect nature of MAO as an activator in metallocene-mediated olefin
polymerization led to the investigation of other strong Lewis acids as activators for such
processes. One of the more important discoveries was the use of perfluoroaryl boranes as
activators for olefin polymerization pre-catalysts.
The first pentafluorophenyl substituted boranes were introduced over 40 years ago
and were prepared using C6F5SnMe3 as a transmetallation reagent with BCl3.28 This
5
family of compounds was extensively studied at the time but did not become prominent
until B(C6F5)3 was found to abstract anionic moieties from transition metals.29 This
discovery expanded the chemistry of a wide variety of electrophilic organotransition
metal cations for use in the production of high quality polyolefin resins and in the
production of certain plastics.30-32 These discoveries have led to a renewed interest in
B(C6F5)3, not only as a catalyst activator, but also as a strong Lewis acid for other
purposes.
The compound B(C6F5)3 was first synthesized in the early 1960’s and work by
Massey and Park showed very high thermal stability and high affinity for very weak
Lewis bases.28,33 At the time when perfluoroaryl boranes were discovered it was known
that such compounds were not stable due to strong thermodynamic driving force for the
formation of B–F bonds. The pentafluorophenyl moiety, however, is resistant to that
pathway and B(C6F5)3 is stable to 270 °C with minimal decomposition.
Unlike
haloboranes, the B–C bonds in B(C6F5)3 are more stable to protic acids leading to a larger
range of tolerance for chemical reactivity. The aryl groups also provide steric protection
to the boron center and confer crystallinity to the different adducts that can be formed.
This allowed many complexes with these Lewis acids to be characterized structurally, a
feature not available with MAO. Because the use of B(C6F5)3 and some related boranes
in olefin polymerization applications have been reviewed extensively,2,34,35 that aspect
will be left out of this chapter. Instead comments on these complexes, Lewis acidity, and
recent modifications will be discussed along with a few other uses.
The catalytic activity seen using B(C6F5)3 and its aluminum and gallium analogs
as abstraction reagents is related to the strength of their Lewis acidity. According to Roof
6
and coworkers,36 catalytic activities for alkene polymerizations are highly dependent on
the type of anion used, and activity increases as the anion becomes less coordinated to the
cationic metal center.
The weak nucleophilicity of fluorine atoms and the strong
electron-withdrawing nature of C6F5 groups are major contributors to the weakly
coordinating ability of the anions formed by abstractions with Lewis acids. Strauss has
reviewed the requirements for compounds to be a good weakly coordinating anion.37
This weak coordinating ability of the resulting borane anion is of interest because
some of the strongest known Lewis acids are highly reactive with the cationic metal
centers generated during metallocene-mediated olefin polymerization.
Simple
trihaloboranes (BF3 and BCl3) irreversibly transfer F‾ or Cl‾ to the metal center poisoning
the catalyst and stopping polymerization. Marks38 proposed that the two key features for
effective cocatalysts are high native Lewis acidity of electron-deficient centers and lack
of labile nucleophilic substituents that might serve as catalyst poisons. He proposes that
in the absence of halogens or other donors, “base-free” cationic metallocenes can form μMe dinuclear species (5) which stabilizes the highly electrophilic metal center and unlike
base coordination does not poison the catalyst.
Me Me
H H
Zr C Zr
H
5
7
MeB(C6F5)3
Lewis acidity of the cocatalyst plays a key role in the activation and activity of the
metallocene catalysts. This means that quantifying Lewis acidity of the perfluoroaryl
borane reagents along with other Lewis acids is of great importance. Several methods
have been developed to quantify Lewis acidity of perfluoroaryl boranes using
thermodynamic data,39,40 chemical reactivity,41 and spectroscopic data.42 White43 and
F
F
B
F
F
F
F
F
F
F
O B
F
F
n
F
3-n
7 n=1
8 n=2
9 n=3
6
31
F
F
3
coworkers used
F
P NMR chemical shifts of Et3PO and the 1H NMR chemical shifts of
crotonaldehyde upon binding of the oxygen atom to the Lewis acid to estimate the Lewis
acidity of a series of B(C6F5)3 derivatives. The validity of these methods is widely
accepted, and there is correlation between Δδ and the strength of the Lewis acid.44,45
White43 synthesized a series of compounds 6-9 and tested the change in Lewis acidity as
the number of aryloxy arms increased. The correlation of increasing hard Lewis acidity
of compounds 7-9 compared to 6 with the increasing number of aryloxy arms was
observed. The explanation for such a phenomenon resides in the presence of electronwithdrawing C6F5 groups and electronegative oxygen substituents in borinic and boronic
esters of this type.
8
With the increased interest in Lewis acidic organoboranes, a plethora of borane
derivatives have been synthesized. Compounds 10-14 represent a few examples.46 Marks
has extensively studied these fluorinated arylborane complexes that he considers to be
“superacidic”. He claims that according to reaction enthalpies, compounds in series 14
are as strong, in terms of Lewis acidity, as BCl3 and SbCl5 which are considered two of
the strongest inorganic Lewis acids.
F
F
F
F
F
F
F
F
F
F
B
F
F
F
F
F
B
F
F
F
B(C6F5)2
F
B(C6F5)2
3
F
12
11
3
10
F
F
F
F
F
F
F
F
F
B
F
F
F
F
F
X
B
B
X
F
F
F
F
F
X = Cl, alkyl, C6F5
F
F
14
13
With the past and present interest 47 in perfluoroaryl boranes and their derivatives,
there has been much research done in expanding the same type of chemistry to other
group 13 metals. The C6F5 derivatives of Ga and Al have been synthesized,48,49 along
with other derivatives of fluorinated group 13 compounds.50,51 Some of these derivatives
show incredibly strong Lewis acidic properties and their chemistry has been extensively
studied.27,51-55
9
Despite the wide use and extensive studies of group 13 Lewis acids, there is still
debate over the Lewis acid strength of such compounds.
The trihalides of boron,
aluminum, and gallium are commonly accepted to be very strong Lewis acids, but
discrepancy exists in establishing the strength of similar Lewis acids when going down
the group 13 elements from B to Ga.27,52,56 Certain studies have shown that B(C6F5)3 is a
much stronger Lewis acid than Al(C6F5)3, and that the C6F5 moiety only marginally
increases Lewis acidity over the trihalides.27 In particular Marks and coworkers claim
that Al(C6F5)3 has a much lower methide affinity when compared to B(C6F5)3 based on
calorimetry and NMR studies.52 With many experimental studies showing these trends,
evidence exists that such studies are misleading. The stability of isolated group 13
perfluorophenyls is an example. During the preparation of Al(C6F5)3 the complex is most
stable when isolated as a toluene or benzene adduct.51 The THF adduct of this compound
is stable up to 200 ◦C with only slight decomposition.27 The compound Ga(C6F5)3 shows
similar chemistry with the Et2O adduct being stable and purified by sublimation.
B(C6F5)3 does not form adducts with benzene or toluene and its Et2O adduct dissociates
at 60 °C under vacuum. This experimental data could be interpreted as B(C6F5)3 being a
weaker Lewis acid than its Al and Ga analogues. Recent gas phase DFT calculations57
(summarized in Table 1) have shown agreement with the B(C6F5)3 and boron compounds
being weaker Lewis acids than Al and Ga analogues. The study concludes that the trend
in Lewis acidity is Al > Ga > B and that the C6F5 moiety strongly increases Lewis acidity
in these complexes compared to the group 13 trihalides ECl3.
10
Table 1.1
Calculated dissociation energies (kJ mol-1) of the gas phase
complexes (RI-BP86/def2-TZVPP level of theory)
Donor
_________
CH3‾
F‾
451.2
458.7
426.5
----
383.8
367.7
344.7
4.8
----
405.2
389.1
366.0
97.1
36.5
24.0
528.1
487.5
454.0
AlCl3
143.9
97.4
66.4
482.7
496.8
523.0
Al(C6H5)3
94.4
63.8
34.8
395.6
401.1
442.7
Al(C6H4F)3
94.6
63.7
34.9
420.2
425.9
467.2
Al(C6F5)3
145.5
112.0
63.9
513.6
521.5
552.1
GaCl3
118.3
68.9
56.7
502.4
507.5
456.2
Ga(C6H5)3
66.1
23.1
23.1
382.5
376.2
356.1
Ga(C6H4F)3
66.3
37.4
22.8
407.5
401.1
379.8
Ga(C6F5)3
114.9
74.9
52.9
510.7
506.6
464.7
Acceptor
NH3
H2O
PH3
BCl3
89.3
15.8
13.5
B(C6H5)3
45.8
10.1
B(C6H4F)3
40.7
B(C6F5)3
H‾
Data reproduced from work by Timoshkin57
Recently Tilley and coworkers58 have taken a new approach and synthesized
electron-deficient compounds called perfluoropentaphenylboroles (15, 16). Tilley claims
these compounds provide unique access to highly Lewis acidic compounds of electrondeficient materials. Even though these compounds are highly reactive, their high moisture
sensitivity and poor solubility render them unsuitable for industrial applications.
Nevertheless, these types of compounds are promising and could be tuned for stability.
11
C6F5
Br
B
C6F5
C6F5
C6F5
B
C6F5
C6F5
C6F5
C6F5
C6F5
15
16
1.4 Triamidoamine Group 13 Complexes
Many group 13 complexes incorporating the tris(2-aminoethyl)amine (tren)
framework have been synthesized. The work in this area with aluminum, gallium and
boron was started by Verkade and coworkers with the synthesis of 17-20.59,60 The tren
framework incorporates a trianionic chelating ligand that involves a fourth neutral
nitrogen donor in the apical position. These complexes are typically called azatranes and
the metal coordinated is used as a prefix, for example, aluminum complexes are called
alumatranes. The complexes 17-19 are monomeric and possess three-fold symmetry
down the apical E–N bond for aluminum.
R
N
E
N
N
R
R
N
E
17 B
18 B
19 Al
N
N Al
N
Me
Me Me N
N
Me
Me Me
N
Al N
N
R
Me
SiMe3
SiMe3
20
for aluminum. Moving from the bulky SiMe3 substituent on nitrogen (17-19) to Me
results in the formation of a dimer (20), which is the first pentacoordinate Al center
supported exclusively by nitrogen ligands. Several more derivatives of these azatranes
12
have been synthesized by Verkade including the incorporation of gallium.59-65
In
compound 19 the geometry of the aluminum center has been confirmed by X-ray
crystallography as trigonal monopyramidal which is a rare geometry for aluminum.
These complexes were initially generated as MOCVD precursors to nitride films of E (E
= Al, Ga, B), and since C–E bonds are absent there may be a minimization of carbon
retention.
The importance of these complexes for the purpose of our work was brought to
attention in 2000 by Nelson and coworkers5 when they discovered that Al(III) complexes
(21-23) with trigonal monopyramidal coordination geometry around the Al center were
active Lewis acid catalysts for cycloaddition reactions involving ketenes and aldehydes
while tetrahedral analogues were not. The work by Nelson was based on similar work by
Bertrand66 who proposed using nitrogen donor ligands to generate tetracoordinated group
i
Bn
Pr
i
N
N
Tf
Me
Pr
N
Al
N
N
Tf
Me
21
Al
Tf
Me
22
N
Tf
O
N
Tf
Al
Me
23
N
Tf
13 complexes. Complexes 24-29 were used as catalyst precursors for the ring-opening
polymerization of propylene oxide. Bertrand claims that in all cases the rigid bicyclic
core imposes trigonal-monopyramidal geometry around the metal. It was this realization
that led Nelson to pursue the use of this coordination geometry for group 13 metals in
order to increase Lewis acidity around the metal center and increase reactivity for organic
13
N
Me3Si
SiMe3
Me
N
N
M
N
N
Cl
SiMe3
Me3Si
M= Al, Ga, In
24-26
transformations.
Al
N
SiMe3
R
R= Me, H, Cl
27-29
Nelson also proposed that the active intermediates in these
transformations were trigonal bipyramidal alumatranes.
Once this geometry for
aluminum complexes was discovered as a reactive species for some of these organic
transformations,5,67-69 Verkade and coworkers synthesized monomeric derivatives of the
alumatranes (30, 31) that they had previously published.6,70
These compounds are
appealing because of their pseudo-threefold symmetry around the metal centers and their
flexible transannular bond between metal and axial nitrogen, along with the possibility of
3d orbital involvement for substrate binding. Complex 31 is isolated in the absence of
base as a dimer, but can be separated into monomers by the coordination of a variety of
bases including H2O, THF, ethylenediamine, and benzaldehyde. Complex 31 facilitates
the addition of trimethylsilylcyanide (TMSCN) to benzaldehyde in 97% yield, while the
dimeric form performs that same reaction in 95% yield. Complex 30 is isolated in good
yield and is the first example of a monomeric proalumatrane which features a base-free
TMP coordination geometry. This was accomplished by replacing the methyl groups
with tert-butyl groups in the 3-position of the tris(2-hydroxy-3,5-dimethylbenzyl)amine
ligand used in 31. This provided steric protection of the metal center and prevented
dimerization.
14
t
t
Bu
Bu
t
Bu
O
O
O
Al
N
30
N
O
O
Al
Al
O
O
O
O
N
31
Similar to this work by Verkade, Gade and coworkers71 have extended this
chemistry to include similar atrane type molecules 32-35 that are chiral and enantiopure.
The ligands used for the preparation of 32-35 are isolated as enantiopure compounds and
corresponding aluminum complexes were isolated by reaction of enantiopure ligand with
one equivalent of Me3Al in greater than 95% yield. It is proposed that these complexes
could serve as chiral catalysts for the formation of enantiopure organic compounds.
R'
N
R
32
33
34
35
N
N
E
R
R
N
E
Al
Al
Al
Al
R'
R'
R
Me
Me
i
Pr
Me
15
R'
Me
CH3SO2
CF3SO2
2,4,6-(CH3)3(C6H2)SO2
1.5 Tripodal Triamine Group 13 Complexes
In 2007, Chen and coworkers72 proposed, based on the results of Nelson, Bertrand
and Verkade, that Lewis acid catalysts are more efficiently designed if they possess a
preorganized pyramidal geometry (Figure 1.1).
The Mason group had previously
proposed this geometry and had been working towards this for many years. Mason and
Chen independently proposed that there will be no penalty in energy for rearrangement of
the geometry upon substrate binding during Lewis acid mediated chemical
transformations. The preorganized geometry consists of a binding pocket with a vacant
sp3 orbital ideally arranged to accept a fourth donor ligand or substrate. Along with the
prearranged geometry, steric protection and electronic tuning at the metal center is easily
Nu
Nu
sp3
C 6F 5 E C F
6 5
C6F5
C6F5
E
C6F5
sp2
C 6F 5
Planar
Pyramidal
Geometry Reorganization
R
R
N
N
Nu
3
E sp
R
N
Preorganized Pyramidal
Figure 1.1
Preorganization of trigonal monopyramidal geometry
16
accessible with substitution of the R groups on nitrogen. The tripodal amido ligands that
Chen is referring to are known and have been well studied for their use with transition
metals and germanium.73 These molecular “claws” are tripodal, trianionic ligands, and
according to Chen, give the perfect framework for this preorganized geometry.
Based on preorganized geometry, Chen and coworkers72,74 isolated complexes 36
and 37 in high yield (70-99%) using the tripodal amido ligands previously used for
transition metals. Both complexes show the preorganized geometry preferred by Chen
for increasing Lewis acid strength. Chen claims that 36 should be significantly more
Lewis acidic because the geometry around the boron center does not allow for N–B p–p
π–interactions, in turn limiting the electron density on boron. In the crystal structure for
36 though, it is clear that the geometry around the boron center is more planar than
pyramidal. This lack of π–interactions is more prominent for complex 37 which binds
THF to help support the aluminum center.
Numerous other compounds were
synthesized, two of which (38, 39) are tripodal around the metal center. Complex 38 is a
dimer in which two LiCl•(OEt2)2 units bridge the two aluminum centers, while 39
contains a four-coordinate aluminum center that has a hydride bridging between
THF
Ar
B Ar Ar
N N
E E
E
C
Ar
N
Al Ar Ar
N N
E E
E
C
N
H
E = SiMe2
Ar = 4-MeC6H4
H
E = SiMe2
Ar = 4-MeC6H4
37
36
17
aluminum and a [Li(OEt2)2]+ cation. The polymerization activity of these compounds
was mixed.
All screened compounds showed poor activity for the ring-opening
polymerization of propylene oxide and caprolactone. Also Cp2ZrMe2 was activated using
36 and the resulting cationic zirconacene showed poor activity for ethylene
polymerization.
H
Ar Et2O OEt2
Si N Ar
Li
Si N
Al Cl
H
Si N
Ar
Ar
Si N Ar
Si N
Al H
Si N
OEt2
Li
OEt2
Ar
2
Ar = 4-MeC6H4
39
Ar = 4-MeC6H4
38
1.6 Multidentate Lewis Acids
Multidentate Lewis acids have been an area of growing interest in recent years for
their use in anion recognition and as activators for olefin polymerization. Uhl and
coworkers75 have synthesized a gallium complex that has six three-coordinate gallium
centers in a heteroadamantane cage while Schnöckel76 synthesized a cyclic hexaaluminum complex. The work by Gabbaï77 has drawn the most attention to this area with
the synthesis of the trigallocycle 40. This complex consists of three Lewis acidic gallium
centers in close proximity to each other and showed the potential to be an acceptor for
anion binding. While no further studies were carried out with 40, it paved the way for
18
Cl
Ga
Ga
O
Ga
40
recent work by Jordan and coworkers78 who investigated multidentate Lewis acids with
defined M–M distances for anion recognition and as activators for olefin polymerization.
Using rigid backbones like 1,8-biphenylene units they were able to synthesize a
tetragallium macrocycle (41) in 53% yield. The complex was not tested as an activator
for olefin polymerization but did show modest ability to bind Cl‾ and Br‾ in solution and
undergo halide exchange.
Cl
Ga
Ga
Cl
Cl
Ga
Ga
Cl
41
19
1.7 Research Statement
Based on the preceding sections, it is clear that complexes of boron, aluminum
and gallium can serve as powerful Lewis acids that can be used for many different
applications. It is also evident that there is a need for the synthesis and implementation
of new Lewis acids, and tripodal nitrogen donor ligands could play a vital role in the
development of these complexes. Aside from initial work by Frank Segla 79 and others8082
in the Mason group, there is no published research on the use of tripodal, tridentate
indolyl based ligands for generation of three-coordinate group 13 complexes. These
should possess highly electrophilic metal centers and have the potential to be strong
Lewis acids. Specifically, the use of tri(3-methylindolyl)methane as a ligand in group 13
and in organometallic chemistry is limited in the literature, and most published material
in this area has been done by the Mason research group.
This dissertation reports on the complexes formed by the reactions of di- and
tri(3-methylindolyl)methanes and tris(pyrrolyl-α-methyl)amine with group 13 metals.
Chapter two describes reactivity of isonitriles with aluminum and gallium alkyls as a
probe to the mechanism of reactivity of carbon monoxide with similar complexes.
Chapter three discusses the formation of μ2-η1:η1-N indolyl bridged bimetallic and
trimetallic aluminum complexes. These compounds were isolated from attempted
synthesis of three-coordinate indolyl based aluminum compounds. They serve as the first
examples of μ2-η1:η1-N bridging indolyl moieties of group 13 metals. Chapter four
describes
four-coordinate
aluminum
and
gallium
complexes
of
tri(3-
methylindolyl)methanes and tris(pyrrolyl-α-methyl)amine. These complexes serve as
precursors to the potential three-coordinate group 13 derivatives that are of interest.
20
Chapter Two
Isonitrile Complexes of Trialkylaluminum and Trialkylgallium
Reagents
2.1 Introduction
Group 13 Lewis acids are an extremely important class of compounds that can be
used to facilitate and promote many different organic transformations. Group 13 trialkyls
are not as strong as the Lewis acids described in chapter one, but they are known for their
ability to react with a wide variety of substrates. Alkenes are known to react with Al–H
and Al–C bonds,83 while hydrogen reacts with Al–C bonds.
Organoaluminum
derivatives are used industrially for the production of linear terminal alkenes and
alcohols, as well as alkylation reactions in chemical syntheses.
Until recently, the
binding of CO and insertion of CO into an Al–C or Ga–C bond was not known. Song
and Mason demonstrated that CO will undergo insertion into an Al–C bond in tBu3Al
under mild conditions to form the acyl bridged dimer shown in eq 1.84 Similarly, CO
inserts into a Ga–C bond in tBu3Ga when higher temperatures and pressures are used.85
These findings are a significant contribution to the chemistry of organic aluminum and
gallium derivatives and are the first examples of CO insertion into Al–C and Ga–C
bonds. Attempts by Song to expand the chemistry of carbon monoxide with aluminum
and gallium alkyls were unsuccessful and no other empirical evidence for carbon
monoxide reactivity with said compounds was observed.
21
t
t
t
2 M Bu3 + 2 CO
hexanes
t
M = Al, Ga
Bu
Bu
C
Bu
(1)
M
M
Bu
t
O
O
t
C
Bu
t
Bu
Cui86 and coworkers subsequently reported the insertion of CO into an Al–C bond
when they reacted CO with the constrained cyclopropene ring in the aluminum complex
shown in eq 2. The inserted product results from relief of ring strain to give the more
stable four-membered ring.
Ar
Ar O
R
N
CO
Al
Al
N
Ar
N
R
R
(2)
N
Ar R
Ar = 2,6-iPr2C6H3
R = SiMe3
To model the proposed reactivity of carbon monoxide with aluminum and gallium
alkyls, we herein describe reactions of isonitriles with aluminum and gallium alkyls.
Isonitriles are isoelectronic to carbon monoxide, but are better σ-donors to metal centers
and weaker π-acceptors. Unlike CO, they do not require π-backbonding from metals to
form stable complexes.
22
The chemistry of isonitriles with aluminum and gallium has been relatively
unexplored with only a few (Ph3Al•C≡NCy,87 Me3Al•C≡NMe,88 Cp3Al•C≡NtBu89)
complexes reported in the literature. In addition to isonitrile complexes, there are reports
of isonitrile insertions into Al–H, Al–C, and Al–Al bonds.
Hoberg90 reported that
insertion of isonitriles into the Al–H bond of DIBAL affords the dimers
[iBu2AlCH═NR]2
(R = tBu, cyclohexyl, benzyl) which are isostructural to the
[tBu2AlC(O)tBu]2 dimer reported by Song. Uhl91 also reported the insertion of tertbutylisonitrile into the Al–H bond of tBu2AlH which resulted in the formation of a similar
dimer [tBu2AlCH═NtBu]2. Similarly, Power92 reported that the sterically bulky alane
(Mes*AlH2) reacts with tert-butylisonitrile in solution to afford a dimeric structure. Both
hydrides on aluminum undergo hydrogen transfer to the quaternary carbon of the
isonitrile which then dimerizes to form [Mes*AlCH2Nt-Bu]2 (eq 3).
t
Bu
N
t
[Mes*AlH2]2 + 2 BuN
C
Mes*
CH2
Al
H2C
Al
Mes*
(3)
N
t
Bu
Shapiro89 and coworkers reported that in the presence of two equivalents of
isonitrile there is double insertion of the isonitrile into the Al–C bond of Cp′3Al (eq 4),
which leads to a four-membered AlC2N ring. Shapiro also notes that in the presence of
just one equivalent of isonitrile a four-coordinate complex Cp′3Al•C≡NtBu is isolated. It
is well known that isonitriles are prone to undergo multiple insertions with a variety of
transition metal complexes, and Uhl93 reported that isonitriles will undergo insertion into
an Al–Al bond.
23
t
Bu
N
Cp'3Al + 2 tBuN
Cp'
C
(4)
Al
N
Cp'
t
Bu
Cp' =
There is also precedent for reactions of isonitriles with Al(I) species. Cui 94 and
coworkers
report
that
the
β-diketiminato
aluminum
carbene
analogue
HC[(CtBu)(NAr)]2Al reacts with two equivalents of 2,6-diisopropylphenylisonitrile (eq
5) by insertion of one isonitrile into the Al–C bond that is formed by coordination of the
other isonitrile to aluminum. The nitrogen atom of the bound isonitrile then coordinates
to the aluminum creating a four-membered AlC2N ring similar to that found in the
compound reported by Shapiro (eq 4).
t
Bu
t
Ar
Bu
N
N
Al
N
t
Bu
Ar
+ 2 C NAr
NAr
(5)
Al
20 °C
N
N
t
Ar
Bu
Ar
Ar
Ar = 2,6-diisopropylphenyl
Cui86 also reports that isonitriles will insert into strained cyclic complexes of
aluminum to form aluminacyclobutenes.
These insertions are based on strained
aluminum complexes that have the same backbone as the β-diketiminato Al(I) derivatives
24
but have strained cyclopropene groups on aluminum. The insertion of the isonitrile is
thought to be driven by relief of ring strain.
Outside of these few examples, the solution chemistry of isonitriles with group 13
compounds is relatively unexplored. There has, however, been a computational study of
isonitriles with group 13 compounds published by Schaefer and coworkers.95 Schaefer
claims that donor-acceptor complexes of isonitriles with group 13 metal alkyls and
hydrides would be unstable and prone to decompose and reorganize by the pathways
shown in Scheme 2.1. Schaefer hypothesizes that the donor-acceptor complexes will
either undergo insertion or double insertion which could lead to dimerization, or that
there could be RX elimination followed by dimer-, trimer-, or tetramerization.
X2
M
C
N
N
X2M
N
C
N
MX2
C
X2M
MX2
C
C
N
X2M C
N
X2M
C
N
MX2
N
C
C
N
X2M
N
C
MX2
-RX
X3M C
NR
X2M CX
NR
XM
X
N
M
X2C
CX2
M
CX2
NR
Scheme 2.1
R
X
N
R
Decomposition pathways of X3M•C≡NR
(M = Al, Ga, In; R = H, CH3; X = H, CH3)
as proposed by Timoshkin and Schaefer95
25
In this chapter, the synthesis and characterization of the first extensive series of
isonitrile complexes of aluminum and gallium are reported. There are 12 new complexes
reported (Figure 2.1), seven of which have been characterized by X-ray crystallography.
These isonitrile complexes serve as models of non-classical CO complexes of aluminum
and gallium that are presumed to be intermediates for the CO insertion observed by
Song.82 Enthalpies of complexation were found using Isothermal Titration Calorimetry
(ITC).
R3M•C≡N–R′
1a
1b
1c
1d
1e
1f
M
Al
Ga
Al
Ga
Al
Al
Figure 2.1
R
t
Bu
t
Bu
Me
Me
i
Bu
Et
R′
t
Bu
t
Bu
t
Bu
t
Bu
t
Bu
t
Bu
2a
2b
2c
2d
2e
2f
M
Al
Ga
Al
Ga
Al
Al
R
t
Bu
t
Bu
Me
Me
i
Bu
Et
R′
2,6-dimethylphenyl
2,6-dimethylphenyl
2,6-dimethylphenyl
2,6-dimethylphenyl
2,6-dimethylphenyl
2,6-dimethylphenyl
Isonitrile complexes of group 13 trialkyls reported herein.
2.2 Experimental
General Procedures
All air- and moisture-sensitive reactions were performed in an inert atmosphere of
purified nitrogen using standard inert atmosphere techniques and an Innovative
Technologies dry box. Trimethylaluminum, triethylaluminum, and triisobutylaluminum
were purchased from Strem Chemical, Inc. and used as received. tert-Butylisonitrile was
purchased from Aldrich, and 2,6-dimethylphenylisonitrile was purchased from Acros and
used as received. Tri-tert-butylaluminum96,97 and tri-tert-butylgallium98 were prepared
using published procedures.
Toluene was distilled from sodium, and hexanes was
26
distilled from calcium hydride prior to use.
Benzene-d6 (C6D6) and chloroform-d
(CDCl3) were dried by storage over activated molecular sieves and degassed with
purified nitrogen. Solution NMR spectra were recorded on a Varian Unity 400 or Varian
AS-600 spectrometer using deuterated solvent as an internal lock. All chemical shifts are
reported relative to TMS. Infrared spectra were obtained on a Perkin Elmer GX FT-IR
infrared spectrometer.
Elemental analyses were performed by Schwarzkopf
Microanalytical Laboratory, Inc.
Mass spectrometry was performed by Ohio State
University.
ITC measurements were obtained in collaboration with Drs. Robert Flowers and
Joseph Teprovich at Lehigh University.
A MicroCal Omega isothermal titration
calorimeter was employed and the instrument was modified with the appropriate inert
seals and equipped with a small port capable of keeping a static inert gas atmosphere over
the sample. These instrumental changes allow for calorimetric analysis of air-sensitive
compounds in organic solvents. The enthalpies of complexation (ΔHc) were determined
from the calorimetric data employing OriginTM data analysis software.
Solutions of
each isonitrile and trialkyl metal were prepared in dry degassed hexanes in a dry box in
0.01 M and 0.10 M concentrations, respectively. The 1.4 mL calorimetry cell was
flushed with dry argon for 30 min and the trialkyl metal solution was then loaded into the
cell. The isonitrile solution was loaded into a 100 μL calorimetry syringe. A ten injection
matrix was used and each 5 μL injection lasted a total of 10 seconds. A two minute
interval was employed between each injection of isonitrile. The averages of two runs are
summarized in Table 2.6.
27
Preparation of tBu3Al·C≡NtBu (1a)
To a 100 mL side arm flask was added tBu3Al (0.750 g, 3.78 mmol) and 20 mL of
hexanes. To this solution was added 0.45 mL (4.0 mmol) of C≡NtBu via syringe. The
colorless solution was stirred for 4 h. The solution was concentrated by half and stored at
─30 °C for 12 h to yield colorless crystals which were isolated by filtration. Yield: 1.05
g, 3.73 mmol, 97%. 1H NMR (CDCl3, 600 MHz): δ 1.59 (s, 9H, C≡NtBu), 0.93 (s, 27H,
AltBu3).
13
C{1H} NMR (CDCl3, 150 MHz): δ 133.4 (s, C≡NC(CH3)3), 58.3 (s,
C≡NC(CH3)3), 32.2 (s, AlC(CH3)3), 30.2 (s, C≡NC(CH3)3), 16.4 (broad s, AlC(CH3)3).
IR (υC≡N, KBr): 2221 cm–1. Anal Calcd for C17H36NAl: C, 72.55; H, 12.89; N, 4.98.
Found: C, 63.44; H, 12.92; N, 3.63.
Preparation of tBu3Ga·C≡NtBu (1b)
To a 100 mL side arm flask was added tBu3Ga (0.910 g, 3.78 mmol) and 20 mL
of hexanes. To this solution was added 0.45 mL (4.0 mmol) of C≡NtBu via syringe. The
colorless solution was stirred for 4 h. The solution was concentrated by half and stored at
─30 °C for 12 h to yield colorless crystals which were isolated by filtration. Yield: 1.19
g, 3.67 mmol, 96%. 1H NMR (CDCl3, 600 MHz): δ 1.56 (s, 9H, C≡NtBu), 1.02 (s, 27H,
GatBu3).
13
C{1H}
NMR (CDCl3, 150 MHz): δ 57.7 (s, C≡NC(CH3)3), 32.9 (s,
GaC(CH3)3), 30.3 (s, C≡NC(CH3)3), 22.9 (s, GaC(CH3)3). IR (υC≡N, KBr): 2205 cm–1.
Anal Calcd for C17H36NGa: C, 62.98; H, 11.19; N, 4.32. Found: C, 57.01; H, 11.33; N,
3.20.
28
Preparation of Me3Al·C≡NtBu (1c)
To a 100 mL side arm flask was added Me3Al (1.0 mL, 2.0 M toluene, 2.0 mmol)
and 20 mL of hexanes. To this solution was added 0.25 mL (2.21 mmol) of C≡NtBu via
syringe. The colorless solution was stirred for 4 h. The volatiles were removed under
vacuum and the resulting solid was isolated and recrystallized from minimal amount of
hexanes at ─30 °C. Yield: 0.308 g, 1.99 mmol, 94%. 1H NMR (CDCl3, 400 MHz): δ
1.56 (s, 9H, C≡NtBu), ─0.91 (s, 9H, AlMe3).
13
C{1H} (CDCl3, 100 MHz): δ 133.41 (s,
C≡NC(CH3)3), 58.02 (s, C≡NC(CH3)3), 30.06 (s, C≡NC(CH3)3), ─9.32 (s, AlCH3).
IR (υC≡N, KBr): 2224 cm–1.
Preparation of Me3Ga·C≡NtBu (1d)
To a 100 mL side arm flask was added Me3Ga (0.260 g 2.25 mmol) via syringe
and charged with 20 mL of hexanes. To this solution was added 0.25 mL (2.21 mmol) of
C≡NtBu via syringe. The colorless solution was stirred for 4 h. Volatiles were removed
under vacuum and solid was isolated and recrystallized from minimal amount of hexanes
at ─30 °C. Yield: 0.422 g, 2.13 mmol, 95%.
Preparation of iBu3Al·C≡NtBu (1e)
To a 100 mL side arm flask was added iBu3Al (0.520 g, 2.63 mmol). To this was
added 0.30 mL (2.65 mmol) of C≡NtBu via syringe. The colorless solution was allowed
to stir for 2 h and excess isocyanide was evaporated in vacuo. A colorless liquid was
isolated. Yield: 0.711 g, 2.53 mmol, 96%. 1H NMR (C6D6, 600 MHz): δ 2.24 (m, 3H,
AlCH2CH(CH3)2), 1.31 (d, 3JHH = 6.6 Hz, 18H, AlCH2CH(CH3)2), 0.62 (s, 9H, C≡NtBu),
29
0.47 (d, 3JHH = 7.2 Hz, 6H, AlCH2CH(CH3)2). 13C{1H} NMR (CDCl3, 100 MHz): δ 57.7
(s, C≡NC(CH3)3), 30.0 (s, C≡NC(CH3)3), 28.4 (s, AlCH2CH(CH3)2), 27.3 (s,
AlCH2CH(CH3)2), 22.2 (s, AlCH2CH(CH3)2). IR (υC≡N, nujol): 2218 cm–1.
Preparation of Et3Al·C≡NtBu (1f)
To a 100 mL side arm flask, was added Et3Al (0.300 g, 2.63 mmol). To this was
added 0.30 mL (2.65 mmol) of C≡NtBu via syringe. The colorless solution was stirred
for 2 h and excess isocyanide was pumped off in vacuo. A colorless liquid was isolated.
Yield: 0.501 g, 2.59 mmol, 98%. 1H NMR (CDCl3, 400 MHz): δ 1.56 (s, 9H, C≡NtBu),
1.00 (t, 3JHH = 8.0 Hz, 9H, Al–CH2CH3), ─0.25 (q, 3JHH = 8.0 Hz, 6H, Al–CH2CH3).
13
C{1H} NMR (CDCl3, 100 MHz): δ 57.4 (s, C≡NC(CH3)3), 30.3 (s, C≡NC(CH3)3), 10.4
(s, AlCH2CH3), ─0.8 (s, AlCH2CH3). IR (υC≡N, nujol): 2218 cm–1.
Preparation of tBu3Al·C≡N(2,6-Me2C6H3) (2a)
To a 100 mL side arm flask was added tBu3Al (0.750 g, 3.78 mmol) and 20 mL of
hexanes. To this solution, 0.50 g (3.8 mmol) of C≡N(2,6-Me2C6H3) in 15 mL of toluene
was added via syringe. The colorless solution was stirred for 4 h and the solution was
concentrated by half and stored at ─30 °C for 12 h to produce colorless crystals which
were isolated by filtration. Yield: 1.21 g, 3.68 mmol, 97%. 1H NMR (CDCl3, 600 MHz):
δ 7.34 (t, 3JHH = 7.2 Hz, 1H, p-CH), 7.20 (d, 3JHH = 7.2 Hz, 2H, m-CH), 2.49 (s, 6H,
C≡N(2,6-Me2C6H3)), 1.02 (s, 27H, tBu).
13
C{1H} NMR (CDCl3, 150 MHz): δ 136.2,
131.1, 128.4, 32.2 (s, AlC(CH3)3), 18.9 (s, C≡N(2,6-Me2C6H3), 16.6 (s, AlC(CH3)3). IR
30
(υC≡N, KBr): 2197 cm–1. Anal Calcd for C21H36NAl: C, 76.55; H, 11.01; N, 4.25; Al, 8.19.
Found: C, 73.15; H, 11.30; N, 4.30; Al, 8.77.
Preparation of tBu3Ga·C≡N(2,6-Me2C6H3) (2b)
To a 100 mL side arm flask was added tBu3Ga (0.910 g, 3.78 mmol) and 20 mL
of hexanes. To this solution was added 0.50 g (3.8 mmol) of C≡N(2,6-Me2C6H3) in 15
mL of toluene via syringe. The colorless solution was stirred for 4 h, and the solution
was concentrated by half and stored at ─30 °C for 12 h to produce colorless crystals that
were isolated by filtration. Yield: 1.37 g, 3.68 mmol, 97%. 1H NMR (CDCl3, 600 MHz):
δ 7.36 (t, 3JHH = 7.8 Hz, 1H, p-CH), 7.20 (d, 3JHH = 7.8 Hz, 2H, m-CH), 2.50 (s, 6H,
C≡N(2,6-Me2C6H3)), 1.02 (s, 27H, GatBu3).
13
C{1H} NMR (CDCl3, 150 MHz): δ 136.6
(s), 131.5 (s), 128.7 (s), 32.4 (s, GaC(CH3)3), 19.2 (s, C≡N(2,6-Me2C6H3), 16.8 (s,
GaC(CH3)3). IR (υC≡N, KBr): 2183 cm–1. Anal Calcd for C21H36NGa: C, 67.76; H, 9.75;
N, 3.76. Found: C, 65.71; H, 10.51; N, 3.60.
Preparation of Me3Al·C≡N(2,6-Me2C6H3) (2c)
To a 100 mL side arm flask was added Me3Al (1.0 mL, 2.0 M in toluene, 2.0
mmol) and 20 mL of hexanes. To this solution, 0.25 g (1.9 mmol) of C≡N(2,6-Me2C6H3)
in 15 mL of toluene was added via syringe. The colorless solution was stirred for 4 h,
and the volatiles were removed under vacuum. The resulting solid was isolated and
recrystallized from a minimal amount of hexanes followed by storage at ─30 °C. Yield:
0.375 g, 1.85 mmol, 95%. 1H NMR (CDCl3 400 MHz): δ 7.29 (t, 3JHH = 8.4 Hz, 1H, pCH), 7.15 (d, 3JHH = 8.4 Hz, 2H, m-CH), 2.43 (s, 6H, C≡N(2,6-Me2C6H3)), ─0.38 (s, 9H,
31
AlMe3).
13
C{1H} NMR (CDCl3, 100 MHz): δ 135.9 (s), 130.6 (s), 128.4 (s), 18.8 (s,
C≡N(2,6-Me2C6H3), ─5.9 (s, AlCH3). IR (υC≡N, KBr): 2203 cm–1.
Preparation of Me3Ga·C≡N(2,6-Me2C6H3) (2d)
To a 100 mL side arm flask was added Me3Ga (0.230 g, 2.0 mmol) and 20 mL of
hexanes. To this solution was added 0.25 g (1.9 mmol) of C≡N(2,6-Me2C6H3) in 15 mL
of toluene via syringe.
The colorless solution was stirred for 4 h. Volatiles were
removed under vacuum and the resulting solid was isolated and recrystallized from
minimal amount of hexanes followed by storage at ─30 °C. Yield: 0.461 g, 1.87 mmol,
96%.
Preparation of iBu3Al·C≡N(2,6-Me2C6H3) (2e)
To a 100 mL side arm flask was added iBu3Al (0.755 g, 3.81 mmol) and 20 mL of
hexanes. To this solution was added 0.50 g (3.80 mmol) of C≡N(2,6-Me2C6H3) in 15 mL
of toluene via syringe. The red solution was stirred for 4 h, and volatiles were removed
in vacuo to yield a red liquid. Yield: 1.19 g, 3.62 mmol, 95%. 1H NMR (CDCl3, 600
MHz): δ 7.32 (t, 3JHH = 7.8 Hz, 1H, p-CH), 7.17 (d, 3JHH = 7.8 Hz, 2H, m-CH), 2.44 (s,
6H, C≡N(2,6-Me2C6H3)), 1.85(m, 3H, AlCH2CH(CH3)2), 0.94 (3JHH = 6.6 Hz, d, 18H,
AlCH2CH(CH3)2), 1.29 (d, 3JHH = 7.2 Hz, 6H, AlCH2CH(CH3)2).
13
C{1H} (CDCl3, 150
MHz): δ 136.4 (s), 131.2 (s), 128.6 (s), 28.5 (s, AlCH2CH(CH3)2), 27.44 (s,
AlCH2CH(CH3)2), 22.57 (s, AlCH2CH(CH3)2), 18.85 (s, C≡N(2,6-Me2C6H3). IR (υC≡N,
nujol): 2193 cm–1.
32
Preparation of Et3Al·C≡N(2,6-Me2C6H3) (2f)
To a 100 mL side arm flask was added Et3Al (0.440 g, 3.85 mmol) and 20 mL of
hexanes. To this solution was added 0.50 g (3.8 mmol) of C≡N(2,6-Me2C6H3) in 15 mL
of toluene via syringe. The colorless solution was stirred for 4 h, and volatiles were
removed in vacuo resulting in a slight green liquid. Yield: 1.21 g, 3.68 mmol, 97%. 1H
NMR (CDCl3, 600 MHz): δ 7.33 (t, 3JHH = 7.2 Hz, 1H, p-CH), 7.18 (d, 3JHH = 7.8 Hz, 2H,
m-CH), 2.45 (s, 6H, C≡N(2,6-Me2C6H3). 1.07 (t, 3JHH = 8.4 Hz , 6H, Al–CH2CH3),
─0.11 (br m, 9H, Al–CH2CH3. 13C{1H} (CDCl3, 150 MHz): δ 136.3 (s), 131.2 (s), 128.6
(s), 18.9 (s, C≡N(2,6-Me2C6H3), 10.6 (s, AlCH2CH3), ─0.5 (s, AlCH2CH3). IR (υC≡N,
nujol): 2194 cm–1.
2.3 X-ray Crystallography
Crystals of 1a, 1b, 1d and 2a-2d were grown from highly concentrated toluene solutions
stored at ─30 °C. The X-ray diffraction data were collected on a Siemens three-circle
platform diffractometer equipped with a 4K CCD detector. The frame data were acquired
with the SMART 5.62599 software using Mo Kα radiation (λ = 0.71073 Å). Cell
constants were determined with SAINT 6.22100 from the complete dataset. A complete
sphere of data was collected using ω (0.3◦) scans with a run time of 30 s/frame (1a, 1b,
1d, 2b, 2d) and 40 s/frame (2a, 2c) at different Φ angles. A total of 1315 frames (1a),
2132 frames (2a), 2126 frames (1b, 2b), 1180 frames (1d), 2285 frames (2c), or 2120
frames (2d) were collected for the dataset. An additional 50 frames, identical to the first
50, were collected to determine crystal decay. The frames were integrated using the
SAINT 6.22 software, and the data were corrected for absorption and decay using the
33
SADABS101 program. The structures were solved by direct methods and refined by leastsquares methods on F2, using the SHELXTL program suite.102 All hydrogen atoms were
placed in calculated position and included in the refinement as riding models. The
structure for 1c was solved with direct methods in Pna21 and then transformed into the
correct space group Pnma.103 The tBu group is severely disordered over a mirror plane.
The model refined contained 5 positions for each methyl group in a ratio of 0.2: 0.2: 0.4:
0.1: .1. Details of data collection and refinement are provided in Table 2.1. Further
details, including atomic coordinates, distances and angles are found in the CIF files.
34
Table 2.1.
Crystal data and structure refinement details
1a
1b
1d
Formula
C17H36AlN
C17H36GaN
C8H18GaN
Fw
281.45
324.19
197.95
Cryst. Syst
monoclinic
monoclinic
orthorhombic
Space group
P2(1)/m
P2(1)/m
Pnma
a, Å
8.3301(19)
8.3397(2)
13.5497(4)
b, Å
12.218(3)
12.2280(2)
9.6064(3)
c, Å
10.525(2)
10.5604(2)
8.6082(2)
α, deg
90.00
90.00
90.00
β, deg
110.735(4)
110.8900(10)
90.00
γ, deg
90.00
90.00
90.00
V, Å3
1001.8(4)
1006.14(3)
1120.48(5)
Z
4
4
4
Dcalcd, g cm-3
1.400
1.070
1.173
temp, °C
─133
─133
─133
μ, mm-1
0.140
1.359
2.400
λ, Å
0.71073
0.71073
0.71073
transm coeff
1.00-0.795
1.00-0.790
1.00-0.808
2θ limits, deg
4.14-52.00
4.12-56.58
5.60-70.92
total no. of data
6801
15239
4952
no. unique data
2060
2620
2353
no. obsd data
1896
2536
1759
no. of params
91
91
89
R1 (I > 2σ(I))
0.0610
0.0333
0.0366
2
0.1402
0.0832
0.1242
0.560, ─0.586
0.533, ─0.552
wR2 (I , all data)
max, min peaks, e/Å3 0.497, ─0.458
a
I > 2σ(I).
b
R1 =
| |Fo| – |Fc| | / |Fo|.
c
wR2 = [ [w (Fo2 – Fc2)2] / [w (Fo2)2]]1/2.
35
Table 2.1 (Continued)
2a
2b
2c
2d
Formula
C21H36AlN
C21H36GaN
C12H18AlN
C12H18GaN
Fw
329.49
372.23
203.25
245.99
Cryst. Syst
triclinic
triclinic
triclinic
triclinic
Space group
P1
P1
P1
P1
a, Å
8.8875(2)
8.9135(2)
7.3776(4)
7.3706(2)
b, Å
11.8471(2)
11.8766(2)
10.6143(6)
10.6485(3)
c, Å
11.9501(2)
11.9732(3)
17.2858(10)
17.2629(4)
α, deg
64.0690(10)
64.1920(10)
92.011(2)
92.170(1)
β, deg
87.1090(10)
87.1740(10)
94.854(2)
95.034(1)
γ, deg
72.3300(10)
72.3710(10)
91.323(2)
91.303(1)
V, Å 3
1073.19(4)
1082.45(4)
1347.47(13)
1348.24(6)
2
2
4
4
1.003
1.212
1.002
1.212
temp, °C
─133
─133
─133
─133
μ, mm-1
0.096
1.272
0.118
2.008
λ, Å
0.71073
0.71073
0.71073
0.71073
transm coeff
1.00-0.850
1.00-0.858
1.00-0.793
1.00-0.773
2θ limits, deg
3.80-66.64
3.80-56.57
2.36-52.00
2.38-56.56
total no. of data
19702
15412
16421
18897
no. unique data
7553
5367
5254
6685
no. obsd data
6228
5143
4712
6198
no. of params
352
352
337
337
R1 (I > 2σ(I))
0.0496
0.0231
0.0574
0.0252
2
0.1168
0.0602
0.1624
0.0657
Z
Dcalcd, g cm
-3
wR2 (I , all data)
max, min peaks, e/Å3 0.536, ─0.190 0.511, ─0.297
0.279, ─0.209 0.317, ─0.318
________________________________________________________________________
a
I > 2σ(I).
b
R1 =
| |Fo| – |Fc| | / |Fo|.
c
wR2 = [ [w (Fo2 – Fc2)2] / [w (Fo2)2]]1/2.
36
2.4 Results and Discussion
2.4.1 Preparation of Isonitrile Complexes
tert-Butyl isonitrile reacted with tBu3Al in hexanes at room temperature (eq 6) to
yield a white solid (1a) upon removal of the solvent in vacuo. Isolation of a solid
indicated that a reaction had taken place since both starting materials are liquids at room
temperature. The 1H NMR spectrum of 1a in CDCl3 shows only two resonances at 1.59
ppm and 0.93 ppm in a 1:3 ratio, consistent with the presence of the donor-acceptor
complex where one isonitrile is coordinated to the aluminum alkyl. There is no evidence
R3M + C
hexanes
25 °C
NtBu
1a
1b
1c
1d
1e
1f
M
Al
Ga
Al
Ga
Al
Al
R3M C
NtBu
(6)
R
t
Bu
t
Bu
Me
Me
i
Bu
Et
in the 1H NMR spectrum for two different aluminum alkyl resonances as would be
expected if insertion was followed by dimerization. The resonances seen in the 1H NMR
spectrum correspond to the tert-butyl group on the isonitrile (1.59 ppm) and the tert-butyl
groups bound to aluminum (0.93 ppm). The infrared spectrum of 1a obtained in a KBr
pellet showed a C≡N stretch at 2221 cm-1, which is at much higher wavenumber than free
tert-butyl isonitrile (2133 cm-1).
tert-Butyl isonitrile reacted similarly with other aluminum and gallium alkyls as
shown in eq 6. Complexes 1b-1d were isolated as white solids in greater than 90% yield.
The complexes formed with iBu3Al and Et3Al (1e, 1f) were isolated as yellow liquids in
37
greater than 90% yield. The 1H NMR spectrum for each complex shows one singlet
resonance for the tert-butyl group on the isonitrile and one set of resonances for the alkyl
groups on aluminum or gallium. The chemical shift for the tert-butyl resonance of the
bound isonitrile in all complexes is found near 1.56-1.59 ppm in CDCl3, which is
downfield from the resonance at 1.45 ppm seen for free isonitrile. It is expected that as
the aluminum alkyls change from Me to tBu and moving from aluminum to gallium, the
isonitrile chemical shift would change.
However, it is evident that the shift is not
sensitive to the aluminum trialkyl. The coordinated isonitrile is labile in solution, and in
the presence of excess isonitrile the observed chemical shift is a weighted average of the
bound and free isonitrile shifts. The exchange is rapid on the NMR timescale. Even at
─60 °C, there is only one sharp resonance observed upon addition of excess isonitrile
although slightly shifted towards free isonitrile.
The tert-butyl isonitrile derivatives of Et3Al and iBu3Al are yellow liquids even
after storage at ─78 °C for 24 h. The viscosity of the liquids seems to increase at lower
temperatures, but the complexes remain liquids without solidification or crystallization.
It is important to note that compounds 1c and 1d sublime readily at 20 °C under vacuum
at 0.1 mm Hg.
To see if solid complexes could be isolated, 2,6-dimethylphenylisonitrile was
used to make an analogous series of complexes. This isonitrile derivative is a solid at
room temperature, and the bulky dimethylphenyl group was proposed to help crystallize
the resulting complexes.
38
2,6-Dimethylphenylisonitrile was reacted with tBu3Al in hexanes at room
temperature (eq 7) to yield complex 2a. Complexes 2a-2d were isolated similarly as offwhite solids in greater than 90% yield from highly concentrated hexanes solutions, and
complexes 2e and 2f were isolated as yellow liquids despite using the bulkier 2,6dimethylphenylisonitrile. Complexes 2e and 2f remain liquids even when stored at ─78
°C for 24 hours.
R3M +
C
hexanes
25 °C
N
2a
2b
2c
2d
2e
2f
M
Al
Ga
Al
Ga
Al
Al
R3M C
N
(7)
R
t
Bu
t
Bu
Me
Me
i
Bu
Et
The 1H NMR spectra (CDCl3) of complexes 2a-2f show that the isonitrile
coordination is labile in solution on the NMR time scale and the methyl resonances for
the isonitrile are seen as a time average of the free and bound isonitrile at 2.43-2.50 ppm.
The aryl resonances for the phenyl of the isonitrile show up consistently in the same
position for all complexes.
Addition of excess isonitrile and obtaining a 1H NMR spectrum at ─60 °C in
CDCl3 did not result in resolution of free and bound isonitrile, and only one sharp methyl
resonance was observed. The infrared spectrum of 2a in a KBr pellet shows a C≡N
stretch at 2196 cm-1 which is at a higher wavenumber than observed for the free isonitrile
39
(2125 cm-1). This is consistent with an isonitrile being coordinated in a donor-acceptor
fashion to a group 13 metal.
Despite multiple attempts, satisfactory elemental analysis (EA) of some of these
complexes could not be obtained. Samples for 1a and 1b exhibited considerable lower
percent mass for carbon (10%-12%) and nitrogen (1%-2%) than calculated. Samples did
show acceptable EA for carbon, nitrogen, and hydrogen for 2b and carbon, nitrogen,
hydrogen, and aluminum for 2a. Shapiro89 and Uhl91 also reported low carbon and
nitrogen analysis in the isonitrile complexes that they isolated. They both proposed that
the formation of aluminum nitrides in combustion analysis was the cause for the low
percentages.
Attempts to obtain satisfactory mass spectrometry data were also unsuccessful.
No molecular ion peak was seen for complexes 1a or 1b, only free isonitrile was
observed. Dissociation of the isonitrile is prevalent in solution and the electrospray
technique that was used wasn’t ideal for the complexes being tested.
2.4.2 IR Spectroscopy
It is expected that for an isonitrile bound to a group 13 metal there will be a shift
to higher wavenumbers for the C≡N stretch. The carbon lone pair of the isonitrile is in a
slightly anti-bonding orbital, and when that lone pair is donated to the metal center
without the presence of π-backbonding, the C≡N bond strengthens and a shift to higher
wavenumbers is observed. The same shift is seen for homoleptic isonitrile complexes of
certain transition metals and is typical of the CO stretches observed for non-classical
carbonyls.104
This shift to higher frequency was previously observed for the three
reported isonitrile donor-acceptor complexes of aluminum alkyls.87-89
40
Table 2.2 summarizes the C≡N stretching frequencies in the IR spectra for all of
the complexes isolated. For each of the complexes, there is a significant shift (Δ(νCN)) to
higher wavenumbers for the C≡N stretch when the isonitrile is bound to the metal
compared to the free ligand. The shift is not as significant for the complexes with tBu3Ga
which is expected since the trialkyl gallium complexes are considered less Lewis acidic
than their trialkyl aluminum analogues. As the Lewis acidity of the metal decreases, the
amount of donation from the lone pair on the carbon of the isonitrile will also decrease.
This will cause a decrease in the strengthening of the C≡N bond when coordinated to a
metal.
C≡N Stretching frequencies and coordination shifts for 1a-1f and
2a-2f
_______________________________________________________________________
Complex
νCN (cm-1)
ΔνCN (cm-1)
_____________________________________________________________________
t
1a
Bu3Al•C≡NtBu
2221
+88
Table 2.2.
1c
Me3Al•C≡NtBu
2224
+91
1e
i
Bu3Al•C≡NtBu
2218
+85
1f
Et3Al•C≡NtBu
2218
+85
1b
t
Bu3Ga•C≡NtBu
2205
+72
2a
t
Bu3Al•C≡N(2,6-Me2C6H3)
2195
+70
2c
Me3Al•C≡N(2,6-Me2C6H3)
2203
+78
2e
i
Bu3Al•C≡N(2,6-Me2C6H3)
2193
+68
2f
Et3Al•C≡N(2,6-Me2C6H3)
2195
+70
2b
t
2183
+58
Bu3Ga•C≡N(2,6-Me2C6H3)
Free Isonitrile
C≡NtBu
2133
C≡N(2,6-Me2C6H3)
2125
________________________________________________________________________
41
It was initially thought that changes in the C≡N stretch for the bound isonitrile might be a
gauge of the strength of Lewis acidity for different R3Al species. It can be seen from the
table, however, that there is very little change in the Δ(νCN) values for each of the
different isonitriles when they are bound to different aluminum trialkyls.
2.4.3
Molecular Structures
X-ray crystallography confirmed the molecular structures of 1a, 1b, 1d, and 2a-
2d (Figures 2.2 and 2.3). Complexes 1a and 1b crystallized in the space group P2(1)/m
and the structures were refined with R1 factors of 6.10% and 3.33%, respectively.
Complex 1d crystallized in the space group Pnma and the structure refined with an R1
factor of 3.66%. Complexes 2a and 2b crystallized in the space group P 1 and the
structures were refined with R1 factors of 4.78% and 2.52%, respectively. Complexes 2c
and 2d crystallized in the space group P 1 and the structures were refined with R1 factors
of 4.96% and 2.31%, respectively. The Al–Cisonitrile bond distances for these structures
range from 2.1166(11) Å to 2.121(3) Å and the C≡N bond distances range from 1.148(3)
Å to 1.1489(13) Å.
These are comparable with the values reported for the other
crystallographically characterized donor-acceptor complex reported by Shapiro.89 The
Ga–Cisonitrile bond distances range from 2.167(2) Å to 2.1749(15) Å and the C≡N bond
distances range from 1.140(3) Å to 1.149(2) Å. The M–C–N bond angles range from
173.9(2)° to 179.88(13)°, which are in agreement to that reported by Shapiro. Selected
bond distances and angles are summarized in Table 2.3. As expected, the average Al–
Cisonitrile bond distances are significantly shorter than the Ga–Cisonitrile bond distances.
42
N1
N1
N1
C1
C3A
C1
C22
C22
C23
C31A
C31A
Ga1
C32A
Al1
C21
C3
C33A
C33
C31
C21
C2
C31
C3A
C23
C1
C2
C33A
C2
C3
Ga1
C3
C32A
C33
C32
C4
C32
Figure 2.2
ORTEP diagrams of 1a, 1b and 1d. Thermal ellipsoids are drawn
at the 30% probability level. Hydrogen atoms are omitted for
clarity.
C21
C21
N1
C32
1d
1b
1a
N1
C22
C1
C1
C32
C22
C3
C2
C2
C3
Al1
C23
Ga1
C23
C33
C31
C4
C33 C31
C43
C42
C43
C4
C42
C41
C41
2a
2b
N1
C1
N1
C3
C1
C3
Ga
C4
C2
2d
2c
Figure 2.3
C4
C2
Al1
ORTEP diagrams of 2a-d. Thermal ellipsoids are drawn at the
30% probability level. Hydrogen atoms are omitted for clarity.
43
Table 2.3.
Selected bond distances and angles
__________________________________________________________________
Complex
M–C (Å)
C≡N (Å)
M–C≡N (deg)
__________________________________________________________________
Aluminum Complexes
1a
2.121(3)
1.148(3)
174.9(3)
2a
2.1166(11)
1.1489(13)
175.59(9)
2c
2.1201(14)
1.1484(17)
179.88(13)
Gallium Complexes
1b
2.167(2)
1.143(3)
173.9(2)
1d
2.173(2)
1.140(3)
178.9(12)
2b
2.1679(13)
1.1475(17)
175.15(11)
2d
2.1749(15)
1.149(2)
179.88(18)
__________________________________________________________________
The C≡N bond distance for each complex is almost identical. It is insensitive to the
metal or isonitrile in the structure. This is also seen in transition metal chemistry for CO,
where there is an influence over the IR stretching frequency in different metal carbonyls
but essentially no difference in C≡O bond distance for known crystal structures.
2.4.4 Reactivity of Donor-Acceptor Complexes
Based on the computational studies of Schaefer, it was surprising that only the
donor-acceptor complexes were isolated.
Schaefer concluded that these complexes
would not be stable and would be prone to elimination and alkyl transfer reactions.95 It is
evident that compounds 1a-1f and 2a-2f are stable at room temperature under an inert
atmosphere for up to 3 years without any changes in the 1H NMR spectra. Complexes
1e-1f and 2e-2f do slowly discolor to green and red when stored for several months, but
there is still no change in their 1H NMR spectra. To test the thermal stability of these
complexes, a series of experiments were performed to check for rearrangement or
decomposition of the complexes at elevated temperatures.
44
To analyze the complexes for stability, a system was set up to screen all of the
complexes under the same set of conditions. NMR samples of ten of the complexes were
prepared in C6D6 and slowly heated to 100 °C and checked periodically for reactivity by
1
H NMR spectroscopy. Table 2.4 summarizes the results. In all but two cases, there was
no reactivity seen for the donor-acceptor complexes even after heating to 100 °C for 24
For tert-butyl isonitrile derivatives with Et3Al and iBu3Al there was
hours.
decomposition at 100 °C resulting in a mixture of unidentified products by 1H NMR
spectroscopy.
Complexes 1a-1c and 2a-2f show stability up to 100 °C for 24 h. To check for
reactivity under more harsh conditions, complex 1a was dissolved in toluene and refluxed
Table 2.4.
Reactivity of complexes in C6D6
________________________________________________________________________
Complex
40 °C
60 °C
80 °C
100 °C
8h
12 h
24 h
24 h
_______________________________________________________________________
1a
t
Bu3Al•C≡NtBu
NR
NR
NR
NR
1b
t
NR
NR
NR
NR
1c
Me3Al•C≡NtBu
NR
NR
NR
NR
1e
i
NR
NR
NR
decomp
Bu3Ga•C≡NtBu
Bu3Al•C≡NtBu
t
1f
Et3Al•C≡N Bu
NR
NR
NR
decomp
2a
t
NR
NR
NR
NR
2b
t
Bu3Ga•C≡N(2,6-Me2C6H3) NR
NR
NR
NR
2c
Me3Al•C≡N(2,6-Me2C6H3)
NR
NR
NR
NR
2e
i
Bu3Al•C≡N(2,6-Me2C6H3)
NR
NR
NR
NR
2f
Et3Al•C≡N(2,6-Me2C6H3)
NR
NR
NR
NR
Bu3Al•C≡N(2,6-Me2C6H3)
_______________________________________________________________________
NR = No Reaction
45
under nitrogen for 72 hours. Slowly over the course of 72 hours, the color of the solution
changed from colorless to a bright yellow color. All of the solvents were removed and a
yellow oily residue was isolated and showed three distinct singlets with equal intensity in
the aliphatic region of the 1H NMR spectrum in CDCl3 at 1.20 ppm, 1.16 ppm and 1.10
ppm, respectively. An infrared spectrum of the oil did not show any absorption in the
ranges seen for the donor-acceptor complex (Table 2.2). Many attempts were made to
purify the oil by recrystallization and a single crystal was isolated from a highly
concentrated THF solution stored at ─30 °C for four months. X-ray data was collected
and the structure of the complex (3) is shown in Figure 2.4. Uhl91 previously obtained 3
by insertion of tert-butyl isonitrile into the Al–H bond of tBu2AlH. He also reported the
molecular structure, and the parameters for 3 match those reported by Uhl.
The 1H NMR for Uhl’s reported complex does not match that obtained from the
isolated yellow oil. Uhl sees two distinct sets of resonances for the two different tert-
H1
N1
C1
Al1
C1A
Al2
N1A
H1A
Figure 2.4
ORTEP diagram of 3. Thermal ellipsoids are drawn at the 30%
probability level. Most hydrogen atoms are omitted for clarity.
46
butyl groups in a 2:1 ratio.
The obtained single crystal is believed to be a small
component of the isolated material.
It is proposed that 3 was formed by isonitrile
insertion into the Al–H bond of tBu2AlH as the solution was heated for 72 hours.
Lehmkuhl105 reports that heating tBu3Al to 120 °C for 30 hours will result in β-hydride
elimination to give tBu2AlH and butene (Scheme 2) and, if the process is allowed to
continue for an extended period, butene will reinsert into the Al–H bond and continue
until it all converts into iBu3Al. It is likely that as complex 1a was heated over the period
of 72 hours, there was some conversion into tBu2AlH and the isonitrile inserted to give
complex 3.
t
t
120 °C
30 h
Bu3Al
Bu
t
Bu Al
Me
t
Bu
Al
t
Bu
Me
H
H
Me
H + C
Me
t
CH2
Bu
Al
t
Bu
i
Bu
H
Scheme 2.
β-hydride elimination of tBu3Al at elevated temperatures.
Complex 1c was also tested for reactivity at elevated temperatures. Compound 1c
was dissolved in toluene and heated to reflux for 24 hours which resulted in a red-brown
solution.
Removal of solvents in vacuo resulted in the isolation of a brown solid
material. The 1H NMR spectrum in CDCl3 showed one resonance at ─0.69 ppm and the
13
C NMR spectrum showed two peaks at 125 ppm and ─11.7 ppm. The resonances
upfield of TMS in both the 1H and 13C spectra are in the reported range for methyl groups
on aluminum. There is no evidence for a tert-butyl group on the isonitrile and the IR
spectrum shows a very broad peak for the C≡N at 2218 cm-1. Coates and coworkers106
reported the synthesis of the tetramer [Me2AlCN]4 and, although they do not report any
47
NMR spectroscopic data, they do report a C≡N stretch in the IR at 2218 cm-1 that is very
broad. This is also in the range for the C≡N stretch (2211 cm-1) that Uhl91 reports for the
tetramer [tBu2AlCN]4 which is broad. It is likely that with the heating of 1c, there is
elimination of 2,2-dimethylpropane followed by tetramerization to give the compound
reported by Coates. The peak seen at 125 ppm in the
13
C NMR spectrum is likely the
quaternary carbon of the cyano bridge in the tetramer although Uhl claims that in the
tetrameric complex that they isolate this resonance was unobserved.
It is apparent based on the experiments that were done to check for rearrangement
or decomposition of the donor-acceptor complexes that these complexes are significantly
more stable than was theorized by Schaefer and coworkers95 and that only under harsh
conditions do these complexes undergo rearrangement or decomposition.
2.4.5
Isothermal Titration Calorimetry
Solution calorimetry has been used to investigate enthalpies of complexation for
trimethylaluminum and triethylaluminum complexes with a variety of substrates (Table
2.5). The trialkyl aluminum reagents were reacted with a variety of substrates to measure
by calorimetry the heats of complexation for the donor-acceptor complexes. In these
cases, solution calorimetry was used but isothermal titration calorimetry was not. The
formation of these complexes is exothermic and the heat released can be measured
calorimetrically. The binding of CO to a group 13 trialkyl is also exothermic, but there
are no reported CO coordinated complexes of aluminum trialkyls that are stable at room
temperature.
An understanding of the strength of the isonitrile–Al interaction may be
beneficial for the use of isonitriles as a model for CO binding to group 13 alkyls. We are
48
Table 2.5.
Enthalpies of complexation for complexes of Me3Al and Et3Al
L107,108
ΔH (kcal/mol)
Me3Al•L
L109
Me3PO
32.00 ± 0.20
pyridine
27.9
Ph3PO
28.69 ± 0.20
N,N-dimethylaniline
20.0
Me2NH
30.84 ± 0.26
CyNMe2
25.7
Me3N
29.96 ± 0.19
THF
22.5
pyridine
27.56 ± 0.1
Et2O
19.7
NEt3
26.47 ± 0.18
1,4-dioxane
19.2
THF
22.90 ± 0.19
PEt3
22.12 ± 0.33
PMe3
21.02 ± 0.28
Et2O
20.21 ± 0.23
ΔH (kcal/mol)
Et3Al•L
________________________________________________________________________
*Values for Me3Al and Et3Al were corrected for enthalpies of dissociation of the dimers
also interested in using calorimetry data to gauge the Lewis acidity of aluminum and
gallium alkyls since the Δ(νC≡N) was not very sensitive.
Isothermal Titration Calorimetry (ITC) is a technique used to measure heats of
interaction, binding affinity, enthalpies of reaction and metal coordination numbers for
solutions. Solution calorimetry has been used to measure reaction enthalpies of inorganic
and organometallic complexes including materials that are air- and moisture-sensitive,110
but no ITC studies with aluminum or gallium alkyls have been reported. To test for
strengths of interactions of the isonitriles with the trialkyl aluminum and gallium
compounds, ITC was used to measure ΔH for the binding of the isonitrile to the metal
trialkyls. This work was done in collaboration with Dr. Robert Flowers and Dr. Joseph
49
Teprovich at Lehigh University. Dr. Robert Flowers is considered a leading expert in the
area of solution titration calorimetry.
Heat generated by addition of the isonitrile in hexanes to a solution of metal
trialkyl in hexanes was measured and thermograms and binding isotherms were
generated. An example thermogram is shown in Figure 2.5 and the calculated binding
Time (min)
0
10
20
µcal/sec
0
-20
kcal/mole of injectant
-40
0
-2
-4
-6
-8
-10
-12
-14
-16
-18
-20
-22
0.000
0.001
0.002
0.003
0.004
Molar Ratio
Figure 2.5
ITC thermogram for titration of iBu3Al with tBuN≡C.
(Top) Heat change associated with addition of 5 μL aliquots
of tBuN≡C (0.010 M) to iBu3Al (1.4 mL, 0.10 M) at 25 °C.
(Bottom) Binding isotherm.
enthalpies are summarized in Table 2.6. One trial of each complex was run while at
Lehigh and a second trial of each was run by Dr. Joseph Teprovich subsequently. The
two trials were averaged to give the values that are reported in the table. Me3Al and
50
Table 2.6.
ITC thermodynamic data summary
________________________________________________________________________
Complex
ΔH (kcal/mol)
________________________________________________________________________
1a
t
Bu3Al•C≡NtBu
24.399 ± 0.558
1b
t
Bu3Ga•C≡NtBu
16.998 ± 0.303
1c
Me3Al•C≡NtBu
21.652 ± 0.301*
1e
i
Bu3Al•C≡NtBu
20.872 ± 0.278
1f
Et3Al•C≡NtBu
21.316 ± 0.380*
2a
t
Bu3Al•C≡N(2,6-Me2C6H3)
25.899 ± 0.678
2b
t
Bu3Ga•C≡N(2,6-Me2C6H3)
16.755 ± 0.320
2c
Me3Al•C≡N(2,6-Me2C6H3)
21.931 ± 0.463*
2e
i
Bu3Al•C≡N(2,6-Me2C6H3)
21.196 ± 0.628
2f
Et3Al•C≡N(2,6-Me2C6H3)
20.891 ± 0.253*
________________________________________________________________________
*Values for Me3Al and Et3Al were corrected for enthalpies of dissociation of the
dimers111,112
Et3Al are dimers in solution and the binding enthalpies that are reported for these
complexes were corrected using half values of their enthalpies of dimerization from
literature.111,112 It is evident that the binding of the isonitrile to the metal trialkyl is
exothermic and has a fairly strong interaction. The binding enthalpies for the isonitrile
coordination are in the range reported by Eyman107,108,113 and Bonitz109 for trialkyl
phosphines coordinating to Me3Al, but not as strong as amine coordination.
The
isonitrile coordination is less exothermic than binding of common phosphine oxides and
trialkyl amines, but more exothermic than the binding of ether or THF. The binding
enthalpies for both isonitriles to the aluminum alkyls are consistent for each isonitrile
51
with tBu3Al being slightly higher. This could be due to the fact that tBu3Al is strictly a
monomer in solution so the reported values required no correction factor. The binding
enthalpies for both isonitriles to tBu3Ga are lower than the corresponding aluminum
alkyls. This is due to gallium trialkyls being less Lewis acidic than aluminum trialkyls
lowering the strength of the binding interaction.
2.5 Conclusions
The first extensive series of isonitrile donor-acceptor complexes of aluminum and
gallium trialkyls is reported. These complexes are stable at elevated temperatures and
show binding that is analogous to non-classical CO complexes of transition metals.
Under harsh conditions, evidence for rearrangement and decomposition is seen. The
coordinated isonitriles are labile in solution and ITC data suggests that the binding is very
exothermic.
52
Chapter Three
Confirmation of Bridging N-Indolyls in 3-Methylindole and Di- and
Tri(3-methylindolyl)methane Complexes of Dialkylaluminum Moieties
3.1 Introduction
Pyrrolyl-,114-121 indolyl-,122-126 and carbazolyl-127 based compounds have been
used as nitrogen-donor ligands to various types of metal complexes. It is known that
these ligands provide significantly different electronic and steric properties compared to
the common amido ligands.128 Mason and coworkers125,126,129 have used chelating di- and
tri(3-methylindolyl)methanes as ligands for group 4 metals and have reported several
advantages including excellent electron-withdrawing ability and reduced π-donating
properties due to extensive delocalization of the nitrogen lone pair over the aromatic
system.
These properties imply a reduced tendency for M–N–M bridging when
compared to typical amido ligands, and there are fewer examples of μ2-η1:η1-N-pyrrolyl
(Figure 3.1), indolyl, and carbazolyl ligands than bridging amido ligands, particularly for
the main group elements.
All examples of the bridging pyrrolyl, indolyl, and carbazolyl ligands with main
group elements have been observed for the alkali metals. The μ2-η1:η1-N coordination
mode for indolyl and carbazolyl ligands has been confirmed structurally by X-ray
crystallography for a few of the dimers including lithio-, potassio- and sodioindole along
53
N
N
N
N
N
N Binding Mode
N Binding Mode
Figure 3.1
M
M
M
Binding descriptions for η1-N and μ2-η1:η1-N coordination modes
with lithio-, potassio- and sodiocarbazole.130-133 The structure of N-sodioindole•TMEDA
(TMEDA = tetramethylethylenediamine) is shown in Figure 3.2. It can clearly be seen
that there is one indolyl bridge group per sodium metal center.
Each sodium is
approximately tetrahedral and capped with a chelating TMEDA group.
N1
Na1
Na2
Figure 3.2
N2
ORTEP diagram of N-sodioindole•TMEDA generated from CIF
file from Cambridge Crystallographic Database132
The μ2-η1:η1-N coordination mode is also observed for pyrrolyl rings in a mesooctamethylporphyrinogen complex with sodium.134
In some cases, the μ2-η1:η1-N
coordination mode is stabilized by π interactions between one or more heterocyclic
carbon atoms and the metal center. This is expected since η5 coordination of pyrrole
54
heterocycles has been seen in some complexes of group 1,133,135-137 2,138 and 14139,140
metals and is prevalent for transition metals.141
There are no reports in the literature of μ2-η1:η1-N coordination of pyrrolyl,
carbazolyl and indolyl moieties for group 13 elements. There are reports of dimer
complexes for aluminum, gallium and indium with η1-N-pyrrolyl and η1-C-pyrrolyl
ligands, but in all cases the dimerization arises from π-association of the metal in one
monomer with one or two pyrrole carbons on adjacent monomers.142-144 The lack of
additional examples suggests that the μ2-η1:η1-N mode for pyrrolyl, carbazolyl and
indolyl is less favorable than the terminal η1-N coordination to main group metals.
Cowley145 reports that six equivalents of pyrrole will react with [Al(NMe2)3]2 to
form [(Me2NH)Al(NC4H4)3]. It was expected that the isolated complex would be the
[Al(NC4H4)3]2 dimer analogous to the [Al(NC4H8)3]2 dimer isolated by Smith and
coworkers (Figure 3.3).146 Amine elimination was not used in the preparation by Smith
NHMe2
N
N
Al
N
N
N
Al
N
N
[(Me2N(H))Al(pyr)3]
[Al(NC4H8)3]2
Figure 3.3
Al N
N
Bridging pyrrolidine, and monomeric pyrrole complexes isolated by
Smith146 and Cowley145
55
but there was Me3N coordinated in the starting Me3N•AlH3. The bridging structure
isolated by Smith and the monomer isolated by Cowley demonstrate the greater
propensity for amido ligands to bridge metal centers compared to pyrroles.
Concurrent with the work described in this chapter, Anirban Das and Bassam
Fneich of the Mason group isolated aluminum complexes that incorporated the di(3methylindolyl)pyridylmethane
and
di(3-methylindolyl)-1-methylimidazolemethane
ligands (Figure 3.4). Although two different structures for 1 and 2 were proposed based
on NMR spectroscopic data, X-ray crystallographic characterization of 1 confirmed the
presence of an μ2-η1:η1-N-indolyl moiety in which one indolyl arm bridges two
dialkylaluminum centers.81
R
R
N
Al
N R
Al R
N
N
R
Al
Al
R
N
N
N
1
R= Me, Et
Figure 3.4
R
R
2
Bridging dialkylaluminum complexes of di(3methylindolyl)methanes
In this chapter the synthesis and characterization of group 13 complexes with 3methylindole, di(3-methylindolyl)phenylmethane, and tri(3-methylindolyl)methane are
reported. Within this report are the first examples of μ2-η1:η1-N-indolyl moieties bridging
group 13 elements, specifically aluminum. X-ray crystallography confirmed the presence
of the bridging 3-methylindolyl group in 7a, 8, and 9a-c where there is one 356
R
R
Al
N
N
Al
R
R
R
Al
R
R
Me
Al
N
N
Al Al
Me
N
N
Me
R
Al
R
Me
R
N
Al
Al
R
N
R
N
R
R
R
7a Me
7b Et
7c iBu
8
R
9a Me
9b Et
9c iBu
methylindolyl moiety per aluminum, and NMR spectroscopic data supports the claim
that, even though the process is fluxional, the bridging moiety remains intact in solution.
3.2 Experimental
General Procedures
All air- and moisture-sensitive reactions were performed in an inert atmosphere of
purified nitrogen using standard inert atmosphere techniques and an Innovative
Technologies dry box. Trimethylaluminum, triethylaluminum, and triisobutylaluminum
were purchased from Strem Chemical, Inc. 3-Methylindole was purchased from Aldrich
Chemicals
and
used
as
received.
Tri-tert-butylaluminum,97,147
di(3-
methylindolyl)phenylmethane,129 and tri(3-methylindolyl)methane129,148 were prepared
using published procedures.
Toluene was distilled from sodium and hexanes was
distilled from calcium hydride prior to use.
57
Benzene-d6 (C6D6) and chloroform-d
(CDCl3) were dried by storage over activated molecular sieves and degassed with
purified nitrogen. Solution NMR spectra were recorded on a Varian VXRS-400 or a
Varian AS-600 spectrometer using deuterated solvent as an internal lock. Chemical
shifts are reported relative to TMS.
13
C NMR chemical shift assignments for C4, C5, C6,
and C7 were aided by 2D-COSY, 2D-HMQC and 2D-HMBC experiments. The accepted
numbering scheme of the indole substituent is shown in Figure 3.5 and is used for all
spectral assignments.
Elemental analyses were performed by Schwarzkopf
Microanalytical Laboratory Inc., or Galbraith Laboratories, Inc.
4
5
3a
3
2
6
7
7a N 1
H
Figure 3.5 Numbering scheme for indole
Synthesis of [3-methylindolyl(AlMe2)]2 (7a)
To a 100 mL side arm flask was added 3-methylindole (0.262 g, 2.00 mmol) and
20 mL of toluene. A toluene solution of trimethylaluminum (1.0 mL, 2.0 M, 2.0 mmol)
was added via syringe. Gas evolution proceeded immediately, followed by precipitation
of an off-white solid. The mixture was stirred for 2 h and a solid material was isolated by
filtration followed by washing with cold hexanes (5 mL). Yield: 0.318 g, 1.70 mmol,
85%. 1H NMR (CDCl3, 600 MHz) syn isomer: δ 7.86 (d, 3JHH = 9.6 Hz, 2H, H7), 7.61 (d,
3
JHH = 9.6 Hz, 2H, H4), 7.40-7.34 (m, 6H, H2, H5, H6), 2.36 (s, 6H, indole CH3), ─0.50
(s, 6H, CH3), ─0.84 (s, 6H, CH3). 1H NMR (CDCl3, 600 MHz) anti isomer: δ 7.75 (d,
3
JHH = 10.8 Hz, 2H, H7), 7.61 (d, 3JHH = 10.2 Hz, 2H, H4), 7.40-7.34 (m, 6H, H2, H5,
H6), 2.37 (s, 6H, indole CH3), ─0.71 (s, 12H, CH3). 13C{1H} NMR (CDCl3, 150.8 MHz):
58
145.6 (s, C3a), 135.5 (s, C7a anti), 135.4 (s, C7a syn), 133.2 (s, C2 syn), 132.6 (s, C2
anti), 123.8 (s, C6 syn), 123.6 (s, C6 anti), 123.3 (s, C5 syn), 123.3 (s, C5 anti), 123.0 (s,
C3), 119.7 (s, C4 anti), 119.6 (s, C4 syn), 118.7 (s, C7), 10.4 (s, CH3), 7.4 (s, AlCH3).
Anal Calcd for C22H28N2Al2: C, 70.57; H, 7.54; N, 7.48; Al, 14.41. Found: C, 69.20; H,
7.67; N, 7.38; Al, 15.25.
Synthesis of [3-methylindolyl(AlEt2)]2 (7b)
To a 100 mL side arm flask was added 3-methylindole (0.403 g, 3.07 mmol) and
35 mL of toluene. Triethylaluminum (0.350 g, 3.07 mmol) in 10 mL of toluene was
added via syringe. The solution turned light yellow which darkened over 12 h of stirring.
Solvent was removed in vacuo which resulted in pure 7b as a yellow solid. Solid 7b can
be recrystallized from a highly concentrated hexanes solution. Yield: 0.647 g, 3.01
mmol, 97%. 1H NMR (CDCl3, 600 MHz) syn isomer: δ 7.96 (d, 3JHH = 7.8 Hz, 2H, H7,
syn), 7.58 (d, 3JHH = 7.8 Hz, 2H, H4), 7.39-7.34 (m, 6H, H2, H5, H6), 2.36 (s, 6H, indole
CH3), 0.67 (t, 3JHH = 7.8 Hz, 6H, AlCH2CH3), 0.39 (t, 3JHH = 7.8 Hz, 6H, AlCH2CH3),
0.19 (q, 3JHH = 7.8 Hz, 4H, AlCH2CH3), 0.00 (q, 3JHH = 7.8 Hz, 4H, AlCH2CH3). 1H
NMR (CDCl3, 600 MHz) anti isomer: δ 7.82 (d, 3JHH = 7.8 Hz, 2H, H7), 7.58 (d, 3JHH =
7.8 Hz, 2H, H4), 7.39-7.34 (m, 6H, H2, H5, H6), 2.38 (s, 6H, indole CH3), 0.52 (t, 3JHH =
7.8 Hz, 12H, AlCH2CH3), 0.07 (m, 8H, AlCH2CH3).
13
C{1H} NMR (CDCl3, 150.8
MHz): δ 145.3, 145.2, 135.2, 135.0, 132.3, 131.8, 129.3, 128.4, 123.7, 123.6, 123.3,
123.2, 122.9, 122.8, 119.5, 118.0, 117.9, 10.08, 10.1, 8.10 (s, CH3, syn), 7.78 (s, CH3,
anti), 7.63 (s, CH3, syn), 2.35 (s, CH2, syn), 1.47 (s, CH2, anti), 0.84 (s, CH2, syn). 1H
NMR (C6D6, 600 MHz) syn isomer: δ 8.10 (d, 3JHH = 7.8 Hz, 2H, H7), 7.40 (m, 2H, H4),
7.31-7.28 (m, 4H, H2, H6), 7.24-7.21 (m, 2H, H5), 2.10 (s, 6H, indole CH3), 0.84 (t, 3JHH
59
= 8.4 Hz, 6H, AlCH2CH3), 0.61 (t, 3JHH = 8.4 Hz, 6H, AlCH2CH3), 0.40 (q, 3JHH = 8.4
Hz, 4H, AlCH2CH3), 0.14 (q, 3JHH = 7.8 Hz, 4H, AlCH2CH3). 1H NMR (C6D6, 600 MHz)
anti isomer: δ 7.93 (d, 3JHH = 7.8 Hz, 2H, H7), 7.40 (m, 4H, H4, H2), 7.31-7.28 (m, 2H,
H6), 7.24-7.21 (m, 2H, H5), 2.09 (s, 6H, indole CH3), 0.72 (t, 3JHH = 8.4 Hz, 12H,
AlCH2CH3), 0.27 (m, 8H, AlCH2CH3). 13C{1H} NMR (C6D6, 150.8 MHz): δ 145.39 (s,
C3a syn), 145.26 (s, C3a, anti), 135.11 (s, C7a, anti), 134.97 (s, C7a, syn), 132.12 (s, C2,
syn), 131.60 (s, C2, anti), 123.89 (s, C6, syn), 123.76 (s, C6, anti), 123.41 (s, C5, syn),
123.39 (s, C5, anti), 122.93 (s, C3, anti), 122.82 (s, C3, syn), 119.70 (s, C4, anti), 119.64
(s, C4, syn), 117.94 (s, C7, anti), 117.89 (s, C7, syn), 9.50 (s, indole CH3), 8.10 (s, CH3,
syn), 7.80 (s, CH3, anti), 7.66 (s, CH3, syn), 2.34 (s, CH2, syn), 1.60 (s, CH2, anti), 1.05
(s, CH2, syn). Anal Calcd for C26H36N2Al2: C, 72.53; H, 8.43; N, 6.51; Al, 12.53. Found:
C, 69.48; H, 8.11; N, 6.40; Al, 13.05.
Synthesis of [3-methylindolyl(AliBu2)]2 (7c)
To a 100 mL side arm flask was added 3-methylindole (0.747 g, 5.70 mmol) and
50 mL of toluene. A toluene solution of triisobutylaluminum (5.7 mL, 1.0 M, 5.70
mmol) was added via syringe. The colorless solution stirred for 4 h and solvent was
removed in vacuo. The resulting white solid was dissolved in 10 mL of toluene and
crystallized following storage at ─30 °C for 12 h. Yield: 1.47 g, 5.47 mmol, 96%. 1H
NMR (C6D6, 600 MHz) syn isomer: δ 8.21 (d, 3JHH = 7.8 Hz, 2H, H7), 7.40 (d, 3JHH = 7.8
Hz, 2H, H4), 7.31-7.25 (m, 4H, H2 syn, H6), 7.21-7.19 (m, 2H, H5), 2.12 (s, 6H, indole
CH3), 1.80 (m, 2H, CH), 1.52 (m, 2H, CH), 0.82 (d, 6H, CH3), 0.52-0.43 (m, 14H, CH2,
CH3). 1H NMR (C6D6, 600 MHz) anti isomer: δ 7.98 (d, 3JHH = 8.4 Hz, 2H, H7), 7.47 (s,
60
2H, H2), 7.40 (d, 3JHH = 7.8 Hz, 2H, H4), 7.31-7.25 (m, 2H, H6), 7.21-7.19 (m, 2H, H5),
2.13 (s, 6H, indole CH3), 1.65 (m, 4H, CH), 0.73 (d, 12H, CH3), 0.59 (d, 12H, CH3),
0.52-0.43 (m, 8H, CH2).
13
C{1H} NMR (C6D6, 150.8 MHz): δ 146.15 (s, C3a, syn),
145.64 (s, C3a, anti), 135.53 (s, C7a, anti), 135.40 (s, C7a, syn), 133.72 (s, C2, syn),
133.01 (s, C2, anti), 123.52 (s, C6), 123.34 (s, C5, syn), 123.32 (s, C5, anti), 122.42 (s,
C3, anti), 122.23 (s, C3, syn), 119.60 (s, C4), 119.37 (s, C7, anti), 119.21 (s, C7, syn),
27.88 (s, CH3, syn), 27.61 (s, CH3, anti), 27.57 (s, CH3, anti), 27.20 (s, CH3, syn), 26.22
(s, CH, syn), 25.92 (s, CH, anti), 25.69 (s, CH, syn), 25.62 (br s, CH2, syn), 23.74 (br s,
CH2, anti), 22.01 (br s, CH2, syn), 9.47 (s, indole CH3, anti), 9.46 (s, indole CH3, syn).
Anal Calcd for C34H52N2Al2: C, 75.24; H, 9.66; N, 5.16. Found: C, 73.24; H, 8.64; N,
5.06.
Synthesis of [{di(3-methylindolyl)phenylmethane}(AlMe2)2] (8)
To a 100 mL side arm flask was added di(3-methylindolyl)phenylmethane (0.350
g, 1.00 mmol) and 25 mL of toluene. A toluene solution of trimethylaluminum (1.0 mL,
2.0 M, 2.0 mmol) was added via syringe. Gas evolution proceeded immediately and the
solution slowly turned dark green over 12 h. Solvent was removed in vacuo and the
remaining green oil was dissolved in 15 mL of hexanes. The solution was stored at ─30
°C for 12 h to yield a green solid which was isolated by filtration. Attempts to isolate 8
as a pure sample separate from excess Me3Al was not successful. The presence of excess
Me3Al broadens all resonances in the
1
H NMR spectrum making assignments
unsuccessful.
61
Synthesis of [{tri(3-methylindolyl)methane}(AlMe2)3] (9a)
To a 100 mL side arm flask was added tri(3-methylindolyl)methane (0.269 g,
0.667 mmol) and 30 mL of toluene, followed by heating to 50 °C in an oil bath. A
toluene solution of trimethylaluminum (1.0 mL, 2.0 M, 2.0 mmol) was added via syringe.
The reaction solution turned bright yellow and darkened as the solution was cooled to 25
°C and stirred for 12 h. The solvent was then removed in vacuo, resulting in a yellow
solid, which was dissolved in a mixture of 10 mL of toluene and 5 mL of hexanes
followed by cooling to ─30 °C for 48 h. The resulting white crystalline material was
isolated by filtration. Yield: 0.338 g, 0.590 mmol, 88%. 1H NMR (C6D6, 600 MHz): δ
7.87 (d, 3JHH = 7.8 Hz, 3H, H7), 7.28 (d, 3JHH = 7.8 Hz, 3H, H4), 7.11 (m, 6H, H5, H6),
6.08 (s, 1H, CH), 2.12 (s, 9H, indolyl CH3), 0.45 (s, 9H, AlCH3), ─2.27 (s, 9H, AlCH3).
13
C{1H} NMR (C6D6, 150.8 MHz): δ 143.23 (s, C3a), 140.03 (s, C2), 137.35 (s, C7a),
125.20 (s, C5), 124.82 (s, C6), 121.66 (s, C3), 120.09 (s, C4), 117.16, (s, C7), 33.58 (s,
CH), 8.50 (s, CH3), ─6.65 (br s, AlCH3), ─19.34 (br s, AlCH3). 1H NMR (CDCl3, 600
MHz): δ 7.69 (m, 3H, H7), 7.48 (m, 3H, H4), 7.31 (m, 6H, H5, H6), 6.14 (s, 1H, CH),
2.45 (s, 9H, indolyl CH3), 0.04 (s, 9H, AlCH3), ─2.74 (s, 9H, AlCH3).
13
C{1H} NMR
(CDCl3, 150.8 MHz): δ 142.78 (s, C3a), 139.72 (s, C2), 137.14 (s, C7a), 124.73 (s, C5),
124.56 (s, C6), 121.53 (s, C3), 119.95 (s, C4), 116.95, (s, C7), 33.32 (s, CH), 8.96 (s,
CH3), ─7.18 (br s, AlCH3), ─19.90 (br s, AlCH3). Anal Calcd for C34H40N3Al3: C, 71.44;
H, 7.05; N, 7.35; Al, 14.16. Found: C, 71.09; H, 7.56; N, 7.32; Al, 14.87.
62
Synthesis of [{tri(3-methylindolyl)methane}(AlEt2)3] (9b)
To a 100 mL side arm flask was added tri(3-methylindolyl)methane (0.442 g, 1.09
mmol) and 50 mL of toluene, followed by heating to 50 °C in an oil bath.
Triethylaluminum (0.375 g, 3.27 mmol) in 10 mL of toluene was added via syringe. The
resulting solution turned slight yellow, which slowly darkened over 24 h. Solvent was
removed in vacuo to yield a yellow oil. The oil was dissolved in 15 mL of hexanes and
stored at ─30 °C for 24 h to yield a yellow crystalline solid that was isolated by filtration.
Yield: 0.72 g, 0.86 mmol, 79%. 1H NMR (C6D6, 600 MHz): δ 7.97 (m, 3H, H7), 7.22
(m, 3H, H4), 7.08 (m, 6H, H5, H6), 6.00 (s, 1H, CH), 2.08 (s, 9H, indolyl CH3), 1.44 (t,
3
JHH = 9.0 Hz, 9H, AlCH2CH3), 1.31 (q, 3JHH = 9.0 Hz, 6H, AlCH2CH3), ─0.13 (t, 3JHH =
9.0 Hz, 9H, AlCH2CH3), ─1.57 (q, 3JHH = 9.0 Hz, 6H, AlCH2CH3). 13C{1H} NMR (C6D6,
150.8 MHz): δ 143.57 (s, C3a), 140.15 (s, C2), 137.56 (s, C7a), 125.00 (s, C5), 124.98 (s,
C6), 121.30 (s, C3), 119.93 (s, C4), 117.54, (s, C7), 33.59 (s, CH), 10.34 (s, CH3), 8.63
(s, AlCH2CH3), 8.20 (s, AlCH2CH3), 3.54 (br s, AlCH2CH3), ─7.88 (br s, AlCH2CH3).
1
H NMR (CDCl3, 600 MHz): δ 7.82 (d, 3H, H7), 7.47 (d, 3H, H4), 7.32 (m, 6H, H6,
H5), 6.12 (s, H, CH), 2.45 (s, 9H, indolyl CH3), 1.14 (t, 3JHH = 8.2 Hz, 9H, AlCH2CH3),
0.96 (q, 3JHH = 8.2 Hz, 6H, AlCH2CH3), ─0.49 (t, 3JHH = 8.7 Hz, 9H, AlCH2CH3), ─1.94
(q, 3JHH = 8.7 Hz, 6H, AlCH2CH3). 13C{1H} NMR (CDCl3, 150.8 MHz): δ 143.17, 139.88
(s, C), 137.33 (s, C), 124.66 (s, C5), 124.58 (s, C6), 121.13 (s, C), 119.74 (s, C4), 117.4,
(s, C7), 33.32 (s, CH), 9.94 (s, CH3), 9.06 (s, AlCH2CH3), 7.69 (s, AlCH2CH3), 2.9 (br s,
AlCH2CH3), ─8.5 (br s, AlCH2CH3). Anal Calcd for C40H52N3Al3: C, 73.26; H, 7.99; N,
6.41; Al, 12.34. Found: C, 72.05; H, 8.34; N, 6.41; Al, 12.80.
63
Synthesis of [{tri(3-methylindolyl)methane}(HAl3iBu5)] (9c)
To a 100 mL side arm flask was added tri(3-methylindolyl)methane (0.403 g, 1.00
mmol) and 50 mL of toluene followed by heating to 50 °C in an oil bath. A toluene
solution of triisobutylaluminum (3.0 mL, 1.0 M, 3.0 mmol) was added via syringe at 50
°C . The resulting solution was kept at 50 °C for 48 h to yield a yellow solution. Solvent
was removed in vacuo to yield a yellow oil. The oil was dissolved in 10 mL of hexanes
followed by cooling to ─30 °C for 12 h which yielded a yellow crystalline solid that was
isolated by filtration. Yield: 0.606 g, 0.79 mmol, 79%.
1
H NMR (C6D6, 600 MHz): δ
8.16 (d, 3JHH = 7.8 Hz, 1H, H7), 8.08 (d, 3JHH = 7.8 Hz, 2H, H7), 7.30 (d, 3JHH = 7.8 Hz,
1H, H4), 7.27 (d, 3JHH = 7.8 Hz, 2H, H4), 7.15 (m, 6H, H5, H6), 6.06 (s, 1H, CH), 2.51
(m, 2H, CH), 2.21 (s, 3H, CH3), 2.16 (s, 6H, CH3), 1.72 (dd, 2JHH = 15 Hz 3JHH = 6.6 Hz,
2H, CH2), 1.52 (dd, 2JHH = 15 Hz 3JHH = 6.6 Hz, 2H, CH2), 1.42 (d, 3JHH = 6.6 Hz, 6H,
CH3), 1.31 (d, 3JHH = 6.6 Hz, 6H, CH3), 0.71 (m, 3H, CH), 0.40 (d, 3JHH = 6.6 Hz, 6H,
CH3), 0.19 (d, 3JHH = 6.6 Hz, 6H, CH3), 0.14 (d, 3JHH = 6.6 Hz, 6H, CH3), ─1.55 (d, 3JHH
= 6.6 Hz, 4H, CH2), ─1.93 (d, 3JHH = 6.6 Hz, 2H, CH2).
13
C{1H} NMR (C6D6, 150.8
MHz): δ 143.95 (s, C3a), 143.49 (s, C3a), 140.34 (s, C2), 137.94 (s, C7a), 137.59 (s,
C7a), 125.21 (s, C5), 125.17 (s, C5), 125.04 (s, C6), 125.00 (s, C6), 122.13 (s, C3),
121.18 (s, C3), 120.11 (s, C4), 120.01 (s, C4), 117.48 (s, C7), 117.37 (s, C7), 33.51 (s,
CH), 29.15 (s, CH2CH(CH3)2), 28.45 (s, CH2CH(CH3)2), 27.65 (s, CH2CH(CH3)2), 27.44
(s, CH2CH(CH3)2), 27.11 (s, CH2CH(CH3)2), 26.86 (s, CH2CH(CH3)2), 24.98 (s,
CH2CH(CH3)2), 24.67 (s, CH2CH(CH3)2), 24.44 (s, CH2CH(CH3)2), 14.19 (s,
CH2CH(CH3)2), 11.41 (s, CH2CH(CH3)2), 8.66 (s, CH3), 8.58 (s, CH3). Anal Calcd for
64
C48H68N3Al3: C, 75.07; H, 8.92; N, 5.47; Al, 10.54. Found: C, 72.33; H, 9.07; N, 5.43;
Al, 10.74.
3.3 X-ray Crystallography
Crystals of 7a were grown from a highly concentrated chloroform solution stored
at ─30 °C. Crystals of 8 were grown from a highly concentrated oil of 8 in toluene stored
undisturbed in the glove box for 3 weeks. Crystals of 9a were grown from a highly
concentrated toluene solution stored at ─30 °C. Crystals of 9b and 9c were grown from
highly concentrated hexanes solutions at ─30 °C. The X-ray diffraction data were
collected on a Siemens three-circle platform diffractometer equipped with a 4K CCD
detector. The frame data were acquired with the SMART 5.62599 software using Mo Kα
radiation (λ = 0.71073 Å). Cell constants were determined with SAINT 6.22100 from the
complete dataset. A complete sphere of data was collected using ω (0.3◦) scans with a
run time of 30 s/frame (7a, 9a, 9b) and 50 s/frame (8, 9c) at different Φ angles. A total of
1262 frames (9c), 1400 frames (8), 1515 frames (9b) or 1415 frames (7a, 9a) were
collected for the dataset. An additional 50 frames, identical to the first 50, were collected
to determine crystal decay. The frames were integrated using the SAINT 6.22 software
and the data were corrected for absorption and decay using the SADABS101 program. The
structures were solved by direct methods and refined by least-squares methods on F2,
using the SHELXTL program suite.102 Details of data collection and refinement are
provided in Table 3.1. Further details, including atomic coordinates, distances and angles
are found in the CIF files.
65
Table 3.1.
Formula
Fw
Cryst. Syst
Crystal data and structure refinement details
7a
C22H28Al2N2
374.42
Monoclinic
8
C29H32Al2N2
462.53
Triclinic
9a•0.6toluene
C38.20H44.80Al3N3
626.91
Triclinic
Space group
P2(1)/c
P1
P1
a, Å
7.9554(4)
11.9211(18)
10.2695(12)
b, Å
18.7424(1)
12.4867(19)
12.3448(14)
c, Å
14.6172(7)
18.489(3)
15.0435(18)
α, deg
90
91.419(3)
77.768(3)
β, deg
104.9450(1)
107.696(3)
86.788(2)
γ, deg
90
101.049(3)
88.308(3)
V, Å3
2105.75(2)
2563.2(7)
1860.6(4)
Z
4
4
2
Dcalcd, g cm-3
1.181
1.199
1.119
temp, °C
─133
─133
─133
μ, mm-1
0.146
0.133
0.130
λ, Å
0.71073
0.71073
0.71073
transm coeff
1.00-0.895
1.00-0.800
1.00-0.861
2θ limits, deg
3.62 to 52.00
2.32 to 52.00
3.38 to 52.00
total no. of data
14293
19281
13288
no. unique data
4133
10067
7270
a
no. obsd data
3778
8574
6868
no. of params
377
591
387
b
R1 (I > 2σ(I))
0.0556
0.0547
0.0548
wR2(I2, all data)c
0.1643
0.1486
0.1733
3
max, min peaks, e/Å 0.478, –0.425
0.481, –0.339
1.023, –0.342
________________________________________________________________________
a
I > 2σ(I). b R1 = | |Fo| – |Fc| | / |Fo|. c wR2 = [ [w (Fo2 – Fc2)2] / [w (Fo2)2]]1/2.
3.4 Results and Discussion
3.4.1 Preparation of di- and tri(3-methylindolyl)methanes
Di- and tri(3-methylindolyl)methanes can be prepared from acid-catalyzed
reactions of two equivalents of 3-methylindole with various aldehydes, or three
equivalents of 3-methylindole with triethylorthoformate. The two ligands (3, 4) of
interest in this chapter were prepared as shown in eqs 1-2 using literature
66
procedures.129,149 Indole moieties are most susceptible to electrophilic attack at C3 so 3methylindole is used for the condensation reactions to force connectivity of the methine
carbon to C2 of the indole, giving the ligands a preferred binding mode. These two
ligands can serve as dianionic, bidentate (3) or trianionic, tridentate (4) ligands, when
deprotonated and bound to a metal, forming six-membered chelate rings.
2
+ PhC(O)H
NH
H+
CH3OH
(1)
Ph
N
H
NH
3
NH
+
3
+ HC(OEt)3
N
H
H
CH3OH
(2)
NH
NH
4
3.4.2 Reactions of 3-methylindole and R3Al (R = Me, Et, iBu)
The initial aim of this research was to generate three-coordinate Lewis acidic
metal complexes via reactions of indoles with aluminum trialkyls. The goals were to
generate these complexes, test their Lewis acidity, and check their ability to bind carbon
monoxide. There are currently no reported complexes of carbon monoxide bound to a
group 13 metal that is stable at room temperature. Theoretical calculations by Hu85 and
67
Pascal85,150 show that the binding of CO to a group 13 alkyl is exothermic and will be
favored at lower temperatures. The binding of CO to a metal is entropically unfavorable
so low temperatures and greater binding enthalpy helps favor this reaction. Generation of
strong Lewis acidic complexes should help the binding of CO to group 13 metals.
As a part of an industrial contract with Zeon Chemicals, Frank Segla and Baohan
Xie reacted indoles and indolyl ligands with different ratios of aluminum alkyls and
successfully used the reaction solutions for the polymerization of epichlorohydrin to high
molecular weight polyethers.151 The aluminum complexes at that time were not isolated
or characterized. The molecular structures of the aluminum complexes used for the
polymerizations are of interest at present.
Based on the previously synthesized ligand frameworks, the use of 3methylindole was a starting point for the investigation. It was chosen based on work
previously done by Baohan Xie and Frank Segla79 of the Mason group who reported the
synthesis of 5 and 6 by reacting six equivalents of 3-methylindole or 2,5-dimethylpyrrole
with [Al(NMe2)3]2 as shown in eqs 3 and 4. X-ray crystallography confirmed that 5
consisted of a four-coordinate aluminum center ligated with three anionic 3methylindolyl moieties and one neutral dimethylamine. While this compound showed
promise, the desired complex would be the three-coordinate base-free Lewis acid without
coordination of the amine.
CH3
6
CH3
NH
+ [Al(NMe2)3]2
N
Al
2
NHMe2
(3)
-4 NHMe2
3
5
68
CH3
6
NH +
CH3
[Al(NMe2)3]2
2
N
Al
- 4 NHMe2
NHMe2
(4)
3
CH3
CH3
6
We started our investigation with reactions of aluminum alkyls with 3methylindole in a 1:1 ratio. 3-Methylindole was added to toluene solutions of R3Al (R =
Me, Et, iBu) in a 1:1 ratio (eq 5). It was expected that the products would contain one
indolyl moiety and two alkyl groups resulting in either dimers (R = Me, Et) with alkyl
groups bridging the aluminum centers, or possibly monomers (R = iBu). Compound 7a
was isolated as an off white solid in 85% yield and X-ray quality crystals were obtained
from a concentrated chloroform solution stored at ─30 °C. The 1H NMR spectrum shows
three different methyl resonances for the alkyl groups on aluminum at ─0.50 ppm, ─0.71
ppm and ─0.84 ppm in CDCl3 with a 1:3:1 ratio. There was no evidence for any NH
protons from unreacted 3-methylindole and there were two methyl resonances for the
indolyl moiety at 2.37 ppm and 2.36 ppm, respectively. There were also two sets of
resonances for H7 at 7.86 ppm and 7.75 ppm, and this indicates that there were two
different compounds isolated in the powder or that there was a fluxional process taking
place between two different isomers of the product.
69
R
R
Al
N
N
Syn Isomer
Al
R
2
NH
R
2 R3Al
toluene
R
R
Al
(5)
Anti Isomer
N
N
Al
R
R
R
7a Me
7b Et
7c iBu
Yield
85%
97%
96%
The specific assignments were made on the basis of gCOSY experiments (Figure 3.6)
which confirmed the assignments of resonances for two sets of indolyl protons H7–H6–
H5–H4. The presence of two sets of indole resonances could be due to syn and anti
isomers of 7a if either a methyl or indolyl bridge were present. Using this assumption,
the 1H NMR spectrum could be assigned based on an indolyl bridge of the aluminum
centers.
The three resonances for aluminum-bound methyls could now be assigned
based on the presence of the syn and anti isomers. In the anti isomer, the methyl groups
on aluminum are chemically equivalent and show up as one resonance at ─0.71 ppm.
The syn isomer results in two methyl resonances at ─0.50 ppm and ─0.84 ppm for the
methyls that are above and below the plane of the four-membered Al2N2 ring. Integration
of the methyl resonances on aluminum and H7 of the indolyl rings shows a 60:40 ratio of
anti to syn isomers in solution.
70
H2 H6 H5
H2anti H4 syn
H7syn
H7anti
H5
H2syn H6
H4
H2anti
H7anti
H7syn
Figure 3.6.
gCOSY spectrum of 7c in benzene-d6 from 7.0 ppm to 8.4 ppm
The resonances in the
13
C NMR spectrum were assigned on the basis of HMQC
(Heteronuclear Multiple Quantum Coherence) and HMBC (Heteronuclear Multiple Bond
Coherence) experiments.152 HMQC gives cross-peaks for direct C–H couplings while
HMBC gives cross-peaks for long range (2-4 bond) C–H coupling. The assigned
chemical shifts are consistent with those previously reported by Mason129 and coworkers
for other di- and tri-indolylmethanes. A representative HMQC spectrum is shown in
Figure 3.7.
71
The indolyl bridged structures were proposed based on 1H NMR spectral
characterization of 7a. It is important to note that NMR spectral characterization did not
rule out the possibility of monomeric structures or methyl bridged dimers.
The
resonances observed for the anti isomer could be assigned to a monomeric structure and
the resonances observed for the syn isomer could be assigned to methyl bridged dimers.
C2
C6D6
C6
C4
C5
C7
C3
H5
H2, H6
H4
H2anti
H7anti
H7syn
Figure 3.7.
HMQC spectrum of 7c in benzene-d6 from 116 to 134 ppm
X-ray crystallography confirmed the structure of 7a (Figure 3.8) as a dimer with
two 3-methylindolyl moieties bridging two aluminum centers. The molecule crystallized
in space group P2(1)/c and the structure was refined with an R1 factor of 5.55%. The
72
structure consists of a whole molecule disorder of two syn isomers with the aluminum
and alkyl atoms overlapping and a refined ratio between the two isomers of 56% to 44%.
Each indolyl moiety bridges two aluminum centers in a μ2-η1:η1-N fashion. This is the
first example of a μ2-η1:η1-N-indolyl coordinated to a group 13 element. Selected bond
distances and angles are summarized in Table 3.2. The Al–N bond distances range from
2.004(4) to 2.037(3) Å, which is comparable to the distances of 2.022(2) and 1.969(2) Å
reported by Das81 for μ2-η1:η1 Al–Nindolyl bond distances. They are also in the range for
N–Al bond distances (1.9588(2) to 1.9673(22) Å) in the bisaluminum complexes bridged
by pyrrolidine moieties reported by Smith and co-workers.146
C28
C15A
C4
C18
C10
C21
C2
C20
Al2
C11
C12
C13
N2
C12
C3
C24
C26
C14
C1
N1A
N2A
Al1
C11A C10A
C25
C18A
C23A
C27A
Al2
C23
C14A
C25A
C26A
C2
C17A
C27
C17
C16
C16A
C22
N1
Al1
C4
C13A
C1
C24A
C22
C3
C20A C21A
C28A
C15
Figure 3.8
ORTEP diagrams of 7a. Both syn isomers of the whole molecule
disorder are shown. Thermal ellipsoids are drawn at the 30%
probability level. Hydrogen atoms are omitted for clarity.
73
Table 3.2
Selected bond distances and angles for 7a
Bond distances (Å)
Al1–N1
2.008(3)
Al1–N1a
2.033(4)
Al1–N2
2.016(3)
Al1–N2a
2.027(4)
Al2–N1
2.024(3)
Al2–N1a
2.004(4)
Al2–N2
2.037(3)
Al2–N2a
2.004(4)
Al1–C1
1.947(3)
Al1–C2
1.949(3)
Al2–C3
1.941(3)
Al2–C4
1.946(2)
Bond angles (deg)
N1–Al1–N2
88.51(13)
C3–Al2–C4
117.91(13)
N1–Al2–N2
87.52(13)
C1–Al1–N1
115.18(13)
N1a–Al1–N2a
85.75(16)
C1–Al1–N2
118.88(14)
N1a–Al2–N2a
87.11(16)
C2–Al1–N1
105.36(14)
Al1–N1–Al2
91.05(13)
C2–Al1–N2
105.14(15)
Al1–N2–Al2
90.90(13)
C3–Al2–N1
117.44(14)
Al1–N1a–Al2
91.14(17)
C3–Al2–N2
118.30(14)
Al1–N2a–Al2
91.31(16)
C4–Al2–N1
105.20(14)
C1–Al1–C2
119.04(14)
C4–Al2–N2
105.85(13)
Based on the observed chemistry of Me3Al with one equivalent of 3methylindole, the reactivity study was expanded to other aluminum alkyls. Derivatives
using Et3Al (7b) and iBu3Al (7c) were prepared in high yields in similar manner to 7a.
Complex 7b shows analogous physical and spectral properties to 7a. It is isolated as an
74
off-white powder and can be recrystallized from minimal amounts of hot toluene.
Integration of the 1H NMR spectrum of 7b in CDCl3 also shows a 60:40 ratio of anti to
syn isomers and has three triplet resonances for the methyl component of the ethyl groups
on aluminum at 0.67 ppm, 0.52 ppm, and 0.39 ppm and three quartet resonances for
methylene component at 0.19 ppm, 0.07 ppm, and 0.00 ppm. There is no evidence for
NH protons from unreacted 3-methylindole and there are two doublet resonances for
methyl groups on indolyl moieties at 2.38 ppm and 2.36 ppm. There are also two
resonances for H7 at 7.96 ppm and 7.82 ppm, consistent with two different indolyl
groups in the obtained product.
The ethyl resonances could be assigned based on
integration of the syn and anti H7 protons. Resonances at 0.52 ppm and 0.07 ppm
correspond to the ethyl groups on the anti isomer and those at 0.67 ppm, 0.39 ppm, 0.19
ppm, and 0.00 ppm represent the ethyl resonances for the syn isomer. Crystals of 7b
were grown from a highly concentrated toluene solution and checked for diffraction.
After many attempts to obtain a suitable unit cell from matrix runs it was deemed that the
crystals were not suitable for a complete data set collection.
Complex 7c is also analogous to 7a and 7b and is isolated as an off-white solid.
Integration of the 1H NMR spectrum of 7c also shows a 60:40 ratio of anti and syn
isomers in solution. Three sets of iso-butyl resonances on aluminum can clearly be seen
along with two sets of resonances for both the methyl and H7 protons on the indolyl
moiety. Similar to 7b, crystals of this complex can be grown from a highly concentrated
toluene solution, but they were not suitable for X-ray diffraction.
Attempts to synthesize similar complexes using tBu3Al were unsuccessful. The
1
H NMR spectra in CDCl3 of isolated materials from these attempts showed a mixture of
75
indolyl resonances and a plethora of alkyl resonances in the range between 0.80 ppm and
1.40 ppm, which is the area where tert-butyl resonances on aluminum are normally seen.
All attempts made to purify and isolate products from these mixtures were unsuccessful.
3.4.3 Variable Temperature NMR of 7a-b
A variable-temperature (VT) NMR study was performed to test for exchange of
the syn and anti isomers of 7a and 7b. VT plots (Figures 3.9 and 3.10) for 7a and 7b
show exchange between the syn and anti isomers of the complexes. For both 7a and 7b
there is broadening of the aluminum alkyl resonances as the interconversion of isomers
becomes more rapid at higher temperatures.
For 7a, coalescence of the methyl
resonances occurs at 45 °C, and the methyl resonances sharpen at higher temperatures.
For 7b coalescence of the ethyl resonances occurs at 50 °C and there is sharpening of the
ethyl resonances at higher temperatures. As coalescence of the alkyl resonances for 7a
and 7b occurs, there is also coalescence of the H7 indolyl protons. At this time neither a
mechanism for the interconversion of the two isomers nor models to calculate
thermodynamic parameters have been determined.
Schleyer and coworkers have reported 1H NMR studies for the N-sodio-N-N-N′N′-tetramethylethylenediamine complex shown in Figure 3.2. The 1H NMR data shows a
3:1 ratio of anti to syn isomers in solution at ─80 °C and coalescence of the two isomers
at ─59 °C. The 3:1 ratio observed for the anti/syn isomers is similar to the ratio observed
for 7a-7c. In the crystal structure for this complex, the anti isomer is observed. They
report that based on MNDO calculations there is no energetic preference for the anti over
the syn isomer, meaning that the effect that determines arrangement in the solid state is
not relevant to the solution phase.
76
Indolyl CH3
AlCH3
H2, H4, H5, H6, H7
Figure 3.9
Variable-temperature 1H NMR plot of 7a in CDCl3 from -10 to 60 °C
H2, H4, H5, H6, H7
Indolyl CH3
AlCH2CH3
Figure 3.10
Variable-temperature 1H NMR plot of 7b in CDCl3 from 20 to 60 °C
77
3.4.4
Reaction of Di(3-methylindolyl)phenylmethane and Me3Al
Based on the results obtained from reactions of one equivalent of 3-methylindole
with one equivalent of aluminum alkyl, the chemistry was expanded to include reactions
of the di- and tri(3-methylindolyl)methanes with aluminum alkyls. It appeared that the
bridging mode for the indolyl moiety would also be favored in the constrained system of
the ligand framework. To test this, di(3-methylindolyl)phenylmethane was reacted with
two equivalents of Me3Al to yield complex 8 (eq 6). A single crystal was obtained from
a highly concentrated toluene solution left undisturbed in the glove box for three weeks.
Complex 8 was not isolated as a pure product other than the single crystal grown from the
oil. Numerous attempts were made to isolate and purify larger quantities of 8 for
characterization, but these were unsuccessful. Isolated products showed multiple broad
aluminum methyl and di(3-methylindolyl)phenylmethane resonances.
This is
presumably due to excess Me3Al that is always found as an impurity in the purification of
8. A similar broadening is seen in the NMR spectra of 7a when excess Me3Al is present.
Thus, the structure of complex 8 in solution is unknown.
NH
+ 2 Me3Al
Me
- 2 CH4
toluene
N
Al Al
Me
NH
N
8
78
Me
Me
(6)
X-ray crystallography confirmed the solid-state structure of 8 (Figure 3.11) as a
bimetallic dimer with two aluminum centers, each bridged by a μ2-η1:η1-N indolyl
moiety. The molecule crystallized in space group P 1 and the structure was refined with
an R1 factor of 5.47%. Selected bond distances and angles are summarized in Table 3.3.
The structure consists of two molecules in the asymmetric unit and has a disordered
phenyl group in each molecule. Each phenyl group is refined with a ratio of 56% to 44%.
Each indolyl arm of the di(3-methylindolyl)phenylmethane ligand is bridging two
different pseudo-tetrahedral aluminum centers in a μ2-η1:η1-N fashion. The Al–Nindolyl
bond distances range from 1.9722(2) to 2.0339(2) Å, comparable to the distances
reported earlier in this chapter (section 3.4.2). It is of interest to note that the bridge ring
is asymmetric and that two of the Al–Nindolyl bonds are significantly shorter than the
others.
C4
Al2
N2
C5
N1
Al1
C3
C2
Figure 3.11
ORTEP diagram of 8. Thermal ellipsoids are drawn at the 30%
probability level. Hydrogen atoms are omitted for clarity.
79
Table 3.3
Selected bond distances and angles for C29H32Al2N2 (8)
Bond distances (Å)
Al1–N1
1.9785(2)
Al1–C2
1.954(2)
Al1–N2
2.0339(2)
Al1–C3
1.964(2)
Al2–N1
2.002(2)
Al2–C4
1.943(3)
Al2–N2
1.9722(2)
Al2–C5
1.963(3)
Bond angles (deg)
N1–Al1–N2
77.82(8)
C2–Al1–N2
116.29(10)
N1–Al2–N2
78.73(7)
C3–Al1–N1
115.52(9)
Al1–N1–Al2
91.49(8)
C3–Al1–N2
111.55(9)
Al1–N2–Al2
90.73(7)
C4–Al2–N1
113.14(13)
C2–Al1–C3
115.97(12)
C4–Al2–N2
121.06(12)
C4–Al2–C5
112.74(14)
C5–Al2–N1
115.20(11)
C2–Al1–N1
114.09(10)
C5–Al2–N2
111.96(11)
3.4.5
Reactions of Tri(3-methylindolyl)methane and R3Al (R = Me, Et, iBu)
With the apparent preference of indolyl bridges over alkyl bridges, this study was
expanded
to
include
the
tri(3-methylindolyl)methane
ligand.
Tri(3-
methylindolyl)methane was stirred with three equivalents of Me3Al in toluene at 40 °C
for 24 hours (eq 7). The off-white solid 9a was isolated in 88% yield and is air- and
moisture-sensitive. The 1H NMR spectra of 9a were obtained in both CDCl3 and C6D6
although only the latter will be discussed based on a better resolution of the aromatic
resonances in C6D6. The 1H NMR spectrum in C6D6 shows one methine resonance at
6.08 ppm, and one methyl resonance for the 3-methylindolyl moieties at 2.45 ppm
80
indicating that all three arms of the ligand are chemically equivalent. There are two sets
of resonances for the methyl groups on aluminum at 0.45 ppm and ─2.27 ppm, each
integrating to nine protons. This indicates a highly symmetrical structure in solution and
integration confirms that there are six Me–Al moieties per tri(3-methylindolyl)methane
ligand, thus establishing the stoichiometry of the product. NMR spectroscopic data
suggests the structure shown in eq 7 based on the ability of indolyls to bridge aluminum
centers observed throughout this chapter. The large difference in chemical shift of the
aluminum-bound methyls is due to different chemical environments, one set that is above
and one set below the six-membered Al3N3 ring formed by the bridging indolyls. There
is a considerable shift of almost 3 ppm upfield for one set of methyls on aluminum. This
is assigned to the methyls that sit below the six-membered ring situated between the
R
Al
NH
CH
R
N
+ 3 R3Al toluene
R
N
R
Al
N
(7)
R
Al
3
R
R
9a Me
9b Et
Yield
88%
79%
aromatic rings of two different indolyl moieties; the ring current effect of these aromatic
rings causes this large upfield shift. The shielding effect on the aluminum methyls is also
seen in the
13
C NMR spectrum where the shifts are ─6.65 ppm and ─19.90 ppm,
respectively. This is an almost 13 ppm shift upfield due to the ring current effect on the
81
bridging indolyl moieties. The aromatic region of the
13
C NMR spectrum shows only
one set of indolyl resonances which are comparable to those reported by Das for indolyl
moieties bridging dialkyl aluminum centers.81 There is only one methine resonance at
33.32 ppm and one resonance for methyls on the indolyls at 8.96 ppm. The 1H NMR
spectrum does not change at reduced or elevated temperatures suggesting that this
complex is static in solution, unlike complexes 7a-c.
Crystals of 9a were isolated from a highly concentrated toluene solution stored at
─30 °C for 24 hours. X-ray crystallography confirmed the proposed structure as shown
in Figure 3.12.
The molecular structure consists of three chemically equivalent
dimethylaluminum centers each bridged by two μ2-η1:η1-N-3-methylindolyl moieties.
These bridging units form a six-membered Al3N3 ring that has three alkyl groups above
and three below the plane of the ring. The molecule crystallized in space group P 1 ,and
the structure was refined with an R1 factor of 5.48% (see Table 3.1). Bond distances and
C5
Al2
N2
C6
C4
Al3
N1
C2
C7
N3
Al1
C3
Figure 3.12
ORTEP diagram of 9a. Thermal ellipsoids are drawn at the 30%
probability level. Hydrogen atoms are omitted for clarity.
82
angles within the indolyl moieties compare favorably with the reported literature values
for other diindolyl methane ligands.129
Selected bond distances and angles are
summarized in Table 3.4. Each indolyl arm of the tri(3-methylindolyl)methane ligand is
bridging two different pseudo-tetrahedral aluminum centers in a μ2-η1:η1-N fashion. The
Al–Nindolyl bond distances range from 1.9876(18) to 2.0044(18) Å, which are comparable
to the ranges reported earlier in this chapter.
Table 3.4
Selected bond distances and angles for 9a
Bond distances (Å)
Al1–N1
2.0044(18)
Al1–C2
1.954(2)
Al1–N3
1.9882(17)
Al1–C3
1.952(2)
Al2–N1
1.9876(18)
Al2–C4
1.953(2)
Al2–N2
1.9940(18)
Al2–C5
1.953(2)
Al3–N2
1.9930(18)
Al3–C6
1.954(2)
Al3–N3
1.9938(18)
Al3–C7
1.948(2)
Bond angles (deg)
N1–Al1–N3
93.80(7)
C2–Al1–C3
119.78(10)
N1–Al2–N2
93.70(7)
C4–Al2–C5
119.02(11)
N2–Al3–N3
94.60(7)
C6–Al3–C7
117.41(11)
Al1–N1–Al2
122.19(9)
Al2–N2–Al3
120.82(8)
Al3–N3–Al1
119.78(8)
83
It was postulated that 9a could serve as a precursor to the tridentate
monoaluminum complex illustrated in eq 8.
Roesky153 reported that at elevated
temperatures, Me3Al elimination from C6F5AlMe2 was a synthetic route to the formation
of (C6F5)3Al. Attempts to generate the tridentate monoaluminum complex were not
successful. Complex 9a is stable under vacuum to at least 175 °C and in refluxing
xylenes for at least 72 hours without any change to its 1H NMR spectrum.
Me
Me Al
Al
N
N
Me Al
Me
Me
Al
N
Me
N
N
N
(8)
- 2 Me3Al
Reaction of three equivalents of triethylaluminum and one equivalent of tri(3methylindolyl)methane gave 9b as a yellow solid in 77% yield. The 1H NMR spectrum
shows analogous patterns to that for 9a with three equivalent indolyl moieties and two
distinct alkyl groups on aluminum. There is a doublet at 7.97 ppm for H7, doublet at
7.22 ppm for H4, and a singlet methine resonance at 6.00 ppm. Two sets of ethyl
resonances on aluminum are observed, with triplet methyl resonances at 1.44 ppm and
─0.13 ppm, and quartet methylene resonances at 1.31 ppm and ─1.57 ppm in C6D6.
There is only one set of 13C resonances in C6D6 for indolyl moieties and two distinct sets
of ethyl resonances on aluminum at 9.06 ppm and 7.69 ppm for methyls and 2.9 ppm and
─8.5 ppm for methylene protons. As with compound 9a, there is a large upfield shift for
the alpha carbon and proton for the alkyl groups that are below the six-membered Al3N3
84
ring due to the ring current of the bridging indolyl moieties that they are situated
between.
Crystals of 9b were grown from a highly concentrated hexanes solution that was
stored at ─30 °C for 48 hours. A complete dataset was collected on a single crystal but
the data quality was poor as indicated by an internal R value of 12.5% after integration.
A preliminary solution as seen in Figure 3.13 confirmed the three-dimensional
connectivity of the atoms and confirmed the proposed bridging structure as being
analogous to 9a. Considering the poor refinement from integration, bond distances and
angles will not be discussed in this dissertation.
Al1
Al3
N3
N1
N2
Al2
Figure 3.13
ORTEP diagram of 9b. Thermal ellipsoids are drawn at the 30%
probability level. Hydrogen atoms are omitted for clarity.
Tri(3-methylindolyl)methane was reacted with three equivalents of iBu3Al in an
effort to generate a complex similar to 9a and 9b (eq 9). A yellow solid 9c was obtained
in 79% yield after recrystallization from hexanes.
85
i
i
Bu
Bu Al
N
NH
CH
N
i
+ 3 Bu3Al
Bu
Al
toluene
N
H Al
i
Bu
3
i
i
(9)
Bu
9c
From the 1H NMR spectrum shown in Figure 3.14, it was obvious that 9c was not
analogous to 9a or 9b. There are five distinct sets of resonances for isobutyl groups on
aluminum with the methyls being at 1.42 ppm, 1.31 ppm, 0.40 ppm, 0.19 ppm, and 0.14
ppm in C6D6, each integrating to six protons.
There are four sets of methylene
resonances at 1.72 ppm, 1.52 ppm, ─1.55 ppm and ─1.93 ppm. The sets at 1.72 and 1.52
ppm integrates to four protons representing two isobutyl groups and is seen as
diastereotopic methylenes with an ABX splitting pattern. The two doublet resonances
that are upfield at ─1.55 and ─1.93 integrate to four protons and two protons,
respectively, therefore representing two and one iso-butyl groups. They do not display the
ABX splitting pattern that is observed for the other set. Based on the structures of 9a and
9b it was proposed that 9c could have a similar structure but with five isobutyl groups as
opposed to six. This would also explain the two distinct sets of resonances for the indolyl
moieties. There are two doublets at 8.16 ppm and 8.08 ppm for H7, and two doublets at
7.30 ppm and 7.27 ppm for H4. The resonances at 8.16 ppm and 7.30 ppm each integrate
to one proton while the resonances at 8.08 ppm and 7.27 ppm integrate to two. There are
also two different resonances for the methyls on indole at 2.21 ppm and 2.16 ppm that
integrate to three protons and six protons, respectively. Only one methine resonance is
86
seen at 6.06 ppm. This data shows that in addition to the five isobutyl groups on
aluminum, there is only one tri(3-methylindolyl)methane ligand that has inequivalent
indolyl moieties. To account for this, it is proposed formation of 9c may result from βhydride elimination
Indolyl CH3
CH3 CH3
CH3
CH2
CH
Figure 3.14.
CH2
CH2
CH
1
H NMR spectrum of aliphatic region of 9c in benzene-d6 from
─2.0 ppm to 2.6 ppm.
from one of the isobutyl groups to form an Al–H species on one of the bridged aluminum
centers.
The broad singlet at 5.42 ppm is tentatively assigned to the hydride on
aluminum. An IR spectrum of 9c in KBr shows a broad intense peak at 1866 cm-1 which
is in the range reported for Al–H stretches.154 Trace amounts of diisobutylaluminum
hydride (DIBAL) are always present in triisobutylaluminum and it was proposed that it
could be the source of the hydride species. The presence of 5-10% DIBAL impurity
cannot, however, account for the 79% yield of 9c. The amount of the hydride species
that was isolated is much more than could be strictly coming from the DIBAL impurity.
87
Synthesis of 9c was attempted using two equivalents of iBu3Al and one equivalent of
i
Bu2AlH, and using three equivalents of iBu2AlH. These attempts did not yield complex
9c, only unidentified mixtures of indolyl and alkyl aluminum resonances.
Crystals of 9c were grown from a concentrated hexanes solution stored at ─30 °C
for 6 hours. A complete data set was collected on a single crystal, but the data were of
low quality as indicated by an internal R value of 11.6% after integration. Preliminary
solution as seen in Figure 3.15 showed the three-dimensional connectivity of the atoms
and confirmed the proposed bridging structure as being similar to 9a and 9b. Electron
density is seen on Al1 and the SHELXTL software package calculates hydrogen to be in
the void space. Bond distances and angles will not be discussed due to poor refinement
after integration.
Al3
N3
Al1
Al1
N2
N1
Figure 3.15
ORTEP diagram of 9c. Thermal ellipsoids are drawn at the 30%
probability level. Hydrogen atoms are omitted for clarity.
The ORTEP diagram of 9c helps explain the peaks that were observed in the 1H
NMR spectrum. The hydride on the aluminum pointing above the plane of the sixmembered Al3N3 ring results in two equivalent isobutyl groups above the plane and
88
inequivalent isobutyl groups in a 2:1 ratio below the plane. The hydride and inequivalent
isobutyl groups result in inequivalent bridging indolyl moieties that are also in a 2:1 ratio.
This shows that the indolyl moieties not only prefer the bridging of two aluminum centers
over the typical η1 binding mode supported with alkyl bridges, but to relieve steric
congestion β-hydride elimination is observed in order to adopt this geometry.
13
C and 1H NMR chemical shifts for alpha nuclei of aluminum alkyl
substituent in benzene-d6
Table 3.5
Complex
13
C Shift for α-C Above Al3N3 Plane
9a
─ 6.65 ppm
9b
2.9 ppm
9c
≈ 24 ppm
1
13
C Shift for α-C Below Al3N3Plane
─ 19.34 ppm
─ 8.8 ppm
≈ 11 ppm
H Shift for α-H Above Plane
1
H Shift for α-H Below Plane
9a
0.45 ppm
─ 2.74 ppm
9b
0.96 ppm
─ 1.94 ppm
9c
1.62 ppm
─ 1.55 ppm, ─ 1.93 ppm
Complexes 9a-c all show interesting shifts in their 1H and
13
C NMR spectra in
C6D6 for the alpha carbon and alpha protons for the alkyl groups on aluminum. The alkyl
groups that are oriented below the six-membered Al3N3 ring are situated between the
aromatic systems of two bridging indolyl moieties. This orientation causes ring current
effects to cause a large shift upfield for the nuclei that are shielded by this ring current.
Table 3.5 summarizes those large shifts for the alpha carbon and alpha protons in
complexes 9a-c. There is an average shift of ≈13 ppm upfield for the alpha carbon and
89
an average shift of ≈3 ppm upfield for the alpha proton. As the length of the alkyl chain
increases there isn’t as much influence beyond the β atoms.
3.5
Conclusions
The first group 13 examples of μ2-η1:η1-N-indolyl moieties 7a-c, 8, 9a-c were
synthesized. All complexes were characterized by elemental analysis and 1H and
13
C
NMR spectroscopy. Complexes 7a, 8, and 9a were characterized by X-ray
crystallography.
These complexes show that indolyl moieties are stronger bridging
ligands than originally proposed. They have stronger bridging ability than Me, Et, and
i
Bu groups, but less than amido ligands.
90
Chapter Four
Group 13 Complexes of Di- and Tri(3-methylindolyl)methanes and
Tris(pyrrolyl-α-methyl)amine
4.1
Introduction
Carbon monoxide is one of the most important carbon feedstocks used in industry
today, and its chemistry with transition metals has been extensively studied. It is of
interest to the Mason group to design and develop group 13 metal complexes that could
potentially bind and activate CO for reactivity. A few CO complexes of main group
metals have been observed, but those required matrix isolation techniques at very low
temperatures (15-40 K).
Adducts have been observed for beryllium,155 boron,156,157
aluminum, gallium and indium.158 Stable CO borane complexes such as H3BCO,159
(BX2)3BCO (X= F, Cl),156 (CF3)3BCO,160 B4X6CO (X = F, Cl, Br, I)161 and B4(CO)2162
have also been reported, but several of these have been prepared by indirect routes rather
than by direct reaction with CO.
There are no room-temperature stable carbonyl complexes of aluminum or
gallium.
This is due to weak binding of CO to metals in the absence of π-backbonding,
likely making coordinated complexes unstable. To help stabilize CO complexes in the
absence of π-backbonding, a highly electrophilic metal center is ideal.
Methods to
achieve such non-classical carbonyl complexes of transition metals have been developed
by Strauss, but not applied to main group metals.104 The binding of CO to a metal is
entropically unfavorable, so low temperatures and greater binding enthalpy help to favor
91
complexation. Generation of strong Lewis acidic complexes should help the binding of
CO to group 13 metals. Tricoordinate aluminum complexes are of interest because they
can potentially be used as highly Lewis acidic metal centers.
Pyrrolyl-,114-121 indolyl-,122-125,128 and carbazolyl127 ligands are of increasing
interest because they induce different electronic and steric properties to main group and
transition metal complexes when compared with common amido ligands. Some of these
differences include strong electron-withdrawing ability when bound in an η1-N mode and
minimal N→M π-donation.
These characteristics should help in generating highly
electrophilic metal centers that might help bind CO. The Mason group has focused on
the use of di- and tri(3-methylindolyl)methane moieties as ligands for main group metals.
These ligands act as reduced π-donating analogues of poly(pyrazolyl)borates and tripodal
triamides.
NH
4
N
1) 4 nBuLi
2) AlCl3
N
Al
N
N
92
Li
(1)
-
NH
2
Ph
NH
1) 4 nBuLi
N
Ph
Al
Ph
2) AlCl3
N
(2)
N
Li+
N
A few aluminum complexes using these ligand systems have been synthesized in
the Mason group.79
Segla reported that AlCl3 reacts with four equivalents of
deprotonated 3-methylindole (eq 1) or two equivalents of deprotonated di(3methylindolyl)phenyl methane (eq 2) to generate four-coordinate anionic aluminum
complexes.
Reaction of tri(3-methylindolyl)methane with LiAlH4 and reaction of
deprotonated tri(3-methylindolyl)methane with AlCl3 resulted in the formation of fourcoordinate complexes 1 and 2, respectively.
These were previously characterized
spectroscopically, but not by X-ray crystallography.
X
[Li(OEt2)4]
Al
N
N
N
1X=H
2 X = Cl
93
Neutral four-coordinate aluminum complexes were isolated by Fneich80 when
di(3-methylindolyl)pyridylmethane was stirred with trialkyl aluminum compounds (eq 3).
The complexes are structurally similar to 1 and 2, but the inclusion of a neutral donor arm
in the ligand framework results in a neutral complex.
R
H
NH
+
N
AlR3
toluene
15 h, 20 oC
N Al N
N
NH
(3)
H
R= Me, Et, iBu, tBu
The isolation of the foor-coordinate aluminum complexes are of particular interest
based on advantages proposed by Mason and Chen72,74 because they would be ideal for
promotion of base coordination. The complexes are already preorganized with trigonal
monopyramidal geometry and alkide, chloride or hydride abstraction should provide
strong Lewis acidic compounds.
In this chapter, the synthesis and spectroscopic characterization of four- and fivecoordinate complexes of aluminum and gallium will be discussed. This includes the
synthesis of four-coordinate anionic aluminum and gallium complexes of tri(3methylindolyl)methane (3a, 3b, 4a-4c), four-coordinate neutral aluminum complexes of
tri(3-methylindolyl)imidazolylmethane (5a-5d), and five-coordinate aluminum and
gallium complexes of tris(pyrrolyl-α-methyl)amine (6a, 6b).
X-ray crystallography
confirmed the structures of 3b, 6b, and 7a. Initial attempts to generate three-coordinate
complexes were unsuccessful.
94
X
[Li(THF)4]
R
N Al
N
M
N
N
N
N
N
H
3a
3b
4a
4b
4c
4.2
M X
Al Cl
Ga Cl
Al H
Al D
Al tBu
HNMe2
N
N
N
M
R
Me
Et
i
Bu
t
Bu
5a
5b
5c
5d
N
M
Al
Ga
6a
6b
Experimental
General Procedures
All air- and moisture-sensitive reactions were performed in an inert atmosphere of
purified nitrogen using standard inert atmosphere techniques and an Innovative
Technologies dry box. 3-Methylindole, AlCl3, LiAlH4, nBuLi, and tBuLi were purchased
from Aldrich Chemicals and used as received.
Tri(3-methylindolyl)methane,129,148
tris(pyrrolyl-α-methyl)amine (TPA),163 [Ga(NMe2)3]2,164 and [Al(NMe2)3]2165 were
prepared using published procedures. Di(3-methylindolyl)imidazolylmethane was made
using the procedure of Das.81 Toluene was distilled from sodium. Hexanes was distilled
from calcium hydride. THF and ether were distilled from sodium benzophenone ketyl
prior to use. Benzene-d6 (C6D6) and chloroform-d (CDCl3) were dried by storage over
activated molecular sieves and degassed with purified nitrogen. Solution NMR spectra
were recorded on a Varian VXRS-400 or a Varian AS-600 spectrometer using deuterated
solvent as an internal lock. Chemical shifts are reported relative to TMS.
95
13
C NMR
chemical shift assignments for C4, C5, C6, and C7 of the indolyl rings were aided by 2DCOSY, 2D-HMQC and 2D-HMBC experiments. Elemental analyses were performed by
Schwarzkopf Microanalytical Laboratory, Inc.
Synthesis of [{tri(3-methylindolyl)methane}AlCl][Li(THF)4] (3a)
The preparation of 3a is a modification of the preparation used by Segla.
Addition of nBuLi (5.8 mL, 1.6 M in hexane, 9.2 mmol) to a solution of tri(3methylindolyl)methane (1.25 g, 3.10 mmol) in 100 mL of THF resulted in a bright yellow
solution that was added via dropping funnel to a THF (40 mL) solution of AlCl3 (0.416 g,
3.10 mmol). The resulting suspension was stirred overnight. Solvents were removed in
vacuo and the residue was redissolved in 40 mL of CH2Cl2 and filtered over Celite on a
fine frit. Solvents were removed from the filtrate in vacuo to yield a purple solid. Yield:
1.24 g, 1.64 mmol, 53%.
1
H NMR (CDCl3, 600 MHz): δ 7.59 (d, 3JHH = 7.8 Hz, 3H,
H7), 7.33 (d, 3JHH = 7.8 Hz, 3H, H4), 7.01 (t, 3JHH = 7.8 Hz, 3H, H6), 6.92 (t, 3JHH = 7.8
Hz, 3H, H5), 6.05 (s, 1H, CH), 3.16 (br s, 16H, THF), 2.40 (s, 9H, CH3), 1.25 (br s, 16H,
THF).
13
C{1H} NMR (CDCl3, 150.8 MHz): δ 143.08 (s, C7a), 141.23 (s, C2), 130.70 (s,
C3a), 119.78 (s, C6), 117.99 (s, C5), 117.53 (s, C4), 113.51 (s, C7), 105.79 (s, C3), 68.1
(s, THF), 33.05 (s, CH), 25.72 (s, THF), 8.70 (s, CH3).
Synthesis of [{tri(3-methylindolyl)methane}GaCl][Li(THF)4] (3b)
Addition of nBuLi (5.8 mL, 1.6 M in hexane, 9.2 mmol) to a solution of tri(3methylindolyl)methane (1.25 g, 3.10 mmol) in 100 mL of THF resulted in a bright yellow
solution that was added via dropping funnel to a THF (40 mL) solution of GaCl 3 (0.546
g, 3.10 mmol). The resulting suspension was stirred overnight. Solvents were removed
96
in vacuo and the residue was redissolved in 40 mL of CH2Cl2 and filtered over Celite on
a fine frit. Solvents were removed from the filtrate in vacuo to yield a purple solid.
Yield: 1.19 g, 1.49 mmol, 48%. 1H NMR (CDCl3, 600 MHz): δ 7.50 (d, 3JHH = 7.8 Hz,
3H, H7), 7.30 (d, 3JHH = 7.8 Hz, 3H, H4), 6.90 (t, 3JHH = 7.8 Hz, 3H, H6), 6.81 (t, 3JHH =
7.8 Hz, 3H, H5), 6.07 (s, 1H, CH), 3.16 (br s, 16H, THF), 2.43 (s, 9H, CH3), 1.26 (br s,
16H, THF).
13
C{1H} NMR (CDCl3, 150.8 MHz): δ 143.08 (s, C7a), 141.23 (s, C2),
130.7 (s, C3a), 119.78 (s, C6), 117.99 (s, C5), 117.53 (s, C4), 113.51 (s, C7), 105.79 (s,
C3), 68.39 (s, THF), 33.05 (s, CH), 25.25 (s, THF), 8.70 (s, CH3).
Synthesis of [{tri(3-methylindolyl)methane}AlH][Li(THF)4] (4a)
The preparation of 4a is a modification of the preparation used by Segla. A THF
solution (50 mL) of tri(3-methylindolyl)methane (0.704 g, 1.7 mmol) was added
dropwise to a toluene (100 mL) suspension of LiAlH4 (0.095 g, 2.5 mmol). Upon
addition, a gas was released, and the green solution was stirred for 12 h. The solution
was concentrated to 30 mL, and the resulting grey solid was filtered over a medium frit
and dried in vacuo. Yield: 1.09 g, 1.50 mmol, 88%. 1H NMR (CDCl3, 600 MHz): δ 7.43
(d, 3JHH = 7.8 Hz, 3H, H7), 7.32 (d, 3JHH = 7.8 Hz, 3H, H4), 6.92 (t, 3JHH = 7.8 Hz, 3H,
H6), 6.84 (t, 3JHH = 8.4 Hz, 3H, H5), 6.01 (s, 1H, CH), 3.31 (br s, 16H, THF), 2.42 (s,
9H, CH3), 1.69 (br s, 16H, THF).
13
C{1H} NMR (CDCl3, 150.8 MHz): δ 143.53 (s, C7a),
142.08 (s, C2), 131.55 (s, C3a), 119.80 (s, C6), 118.18 (s, C5), 117.73 (s, C4), 113.3 (s,
C7), 105.66 (s, C3), 68.31 (s, THF), 33.50 (s, CH), 25.55 (s, THF), 9.15 (s, CH3). IR (υAl–
H,
KBr): 1864 cm–1.
97
Synthesis of [{tri(3-methylindolyl)methane}AlD][Li(THF)4] (4b)
A THF solution (50 mL) of tri(3-methylindolyl)methane (0.704 g, 1.7 mmol) was
added dropwise to a toluene (100 mL) suspension of LiAlD4 (0.105 g, 2.5 mmol). Upon
addition, a gas was released, and the green solution was stirred for 12 h. The solution
was concentrated to 30 mL, and the resulting grey solid was filtered over a medium frit
and dried in vacuo. Yield: 1.12 g, 1.53 mmol, 90%. 1H NMR (CDCl3, 600 MHz): δ 7.43
(d, 3JHH = 7.8 Hz, 3H, H7), 7.32 (d, 3JHH = 7.8 Hz, 3H, H4), 6.93 (t, 3JHH = 7.8 Hz, 3H,
H6), 6.86 (t, 3JHH = 8.4 Hz, 3H, H5), 6.03 (s, 1H, CH), 3.30 (br s, 16H, THF), 2.43 (s,
9H, CH3), 1.66 (br s, 16H, THF).
13
C{1H} NMR (CDCl3, 150.8 MHz): δ 143.85 (s, C7a),
142.07 (s, C2), 131.47 (s, C3a), 119.44 (s, C6), 118.02 (s, C5), 117.34 (s, C4), 113.22 (s,
C7), 105.66 (s, C3), 68.38 (s, THF), 33.51 (s, CH), 25.47 (s, THF), 9.13 (s, CH3).
Synthesis of [{tri(3-methylindolyl)methane}AltBu][Li(THF)4] (4c)
To a 100 mL sidearm flask was added 3a (1.29 g, 1.7 mmol) and 30 mL of THF.
To this solution was added tBuLi (1.0 mL, 1.7 M in hexane, 1.7 mmol) via syringe. The
resulting yellow solution was stirred for 12 h. The slurry was filtered over a fine frit with
a Celite plug, and the solvent was removed from the filtrate in vacuo. Yield: 1.28 g,
1.66 mmol, 97% 1H NMR (CDCl3, 600 MHz): δ 7.49 (d, 3JHH = 7.8 Hz, 3H, H7), 7.40
(d, 3JHH = 7.8 Hz, 3H, H4), 7.00 (t, 3JHH = 7.8 Hz, 3H, H6), 6.88 (t, 3JHH = 8.4 Hz, 3H,
H5), 6.10 (s, 1H, CH), 3.34 (br s, 16H, THF), 2.48 (s, 9H, CH3), 1.70 (br s, 16H, THF)
1.55 (s, 9H, AltBu).
13
C{1H} NMR (CDCl3, 150.8 MHz): δ 142.88 (s, C7a), 139.23 (s,
C2), 131.33 (s, C3a), 119.22 (s, C6), 118.52 (s, C5), 117.11 (s, C4), 112.22 (s, C7),
105.45 (s, C3), 69.10 (s, THF), 32.9 (s, methine), 29.88 (s, AlC(CH3)), 24.87 (s, THF),
9.34 (s, CH3).
98
Synthesis of (1-CH3-2-C3H2N2)HC(3-CH3C8H4N)2AlCH3 (5a)
To
a
100
mL
sidearm
flask
was
added
di(3-methylindolyl)-N-
methylimidazolylmethane (0.600 g, 1.7 mmol) and 50 mL of toluene. To this suspension
n
BuLi (2.1 mL, 1.6 M in hexane, 3.4 mmol) was then added via syringe at 25 °C. An
orange slurry formed immediately and the mixture stirred for 1 h. A solution of MeAlCl2
(1.0 mL, 1.0 M in toluene, 1.7 mmol) was added via syringe. The solution slowly turned
light purple over 1 h as a white precipitate formed. The mixture was filtered over Celite
on a medium frit, then filtered over Celite on a fine frit. The resulting green solution was
concentrated to 15 mL and stored at ─30 °C for 48 h to yield a light green solid which
was isolated by filtration.
Recrystallization of 5a can be achieved using highly
concentrated toluene solutions stored at ─30 °C for 72 h. Yield: 0.563 g, 1.43 mmol,
84%.
3
1
H NMR (CDCl3, 600 MHz): δ 7.40 (d, 3JHH = 7.8 Hz, 2H, indolyl H4), 7.39 (d,
JHH = 7.8 Hz, 2H, indolyl H7), 7.06 (t, 3JHH = 7.8 Hz, 2H, indolyl H6), 6.96 (t, 3JHH = 7.8
Hz, 2H, indolyl H5), 6.89 (d, 3JHH = 1.8 Hz, 1H, imidazolyl H5), 6.47 (d, 3JHH = 1.8 Hz,
1H, imidazolyl H4), 5.90 (s, 1H, CH), 3.70 (s, 3H, imidazolyl CH3), 2.41 (s, 6H, indolyl
CH3), 0.31 (s, 3H, AlCH3). 13C{1H} NMR (CDCl3, 150.8 MHz): δ 153.11 (s, imidazolyl
C2), 142.10 (s, C7a), 137.10 (s, C2), 130.19 (s, C3a), 122.97 (s, imidazolyl C5), 120.89
(s, indolyl C5), 119.86 (s, imidazolyl C4), 118.42 (s, C4), 117.96 (s, C6), 113.13 (s, C7),
106.51 (s, C3), 33.35 (s, imidazolyl-CH3), 32.27 (s, CH), 8.85 (s, indolyl-CH3). Anal
Calcd for C24H23N4Al•0.85C7H8: C, 76.09; H, 6.35; N, 11.85. Found: C, 73.06; H, 6.28;
N, 11.44.
99
Synthesis of (1-CH3-2-C3H2N2)HC(3-CH3C8H4N)2AlCH2CH3 (5b)
To
a
100
mL
sidearm
flask
was
added
di(3-methylindolyl)-N-
methylimidazolylmethane (0.600 g, 1.7 mmol) and 50 mL of toluene. To this suspension
n
BuLi (2.1 mL, 1.6 M in hexane, 3.4 mmol) was added via syringe at 25 °C. An orange
slurry formed immediately, and the mixture was stirred for 1 h. A solution of EtAlCl2
(1.0 mL, 1.0 M in toluene, 1.7 mmol) was then added via syringe. The solution slowly
turned blue over 1 h as a white precipitate formed. The mixture was filtered over Celite
on a medium frit, then filtered over Celite on a fine frit. The resulting green solution was
concentrated to 15 mL and stored at ─30 °C for 48 h to yield a light green solid that was
isolated by filtration. Recrystallization of 5b can be achieved from highly concentrated
toluene solutions stored at ─30 °C for 72 h. Yield: 0.454 g, 1.11 mmol, 64%. 1H NMR
(CDCl3, 600 MHz): δ 7.39 (d, 3JHH = 7.8 Hz, 2H, indolyl H4), 7.37 (d, 3JHH = 7.8 Hz, 2H,
indolyl H7), 7.06 (td, 3JHH = 7.8 Hz, 4JHH = 1.2 Hz, 2H, indolyl H6), 6.96 (td, 3JHH = 7.8
Hz, 4JHH = 1.2 Hz, 2H, indolyl H5), 6.77 (d, 3JHH = 1.2 Hz, 1H, imidazolyl H5), 6.24 (d,
3
JHH = 1.2 Hz, 1H, imidazolyl H4), 5.83 (s, 1H, CH), 3.49 (s, 3H, imidazolyl CH3), 2.38
(s, 6H, indolyl CH3), 1.59 (t, 3JHH = 8.4 Hz, 3H, AlCH2CH3), 1.02 (q, 3JHH = 8.4 Hz, 2H,
AlCH2CH3). 13C{1H} NMR (CDCl3, 150.8 MHz): δ 153.01 (s, imidazolyl C2), 142.05 (s,
C7a), 137.20 (s, C2), 130.21 (s, C3a), 123.30 (s, imidazolyl C5), 120.95 (s, indolyl C5),
119.91 (s, imidazolyl C4), 118.42 (s, C4), 117.98 (s, C6), 113.22 (s, C7), 106.59 (s, C3),
33.08 (s, imidazolyl-CH3), 32.19 (s, CH), 8.83 (s, indolyl-CH3), 8.44 (s, AlCH2CH3),
─4.41 (s, AlCH2CH3).
100
Synthesis of (1-CH3-2-C3H2N2)HC(3-CH3C8H4N)2AlCH2CH(CH3)2 (5c)
To
a
100
mL
sidearm
flask
was
added
di(3-methylindolyl)-N-
methylimidazolylmethane (0.600 g, 1.7 mmol) and 50 mL of toluene. To this suspension
n
BuLi (2.1 mL, 1.6 M in hexane, 3.4 mmol) was added via syringe at 25 °C. An orange
slurry formed immediately and the mixture stirred for 1 h. A solution of iBuAlCl2 (1.0
mL, 1.0 M in toluene, 1.7 mmol) was then added via syringe. The solution slowly turned
green over 1 h as a white precipitate formed. The mixture was filtered over Celite on a
medium frit, then filtered over Celite on a fine frit. The resulting green solution was
concentrated to 15 mL and stored at ─30 °C for 48 h to yield a light green solid isolated
by filtration. Recrystallization of 5c can be achieved using highly concentrated toluene
solutions stored at ─30 °C for 72 h. Yield: 0.567g, 1.34 mmol, 79%. 1H NMR (CDCl3,
600 MHz): δ 7.49 (d, 3JHH = 7.8 Hz, 2H, indolyl H7), 7.47 (d, 3JHH = 7.8 Hz, 2H, indolyl
H4), 7.14 (t, 3JHH = 7.8 Hz, 2H, indolyl H6), 7.04 (t, 3JHH = 7.8 Hz, 2H, indolyl H5), 6.87
(d, 3JHH = 1.2 Hz, 1H, imidazolyl H5), 6.23 (d, 3JHH = 1.2 Hz, 1H, imidazolyl H4), 5.89
(s, 1H, CH), 3.50 (s, 3H, imidazolyl CH3), 2.57 (m, 1H, AlCH2CH(CH3)2), 2.45 (s, 6H,
indolyl CH3), 1.36 (d, 3JHH = 7.8 Hz, 6H, AlCH2CH(CH3)2), 1.23 (d, 3JHH = 7.8 Hz, 2H,
AlCH2CH(CH3)2).
13
C{1H} NMR (CDCl3, 150.8 MHz): δ 153.25 (s, imidazolyl C2),
142.39 (s, C7a), 137.52 (s, C2), 130.55 (s, C3a), 123.50 (s, imidazolyl C5), 121.21 (s,
indolyl C5), 120.19 (s, imidazolyl C4), 118.71 (s, C4), 118.31 (s, C6), 113.67 (s, C7),
106.80 (s, C3), 33.30 (s, imidazolyl-CH3), 32.41 (s, CH), 28.82 (s, AlCH2CH(CH3)2),
21.77 (s, AlCH2CH(CH3)2), 17.95 (br s, AlCH2CH(CH3)2), 9.13 (s, indolyl-CH3). Anal
Calcd for C27H29N4Al•C7H8: C, 77.24; H, 7.05; N, 10.59. Found: C, 75.34; H, 7.40; N,
10.96.
101
Synthesis of (1-CH3-2-C3H2N2)HC(3-CH3C8H4N)2AlC(CH3)3 (5d)
To
a
100
mL
sidearm
flask
was
added
di(3-methylindolyl)-N-
methylimidazolylmethane (0.600 g, 1.7 mmol) and 50 mL of toluene. To this suspension
n
BuLi (2.1 mL, 1.6 M in hexane, 3.4 mmol) was added via syringe at 25 °C. An orange
slurry formed immediately, and the mixture stirred for 1 h. tBuAlCl2 (0.263 g, 1.7 mmol)
was dissolved in 5 mL of toluene and transferred to this slurry. The mixture slowly
turned pink over 1 h as a white precipitate formed. The mixture was filtered over Celite
on a medium frit, then filtered over Celite on a fine frit. The resulting green solution was
concentrated to 15 mL and stored at ─30 °C for 48 h to yield a light green solid that was
isolated by filtration. Recrystallization of 5d can be achieved using highly concentrated
toluene solutions stored at ─30 °C for 72 h. Yield: 0.549 g, 1.26 mmol, 74%. 1H NMR
(CDCl3, 600 MHz): δ 7.48 (d, 3JHH = 7.8 Hz, 2H, indolyl H7), 7.41 (d, 3JHH = 7.8 Hz, 2H,
indolyl H4), 7.09 (t, 3JHH = 7.8 Hz, 2H, indolyl H6), 7.01 (d, 3JHH = 1.2 Hz, 1H,
imidazolyl H5), 6.99 (t, 3JHH = 7.2 Hz, 2H, indolyl H5), 6.59 (d, 3JHH = 1.2 Hz, 1H,
imidazolyl H4), 5.95 (s, 1H, CH), 3.78 (s, 3H, imidazolyl CH3), 2.43 (s, 6H, indolyl
CH3), 1.60 (s, 9H, AlC(CH3)3).
13
C{1H} NMR (CDCl3, 150.8 MHz): δ 153.32 (s,
imidazolyl C2), 142.00 (s, C7a), 137.24 (s, C2), 130.29 (s, C3a), 123.25 (s, imidazolyl
C5), 121.10 (s, indolyl C5), 119.99 (s, imidazolyl C4), 118.45 (s, C4), 118.06 (s, C6),
113.62 (s, C7), 106.87 (s, C3), 33.44 (br s, AlC(CH3)3), 33.43 (s, imidazolyl-CH3), 32.12
(s, CH), 29.21 (s, AlC(CH3)3), 8.88 (s, indolyl-CH3).
102
Synthesis of (tris(pyrrolyl-α-methyl)amine)Al(HNMe2)] (6a)
To a 100 mL sidearm flask was added tris(pyrrolyl-α-methyl)amine (0.2513 g,
1.00 mmol) and 50 mL of toluene. A 10 mL toluene solution of [Al(NMe2)3]2 (0.158 g,
0.500 mmol) was added via cannula and the resulting red suspension was stirred for 16 h
after which all materials were solubilized. The solution was concentrated to 15 mL and
stored at ─30 °C for 24 h, and a light red solid was isolated by filtration. Yield: 0.300 g,
0.94 mmol, 94%.
1
H NMR (CDCl3, 600 MHz): δ 6.69 (s, 3H, H5), 6.22 (s, 3H, H4),
6.04 (s, 3H, H3), 3.96 (s, 6H, CH2), 3.19 (d, 3JHH = 5.4 Hz, 6H, NCH3,). 13C{1H} NMR
(CDCl3, 150.8 MHz): δ 136.3 (s, C2), 122.7 (s, C5), 111.2 (s, C4), 105.2 (s, C3), 52.8 (s,
CH2), 40.1 (s, NCH3).
Synthesis of (tris(pyrrolyl-α-methyl)amine)Ga(HNMe2)] (6b)
To a 100 mL sidearm flask was added tris(pyrrolyl-α-methyl)amine (0.2513 g,
1.00 mmol) and 50 mL of toluene. A 10 mL toluene solution of [Ga(NMe 2)3]2 (0.201 g,
0.500 mmol) was added via cannula and the resulting red suspension was stirred for 16 h
after which all materials were solubilized. The solution was concentrated to 15 mL and
stored at ─30 °C for 24 h and a light red solid was isolated by filtration. Yield: 0.318 g,
0.88 mmol, 88%.
1
H NMR (CDCl3, 600 MHz): δ 6.68 (s, 3H, H5), 6.23 (s, 3H, H4),
6.05 (s, 3H, H3), 3.91 (s, 6H, CH2), 3.18 (d, 3JHH = 6.0 Hz, 6H, NCH3,).
13
C{1H} NMR
(CDCl3, 150.8 MHz): δ 135.1 (s, C2), 122.5 (s, C5), 110.9 (s, C4), 105.3 (s, C3), 51.9 (s,
CH2), 40.6 (s, NCH3).
4.3 X-ray Crystallography
Crystals of 3b were grown from a highly concentrated chlorobenzene solution
stored at ─30 °C. Crystals of 5c were grown from a highly concentrated toluene solution
103
stored at ─30 °C for 72 h. Crystals of 6a were grown from a dilute toluene solution
stored at ─30 °C for 89 h. The X-ray diffraction data were collected on a Siemens threecircle platform diffractometer equipped with a 4K CCD detector. The frame data were
acquired with the SMART 5.62599 software using Mo Kα radiation (λ = 0.71073 Å). Cell
constants were determined with SAINT 6.22100 from the complete dataset. A complete
sphere of data was collected using ω (0.3◦) scans with a run time of 30 s/frame at different
Φ angles. A total of 1415 frames (3b, 5c) or 1365 frames (6a) were collected for the
dataset. An additional 50 frames, identical to the first 50, were collected to determine
crystal decay. The frames were integrated using the SAINT 6.22 software and the data
were corrected for absorption and decay using the SADABS101 program. The structures
were solved by direct methods and refined by least-squares methods on F2, using the
SHELXTL program suite.102 All hydrogen atoms were placed in calculated positions and
included in the refinement as riding models. Details of data collection and refinement are
provided in Table 4.1. Further details, including atomic coordinates, distances and angles
are found in the CIF files. For 3b there is a disordered chlorobenzene molecule in the
asymmetric unit that does not model. The four THF molecules that are coordinated to the
lithium cation are disordered and all of the atoms to each THF do not refine well.
Attempts to model the structure in different space groups did not prove to be successful.
104
Table 4.1. Crystal data and structure refinement details
5c
6a
Formula
C32H32AlN4
C23H29AlN5
Fw
499.60
402.49
Cryst. Syst
triclinic
monoclinic
Space group
P1
P2(1)/n
a, Å
11.3139(11)
12.3285(6)
b, Å
15.6164(14)
10.4147(5)
c, Å
17.2642(16)
17.4485(8)
α, deg
86.455(2)
90
β, deg
87.184(2)
97.7140(10)
γ, deg
76.554(2)
90
V, Å3
2959.1(5)
2220.07(18)
Z
4
4
Dcalcd, g cm-3
1.121
1.204
temp, °C
─133
─133
0.094
0.110
λ, Å
0.71073
0.71073
transm coeff
1.00- 0.837
1.00- 0.892
2θ limits, deg
3.66 to 52.00
3.82 to 52.00
total no. of data
21154
14974
no. unique data
11565
4355
no. obsd data
10423
4093
no. of params
667
391
R1 (I > 2σ(I))b
0.0620
0.0353
wR2 (I2, all data)c
0.1814
0.1083
μ, mm
-1
a
max, min peaks, e/Å3 1.133, ─0.920
0.283, ─0.256
________________________________________________________________________
a
I > 2σ(I).
b
R1 =
| |Fo| – |Fc| | / |Fo|.
c
wR2 = [ [w (Fo2 – Fc2)2] / [w (Fo2)2]]1/2.
105
4.4
Results and Discussion
4.4.1
Synthesis of [{tri(3-methylindolyl)methane}MX]
Based on the results obtained by Frank Segla79 with the synthesis of 1 and 2,
further investigation into tripodal ligand frameworks for aluminum and gallium was
performed as part of this dissertation. The synthesis of 3a was performed in a different
manner than reported by Segla. Deprotonated tri(3-methylindolyl)methane was added to
a solution of AlCl3 in THF, and the solution was stirred overnight (eq 4). Solvents were
removed in vacuo, and the solid residue was dissolved in methylene chloride and filtered
over a fine frit with a Celite plug. Removal of methylene chloride from the filtrate
yielded 3a as a dark purple solid. The 1H NMR spectrum of 3a (Figure 4.1) showed one
set of indolyl resonances for the 3-methylindolyl moiety with two doublets at 7.59 and
7.33 ppm, and two triplets at 7.01 and 6.92 ppm for H7, H4, H6 and H5, respectively.
[Li(THF)4]
Cl
H
NH
NH
N M
N
n
1) 3 BuLi
NH
2) MCl3
N
(4)
H
M
3a Al
3b Ga
There was a singlet resonance at 2.40 ppm for the indolyl methyl and one singlet methine
resonance at 6.05 ppm. The simplicity of the spectrum indicated three equivalent 3methylindolyl moieties. There was one set of resonances for THF at 3.20 ppm and 1.25
106
H7 H4
H6
CH
H5
(a)
Indolyl CH3
THF
THF
(b)
Figure 4.1
1
H NMR spectrum of 3a in chloroform-d; (a) aromatic expansion
(b) full spectrum
ppm, the integration for which indicates four THF molecules coordinated to the lithium
cation.
The
13
C NMR spectrum shows similar results with only one set of tri(3-
methylindolyl)methane resonances and only one set of THF resonances. All resonances
in the 1H and
13
C spectra match those reported by Segla for 1.79 The structure of 3a is
proposed to be an anionic aluminum center ligated by one tri(3-methylindolyl)methane
ligand and one chloride. There is also a lithium cation that is coordinated by four THF
molecules.
Complex 3b was isolated in the same manner as 3a. It is also a dark purple solid
and shows analogous features in the 1H and
13
C NMR spectra to those of 3a. There is
only one set of resonances for tri(3-methylindolyl)methane and one set of resonances for
coordinated THF. Complexes 3a and 3b are analogous to 1 except for the inclusion of
THF as the ligand to the lithium cation. These complexes can be made with either THF
or ether coordinated with comparable yields.
107
Crystals of 3a and 3b were grown from concentrated chlorobenzene solutions. Xray diffraction data were collected on both 3a and 3b. The internal R1 value after
integration for 3a was 13.34% due to a poor quality data set. No suitable space group
was found and preliminary solution of the structure was not conclusive. The internal R1
value for 3b after integration was 3.8%, which is indicative of good data. Finding a
suitable unit cell and space group was difficult, and the space group P1 was chosen for
preliminary solution of the structure, of which the anionic portion is shown in Figure 4.1.
The preliminary structure consists of an anionic gallium center ligated by one tri(3methylindolyl)methane ligand and one chloride. There is also a lithium cation that is
solvated with four THF molecules.
Cl1
N1
N3
Figure 4.1
Ga1
N2
ORTEP diagram of 3b. Thermal ellipsoids are drawn at the 30%
probability level. Hydrogen atoms and disordered lithium cation
are omitted for clarity.
Complex 4a was made using a modified version of the procedure used by Frank
Segla.79 A THF solution of tri(3-methylindolyl)methane was added via dropping funnel
to a slurry of LiAlH4 in toluene and the grey slurry was allowed to stir overnight (eq 5).
After removal of half the solvent, 4a was isolated in good yield as a grey solid. The 1H
NMR spectrum looks similar to that of 3a and 3b.
108
There is one set of aromatic
[Li(THF)4]
X
H
N Al
N
NH
N
(5)
+ LiAlX4
NH
NH
H
X
X
4a HH
4a
4b
4b DD
resonances for 3-methylindolyl moieties at 7.43 ppm, 7.32 ppm, 6.92 ppm, and 6.84 ppm
which corresponds to H7, H4, H6, and H5, respectively. There is only one methine
resonance at 6.01 ppm and a singlet methyl resonance at 2.42 ppm. THF resonances are
observed at 3.31 and 1.61 ppm. As with 3a and 3b, this indicates that all three 3methylindolyl moieties are chemically equivalent. At first, there appeared to be no
definitive evidence in the 1H NMR spectrum of 4a for a hydride on aluminum, which is
not unexpected since aluminum nuclei are quadrupolar and peak broadening is well
known for hydrides on aluminum. If the baseline of the spectrum is expanded however,
there is a broad peak centered near 5.4 ppm but it cannot be conclusively assigned as
hydride. Evidence for the hydride was seen in the IR spectrum obtained in KBr where a
broad Al–H stretch was observed at 1864 cm-1.92
To help confirm the assignment of the Al–H stretch in the IR spectrum, complex
4b was synthesized using LiAlD4 (eq 5). Comparable yields were seen for the synthesis
of both compounds and the 1H and
13
C NMR spectra of 4b are indistinguishable from
those of 4a. The only noticeable difference is the absence of the broad peak at 5.4 ppm in
the baseline expansion of the spectrum of 4b. An IR spectrum of 4b in a KBr pellet is
109
also identical to that of 4a except the broad peak at 1864 cm-1 is missing. This verifies
the presence of a hydride on aluminum and confirms the proposed structures of 4a and 4b
as isostructural to compounds 3a and 3b with hydride and deuteride replacing chloride.
Attempts to crystallize 4a or 4b from concentrated chlorobenzene solutions were not
successful.
4.4.2 Reactivity of 3a-4b
Compounds 3a-4b were prepared as potential precursors to three-coordinate
tripodal group 13 complexes. Complexes 3a and 3b were reacted with two distinct
chloride abstraction reagents in three different solvent combinations as summarized in
Table 4.2. These attempts to generate an isolable neutral Lewis base adduct of threecoordinate tripodal aluminum or gallium as shown in eq 6 were unsuccessful. The only
[Li(THF)4]
Cl
N M
N
N
N M
N
+ M'X
N
+ LiX + M'Cl
(6)
H
H
M
3a Al
3b Ga
M' = Ag, Tl
X = BF4, PF6
complex that could be isolated and characterized by 1H NMR spectroscopy from the salt
abstraction reactions was free, protonated tri(3-methylindolyl)methane indicating
hydrolysis. The use of amines to displace halides from group 13 metal complexes for the
generation of cationic four-coordinate group 13 complexes has been reviewed by
Atwood.166 Reactions of 3a or 3b with Et3N showed promise with the formation of a
110
Table 4.2.
Chloride abstraction reactions
__________________________________________________________________
Complex
Solvent
MX
__________________________________________________________________
3a
THF
AgBF4
3a
Acetonitrile
AgBF4
3a
Methylene chloride
AgBF4
3a
THF
TlPF6
3a
Acetonitrile
TlPF6
3a
Methylene chloride
TlPF6
3a
Excess NEt3
-------
3b
THF
TlPF6
3b
Acetonitrile
TlPF6
3b
Methylene chloride
TlPF6
__________________________________________________________________
white insoluble precipitate assumed to be LiCl, but 1H NMR spectra of the resulting
filtrate only showed evidence for unreacted 3a.
Cation exchange was attempted with Et4NCl and Bu4NCl for complexes 3a and
4a. It was proposed that the use of the tetraalkyl ammonium cations would help in the
crystallization of these complexes; no reactivity was observed.
Reactions of 3a with one equivalent of tBuLi in THF resulted in the formation of
4c. The 1H NMR spectrum is analogous to 3a except there is a singlet resonance at 1.55
ppm which is assigned to the tert-butyl group on the anionic aluminum. These types of
complexes are of interest because they are ideal for the alkide and hydride abstraction
reactions to generate the tripodal neutral aluminum and gallium compounds.
111
Synthesis of (1-CH3-2-C3H2N2)HC(3-CH3C8H4N)2AlR (R = Me, Et, iBu, tBu)
4.4.3
Complexes 5a-d were synthesized to complete the series of compounds that Das
had made using di(3-methylindolyl)imidazolylmethane.81 Complexes analogous to those
in eq 3 using this ligand could be potential precursors to three-coordinate tripodal
cationic aluminum compounds that should be highly Lewis acidic. Das reacted di(3methylindolyl)imidazolylmethane with a variety of aluminum and gallium trialkyls in
attempts to synthesize these complexes (eq 7).81
Despite many attempts only the
bidentate complexes with dialkyl groups on the metal and one free 3-methylindolyl
moiety were obtained.81
H
N
+ MR3
N
NH
N
H
NH
R
M
toluene
o
2 h, 20 C
N
NH
R
(7)
N
M
Al
Al
Al
Al
Ga
R
Me
Et
i
Bu
t
Bu
t
Bu
Deprotonation of di(3-methylindolyl)imidazolylmethane with nBuLi, followed by
addition of Cl2AlR (R = Me, Et, iBu, tBu) yielded complexes 5a-d as light green and
purple solids in high yield as shown in eq 8.
112
The complexes show the same characteristics in the 1H and 13C NMR spectra. The
1
H NMR spectrum of 5a shows one set of indolyl resonances for the 3-methylindolyl
moieties with doublets at 7.40 ppm and 7.39 ppm for H4 and H7, respectively, and triplet
resonances at 7.06 ppm and 6.96 ppm for H6 and H5, respectively. There is one set of
aromatic resonances for the imidazolyl at 6.89 ppm and 6.47 ppm for H5imidazolyl and H4
R
H
N
N
NH
NH
N Al
N
1) 2 nBuLi
N
2) RAlCl2
toluene
15 h, 20 oC
(8)
H
5a
5b
5c
5d
imidazolyl,
N
R
Me
Et
i
Bu
t
Bu
respectively. A singlet resonance at 2.41 ppm is observed for the methyl groups
on the indolyl, and a singlet resonance is observed at 3.70 ppm for the methyl group on
the imidazolyl. A singlet resonance is observed for the aluminum bound methyl at 0.31
ppm. The integration of the indolyl-, imidazolyl-, and aluminum-bound methyls shows a
ratio of 2:1:1 indicating only one alkyl group per aluminum. The H7 proton for the 3methylindolyl moiety is seen upfield of H4 for 5a but shifts downfield of H4 in
complexes 5b-d. This isn’t unexpected based on work by Barnard,124 since it is known
that the chemical shift of H7 is highly influenced by groups that are bound to the metal
113
AltBu
CH3
H7 H4
H5
H6 H5imid
CH
H4imid
(a)
CH3imid
(b)
Figure 4.3
1
H NMR spectrum of 5d in chloroform-d: (a) aromatic expansion
(b) full spectrum
when the indolyl ligands are oriented in a tripodal fashion. A representative 1H NMR
spectrum of 5d is shown in Figure 4.3.
X-ray crystallography confirmed the structure of 5b (Figure 4.4) as the fourcoordinate tripodal aluminum complex ligated by two anionic 3-methylindolyl groups,
one neutral imidazolyl donor, and one ethyl group. The molecule crystallized in the
space group P 1 , and the structure was refined with an R1 factor of 6.20%. Selected bond
distances and angles are summarized in Table 4.3. The Al–Nindolyl bond distances are
1.8699(18) Å and 1.8785(18) Å, while the Al–Nimidazolyl bond distance is 1.9380(18) Å. It
is important to note that the Al–Nindolyl bond distances for the anionic donors are
114
significantly shorter than for the Al–Nimidazolyl neutral donor. This difference in bond
length is similar to results obtained by Fneich and Das shown in equations 3 and 7. 80,81
Alkide abstraction from 5a-5d for the generation of a three-coordinate cationic
aluminum complex was not attempted.
C3
C2
N2
Al1
N1
N3
N4
Figure 4.4
Table 4.3
ORTEP diagram of 5b. Thermal ellipsoids are drawn at the 30%
probability level. Hydrogen atoms are omitted for clarity.
Selected bond distances and angles for 5b
Bond distances (Å)
Al1-N1
1.8699(18)
Al1-N3
1.9380(18)
Al1-N2
1.8785(18)
Al1-C2
1.941(2)
Bond angles (deg)
N1-Al1-N3
94.79(7)
N1-Al1-C2
120.40(10)
N1-Al1-N2
97.15(8)
N2-Al1-C2
123.47(10)
N2-Al1-N3
92.62(8)
N3-Al1-C2
121.33(9)
115
4.4.4
Synthesis of (TPA)M(HNMe2) Complexes (M = Al, Ga)
Concurrent with the work reported herein, Andrew Ramos in the Mason group
synthesized the TPA163 ligand for reactions with trialkylaluminum reagents. This ligand
has an analogous framework to the tripodal tren ligands popularized by Verkade60 and
Schrock167 and is expected to help in the generation of Lewis acidic group 13 complexes.
Ramos observed good reactivity of trialkyl aluminum complexes with the TPA ligand,
but complex mixtures were sometimes isolated. Complexes that were isolated showed
reactivity of one or two arms of the ligand leaving mono- and dialkyl aluminum centers
as shown in eq 9. One of the aims of this dissertation was then to make the neutral
tetradentate trigonal bipyramidal complexes of aluminum and gallium using the TPA
ligand.
A toluene solution of [Al(NMe2)3]2 was added to a toluene suspension of TPA
and the reaction solution was stirred overnight (eq 10). Concentration of solvent and
R
N Al R
N
H
N
NH
N
H
N
HN
+ AlR3
(9)
toluene
R = Me, tBu
R
N
HN
Al
N
HN
116
N
subsequent filtration allowed for isolation of 6a in high yield. The absence of an NH
resonance in the 1H NMR spectrum of 6a indicated that all three pyrrolyl arms of the
ligand reacted. There is one set of aromatic resonances for the pyrrolyl groups at 6.69,
6.22 and 6.04 ppm which correspond to H5, H4, and H3, respectively. The resonance for
the methylene protons is observed at 3.96 ppm and the sharp singlet is more evidence for
reactivity of all three arms resulting in a symmetrical complex. In contrast the methylene
proton resonances are diastereotopic and observed as AB quartets in the complexes
isolated by Ramos due to the inequivalencies in the pyrrolyl arms in his complexes.
Complex 6a has a dimethylamine moiety coordinated to aluminum that is trans to the
tertiary amine, and the doublet resonance at 3.19 ppm is assigned to the methyl groups of
the amine.
HNMe2
N
N
N
M
N
H
N
HH
NN
+ 0.5 [M(NMe2)3]2
toluene
(10)
N
M
6a Al
6b Ga
Complex 6b was isolated using the same procedures as for 6a and similar features
are seen in the
1
H and
13
C NMR spectra.
The
1
H NMR spectrum of 6b is
indistinguishable from that for 6a and there is less than 0.08 ppm shift for all
corresponding resonances of the two compounds.
117
X-ray crystallography confirmed the structure of 6a (Figure 4.5) as the fivecoordinate tripodal aluminum complex with three anionic pyrrolyl arms, one neutral
dimethylamine, and one apical nitrogen bound to aluminum. The molecule crystallized
in the space group P2(1)/n and the structure was refined with an R1 factor of 3.53%.
Selected bond distances and angles are summarized in Table 4.4. The Al–Npyrrolyl bond
distances range from 1.8838(11) Å to 1.8894(11) Å. As expected for a neutral donor, the
Al–N bond distance of 2.0314(11) Å for the coordinated dimethylamine is greater than
the Al–Npyrrolyl bond distances. The apical Al–N distance is considerably greater at
2.1099(10) Å, which indicates a weaker interaction of the apical nitrogen and aluminum
center. Coordination of the apical nitrogen plays an important role in the related tren
systems. The Al–Napical bond distances will be a point of interest in future work with the
Al–TPA systems.
N5
N2
Al1
N3
N4
N1
Figure 4.5
ORTEP diagram of 6a. Thermal ellipsoids are drawn at the 30%
probability level. Hydrogen atoms are omitted for clarity.
118
Table 4.4
Selected bond distances and angles for 6a
Bond distances (Å)
Al1–N1
2.1099(10)
Al1–N4
1.8894(11)
Al1–N2
1.8878(11)
Al1–N5
2.0314(11)
Al1–N3
1.8838(11)
Bond angles (deg)
N2-Al1-N1
81.86(4)
N2-Al1-N4
123.87(5)
N3-Al1-N1
83.39(4)
N2-Al1-N5
93.83(5)
N4-Al1-N1
82.79(4)
N3-Al1-N4
116.36(5)
N5-Al1-N1
174.74(5)
N3-Al1-N5
101.22(5)
N3-Al1-N2
114.93(5)
N4-Al1-N5
97.25(5)
4.5 Conclusions
Three different series of four- and five-coordinate tripodal aluminum and gallium
complexes were synthesized and characterized using 1H and 13C NMR spectroscopy.
Molecular structures for 3b, 5b, and 6a were confirmed using X-ray crystallography.
These complexes may serve as precursors to potential three- or four-coordinate (neutral
or cationic) tripodal group 13 complexes that should be highly Lewis acidic.
119
Chapter 5
Concluding Remarks
The reactivity of di- and tri(3-methylindolyl)methanes and tris(pyrrolyl-αmethyl)amine with several different aluminum and gallium compounds was investigated.
The use of isonitriles as models to reactivity of carbon monoxide with aluminum and
gallium alkyls was also investigated. This study was performed in hopes of generating
highly electrophilic and Lewis acidic group 13 metal centers for the binding and
coordination of carbon monoxide.
Chapter 2 describes the reactivity of two different isonitriles with a series of
aluminum and gallium alkyls. These complexes; R3M•C≡NtBu (M = Al: R = tBu (1a),
Me (1c), iBu (1e), Et (1f); M = Ga: R = tBu (1b), Me (1d)); R3M•C≡N(2,6dimethylphenyl) (M = Al: R = tBu (2a), Me (2c), iBu (2e), Et (2f); M = Ga: R = tBu (2b),
Me (2d)), serve as models of carbon monoxide binding to group 13 alkyls. The
compounds were characterized by NMR and IR spectroscopy and X-ray crystallography.
Isothermal titration calorimetry was used to study the enthalpies of complexation for
coordination of the isonitrile to the group 13 trialkyl. The binding is exothermic, and ΔH
for complexation is approximately 21-25 kJ/mol for the aluminum alkyls and 16-17
kJ/mol for the gallium alkyls. Reactivity studies of these complexes at elevated
temperatures did not lead to insertion products that were desired. These complexes are
120
stable up to 24 h at 100 °C in benzene solutions without any change to the 1H NMR
spectrum.
Chapter 3 describes the synthesis and spectroscopic characterization of group 13
complexes with 3-methylindole (L1), di(3-methylindolyl)phenylmethane (L2), and tri(3methylindolyl)methane (L3) is reported. Within this report are the first examples of μ2η1:η1-N-indolyl moieties bridging group 13 elements, specifically aluminum in the
complexes; [L1AlR2]2 (R = Me (7a), Et (7b), iBu (7c)), (L2Al2Me4) (8), (L3Al3R6) (R =
Me (9a), Et (9b)), (L3Al3HiBu5) (9c). These complexes were characterized by NMR
spectroscopy and elemental analyses. Compounds 7a, 8, and 9a were characterized by
X-ray crystallography which confirmed the presence of the μ2-η1:η1-N-indolyl moieties.
These complexes specifically 9a-9c were proposed to be precursors to neutral threecoordinate tripodal aluminum compounds that would be highly electrophilic and Lewis
acidic. Attempts toward generation of such compounds were unsuccessful.
Chapter 4 describes the synthesis and spectroscopic characterization of four- and
five-coordinate complexes of aluminum and gallium is reported.
This includes the
synthesis of four-coordinate anionic aluminum and gallium complexes of tri(3methylindolyl)methane,
four-coordinate
neutral
aluminum
complexes
of
tri(3-
methylindolyl)imidazolylmethane (L4), and five-coordinate aluminum and gallium
complexes
of
tris(pyrrolyl-α-methyl)amine
(L5).
These
complexes
include:
[(L3MX)][Li(THF4)] (M = Al: X = Cl (3a), H (4a), D (4b), tBu (4c); M = Ga: X = Cl
(3b)); (L4AlR) (R = Me (5a), Et (5b), iBu (5c), tBu (5d); (L5M(HNMe2)) (M = Al (6a),
Ga (6b)). These complexes have been characterized by 1H and
13
C NMR spectroscopy.
X-ray crystallography confirmed the structures of 3b, 6b and 7a. These complexes serve
121
as precursors to potential three- or four-coordinate neutral, Lewis acidic, group 13
compounds although initial attempts to generate these were unsuccessful.
In future research, different methods than those discussed towards the generation
of neutral three-coordinate tripodal aluminum complexes from the compounds discussed
in chapter 3 should be investigated. A potential route would be the use of a strong base
to help promote the elimination of Me3Al in complex 9a. The coordination of base may
also help the stability of the aluminum complex that would be generated. More thorough
attempts for hydride, alkide, or chloride abstraction from complexes described in chapter
4 need to be undertaken. Trityl salts should be explored as alkide or hydride abstraction
reagents. Bases other than Et3N should be used for the attempted removal of chloride
from complexes 3a and 3b in chapter 4.
122
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Appendix: CIF Files for Compounds
CIF File for tBu3Al·C≡NtBu
_audit_creation_method
_chemical_name_systematic
;
?
;
_chemical_name_common
_chemical_melting_point
_chemical_formula_moiety
_chemical_formula_sum
SHELXL-97
_chemical_formula_weight
281.45
'C17 H36 Al N'
'C17 H36 Al N'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Al' 'Al' 0.0645 0.0514
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
_symmetry_space_group_name_H-M
monoclinic
P2(1)/m
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z'
'-x, -y, -z'
'x, -y-1/2, z'
_cell_length_a
_cell_length_b
_cell_length_c
_cell_angle_alpha
_cell_angle_beta
8.3301(19)
12.218(3)
10.525(2)
90.00
110.735(4)
133
_cell_angle_gamma
_cell_volume
_cell_formula_units_Z
_cell_measurement_temperature
_cell_measurement_reflns_used
_cell_measurement_theta_min
_cell_measurement_theta_max
90.00
1001.8(4)
4
-133
893
4.04
30.53
_exptl_crystal_description
_exptl_crystal_colour
_exptl_crystal_size_max
_exptl_crystal_size_mid
_exptl_crystal_size_min
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn
_exptl_crystal_density_method
_exptl_crystal_F_000
_exptl_absorpt_coefficient_mu
_exptl_absorpt_correction_type
_exptl_absorpt_correction_T_min
_exptl_absorpt_correction_T_max
_exptl_absorpt_process_details ?
Cube
Colorless
.2
.2
.2
1.400
'not measured'
474
0.140
multi-scan
0.795
1.000
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
-133
_diffrn_radiation_wavelength
0.71073
_diffrn_radiation_type
MoK\a
_diffrn_radiation_source
'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device_type
'Bruker platform with 6k CCD'
_diffrn_measurement_method
'omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
?
_diffrn_reflns_number
6801
_diffrn_reflns_av_R_equivalents
0.0199
_diffrn_reflns_av_sigmaI/netI
0.0198
_diffrn_reflns_limit_h_min
-9
_diffrn_reflns_limit_h_max
10
_diffrn_reflns_limit_k_min
-13
_diffrn_reflns_limit_k_max
15
_diffrn_reflns_limit_l_min
-12
_diffrn_reflns_limit_l_max
12
_diffrn_reflns_theta_min
2.07
_diffrn_reflns_theta_max
26.00
_reflns_number_total
2060
_reflns_number_gt
1896
_reflns_threshold_expression
>2sigma(I)
_computing_data_collection
'Smart 5.630'
134
_computing_cell_refinement
_computing_data_reduction
_computing_structure_solution
_computing_structure_refinement
_computing_molecular_graphics ?
_computing_publication_material ?
'Saintplus 5.45'
'Saintplus 5.45'
'SHELXS-97 (Sheldrick, 1990)'
'SHELXL-97 (Sheldrick, 1997)'
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0405P)^2^+1.3638P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary
difmap
_atom_sites_solution_hydrogens
geom
_refine_ls_hydrogen_treatment
mixed
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
2060
_refine_ls_number_parameters
91
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.0656
_refine_ls_R_factor_gt
0.0610
_refine_ls_wR_factor_ref
0.1402
_refine_ls_wR_factor_gt
0.1375
_refine_ls_goodness_of_fit_ref
1.044
_refine_ls_restrained_S_all
1.044
_refine_ls_shift/su_max
0.000
_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
135
Al1 Al -0.00281(9) 0.2500 0.26025(7) 0.0161(2) Uani 1 2 d S . .
N1 N -0.3229(3) 0.2500 -0.0298(2) 0.0217(5) Uani 1 2 d S . .
C1 C -0.2051(3) 0.2500 0.0687(3) 0.0232(6) Uani 1 2 d S . .
C2 C -0.1440(4) 0.2500 0.3825(3) 0.0282(6) Uani 1 2 d S . .
C21 C -0.0269(5) 0.2787(3) 0.5283(4) 0.0303(10) Uiso 0.50 1 d P A 1
H21A H -0.0946 0.2791 0.5878 0.045 Uiso 0.50 1 calc PR A 1
H21B H 0.0238 0.3512 0.5291 0.045 Uiso 0.50 1 calc PR A 1
H21C H 0.0647 0.2240 0.5609 0.045 Uiso 0.50 1 calc PR A 1
C22 C -0.2934(6) 0.3284(4) 0.3382(5) 0.0411(11) Uiso 0.50 1 d P . 1
H22A H -0.3564 0.3235 0.4009 0.062 Uiso 0.50 1 calc PR . 1
H22B H -0.3701 0.3094 0.2463 0.062 Uiso 0.50 1 calc PR . 1
H22C H -0.2508 0.4032 0.3386 0.062 Uiso 0.50 1 calc PR . 1
C23 C -0.2235(7) 0.1337(4) 0.3873(5) 0.0423(11) Uiso 0.50 1 d P A 1
H23A H -0.2924 0.1366 0.4458 0.063 Uiso 0.50 1 calc PR A 1
H23B H -0.1309 0.0801 0.4237 0.063 Uiso 0.50 1 calc PR A 1
H23C H -0.2965 0.1120 0.2953 0.063 Uiso 0.50 1 calc PR A 1
C3 C 0.1202(3) 0.10872(17) 0.2523(2) 0.0282(5) Uani 1 1 d . . .
C31A C 0.0007(7) 0.0136(5) 0.1912(6) 0.0376(12) Uiso 0.45 1 d P A 1
H31A H 0.0687 -0.0515 0.1893 0.056 Uiso 0.45 1 calc PR A 1
H31B H -0.0736 0.0322 0.0984 0.056 Uiso 0.45 1 calc PR A 1
H31C H -0.0700 -0.0013 0.2464 0.056 Uiso 0.45 1 calc PR A 1
C32A C 0.2376(6) 0.0733(4) 0.4002(5) 0.0282(10) Uiso 0.45 1 d P A 1
H32A H 0.2965 0.0047 0.3957 0.042 Uiso 0.45 1 calc PR A 1
H32B H 0.1664 0.0624 0.4560 0.042 Uiso 0.45 1 calc PR A 1
H32C H 0.3227 0.1305 0.4407 0.042 Uiso 0.45 1 calc PR A 1
C33A C 0.2382(8) 0.1206(5) 0.1666(6) 0.0390(12) Uiso 0.45 1 d P A 1
H33A H 0.2939 0.0504 0.1644 0.058 Uiso 0.45 1 calc PR A 1
H33B H 0.3259 0.1763 0.2078 0.058 Uiso 0.45 1 calc PR A 1
H33C H 0.1689 0.1427 0.0738 0.058 Uiso 0.45 1 calc PR A 1
C31B C 0.0040(6) 0.0088(4) 0.2501(5) 0.0422(11) Uiso 0.55 1 d P A 3
H31D H 0.0644 -0.0588 0.2448 0.063 Uiso 0.55 1 calc PR A 3
H31E H -0.1024 0.0139 0.1710 0.063 Uiso 0.55 1 calc PR A 3
H31F H -0.0235 0.0083 0.3333 0.063 Uiso 0.55 1 calc PR A 3
C32B C 0.2867(5) 0.1005(4) 0.3757(4) 0.0333(9) Uiso 0.55 1 d P A 3
H32D H 0.3458 0.0321 0.3710 0.050 Uiso 0.55 1 calc PR A 3
H32E H 0.2598 0.1013 0.4591 0.050 Uiso 0.55 1 calc PR A 3
H32F H 0.3610 0.1627 0.3760 0.050 Uiso 0.55 1 calc PR A 3
C33B C 0.1671(7) 0.1010(4) 0.1253(5) 0.0467(12) Uiso 0.55 1 d P A 3
H33D H 0.2251 0.0312 0.1253 0.070 Uiso 0.55 1 calc PR A 3
H33E H 0.2439 0.1615 0.1244 0.070 Uiso 0.55 1 calc PR A 3
H33F H 0.0626 0.1053 0.0444 0.070 Uiso 0.55 1 calc PR A 3
C5 C -0.4778(3) 0.2500 -0.1538(3) 0.0240(6) Uani 1 2 d S . .
C51 C -0.5781(3) 0.1468(2) -0.1497(2) 0.0405(6) Uani 1 1 d . . .
H51A H -0.6147 0.1496 -0.0709 0.061 Uiso 1 1 calc R . .
H51B H -0.5050 0.0825 -0.1424 0.061 Uiso 1 1 calc R . .
H51C H -0.6793 0.1417 -0.2330 0.061 Uiso 1 1 calc R . .
C52 C -0.4170(4) 0.2500 -0.2745(3) 0.0351(7) Uani 1 2 d S . .
H52A H -0.3545 0.3180 -0.2746 0.053 Uiso 0.50 1 calc PR . .
H52B H -0.5164 0.2447 -0.3591 0.053 Uiso 0.50 1 calc PR . .
H52C H -0.3409 0.1873 -0.2675 0.053 Uiso 0.50 1 calc PR . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
136
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Al1 0.0145(4) 0.0178(4) 0.0148(4) 0.000 0.0035(3) 0.000
N1 0.0193(11) 0.0246(12) 0.0193(11) 0.000 0.0045(9) 0.000
C1 0.0215(13) 0.0242(14) 0.0225(14) 0.000 0.0063(12) 0.000
C2 0.0196(13) 0.0442(18) 0.0216(13) 0.000 0.0082(11) 0.000
C3 0.0282(10) 0.0259(10) 0.0254(10) -0.0055(8) 0.0032(8) 0.0060(8)
C5 0.0182(13) 0.0273(14) 0.0194(13) 0.000 -0.0019(10) 0.000
C51 0.0274(11) 0.0434(14) 0.0414(13) 0.0040(11) 0.0008(10) -0.0114(10)
C52 0.0379(17) 0.0434(18) 0.0201(14) 0.000 0.0054(13) 0.000
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Al1 C3 2.024(2) 4_565 ?
Al1 C3 2.024(2) . ?
Al1 C2 2.027(3) . ?
Al1 C1 2.121(3) . ?
N1 C1 1.148(3) . ?
N1 C5 1.475(3) . ?
C2 C22 1.508(5) 4_565 ?
C2 C22 1.508(5) . ?
C2 C21 1.539(4) . ?
C2 C21 1.539(4) 4_565 ?
C2 C23 1.576(5) . ?
C2 C23 1.576(5) 4_565 ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?
C22 C22 1.916(11) 4_565 ?
C22 H22A 0.9800 . ?
C22 H22B 0.9800 . ?
C22 H22C 0.9800 . ?
C23 H23A 0.9800 . ?
C23 H23B 0.9800 . ?
C23 H23C 0.9800 . ?
C3 C31A 1.517(6) . ?
C3 C33B 1.523(5) . ?
C3 C32B 1.532(4) . ?
C3 C31B 1.553(5) . ?
C3 C33A 1.558(6) . ?
C3 C32A 1.578(5) . ?
137
C31A H31A 0.9800 . ?
C31A H31B 0.9800 . ?
C31A H31C 0.9800 . ?
C32A H32A 0.9800 . ?
C32A H32B 0.9800 . ?
C32A H32C 0.9800 . ?
C33A H33A 0.9800 . ?
C33A H33B 0.9800 . ?
C33A H33C 0.9800 . ?
C31B H31D 0.9800 . ?
C31B H31E 0.9800 . ?
C31B H31F 0.9800 . ?
C32B H32D 0.9800 . ?
C32B H32E 0.9800 . ?
C32B H32F 0.9800 . ?
C33B H33D 0.9800 . ?
C33B H33E 0.9800 . ?
C33B H33F 0.9800 . ?
C5 C51 1.522(3) . ?
C5 C51 1.522(3) 4_565 ?
C5 C52 1.526(4) . ?
C51 H51A 0.9800 . ?
C51 H51B 0.9800 . ?
C51 H51C 0.9800 . ?
C52 H52A 0.9800 . ?
C52 H52B 0.9800 . ?
C52 H52C 0.9800 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C3 Al1 C3 117.04(13) 4_565 . ?
C3 Al1 C2 116.23(7) 4_565 . ?
C3 Al1 C2 116.23(7) . . ?
C3 Al1 C1 101.77(7) 4_565 . ?
C3 Al1 C1 101.77(7) . . ?
C2 Al1 C1 99.17(11) . . ?
C1 N1 C5 178.2(3) . . ?
N1 C1 Al1 174.9(2) . . ?
C22 C2 C22 78.9(4) 4_565 . ?
C22 C2 C21 128.0(3) 4_565 . ?
C22 C2 C21 109.0(3) . . ?
C22 C2 C21 109.0(3) 4_565 4_565 ?
C22 C2 C21 128.0(3) . 4_565 ?
C21 C2 C21 26.3(3) . 4_565 ?
C22 C2 C23 29.2(2) 4_565 . ?
C22 C2 C23 105.8(4) . . ?
C21 C2 C23 107.4(3) . . ?
C21 C2 C23 83.6(3) 4_565 . ?
C22 C2 C23 105.8(4) 4_565 4_565 ?
C22 C2 C23 29.2(2) . 4_565 ?
C21 C2 C23 83.6(3) . 4_565 ?
138
C21 C2 C23 107.4(3) 4_565 4_565 ?
C23 C2 C23 128.8(4) . 4_565 ?
C22 C2 Al1 113.9(2) 4_565 . ?
C22 C2 Al1 113.9(2) . . ?
C21 C2 Al1 109.1(2) . . ?
C21 C2 Al1 109.1(2) 4_565 . ?
C23 C2 Al1 111.4(2) . . ?
C23 C2 Al1 111.4(2) 4_565 . ?
C2 C21 H21A 109.5 . . ?
C2 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C2 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C2 C22 C22 50.5(2) . 4_565 ?
C2 C22 H22A 109.5 . . ?
C22 C22 H22A 86.5 4_565 . ?
C2 C22 H22B 109.5 . . ?
C22 C22 H22B 76.3 4_565 . ?
H22A C22 H22B 109.5 . . ?
C2 C22 H22C 109.5 . . ?
C22 C22 H22C 158.9 4_565 . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
C2 C23 H23A 109.5 . . ?
C2 C23 H23B 109.5 . . ?
H23A C23 H23B 109.5 . . ?
C2 C23 H23C 109.5 . . ?
H23A C23 H23C 109.5 . . ?
H23B C23 H23C 109.5 . . ?
C31A C3 C33B 85.1(3) . . ?
C31A C3 C32B 124.8(3) . . ?
C33B C3 C32B 107.7(3) . . ?
C31A C3 C31B 23.0(2) . . ?
C33B C3 C31B 106.9(3) . . ?
C32B C3 C31B 109.5(3) . . ?
C31A C3 C33A 106.3(3) . . ?
C33B C3 C33A 24.1(2) . . ?
C32B C3 C33A 86.0(3) . . ?
C31B C3 C33A 125.6(3) . . ?
C31A C3 C32A 107.0(3) . . ?
C33B C3 C32A 125.9(3) . . ?
C32B C3 C32A 23.96(19) . . ?
C31B C3 C32A 87.9(3) . . ?
C33A C3 C32A 107.4(3) . . ?
C31A C3 Al1 113.9(2) . . ?
C33B C3 Al1 112.3(2) . . ?
C32B C3 Al1 109.92(19) . . ?
C31B C3 Al1 110.4(2) . . ?
C33A C3 Al1 112.1(2) . . ?
C32A C3 Al1 109.8(2) . . ?
C3 C31A H31A 109.5 . . ?
C3 C31A H31B 109.5 . . ?
H31A C31A H31B 109.5 . . ?
C3 C31A H31C 109.5 . . ?
H31A C31A H31C 109.5 . . ?
139
H31B C31A H31C 109.5 . . ?
C3 C32A H32A 109.5 . . ?
C3 C32A H32B 109.5 . . ?
H32A C32A H32B 109.5 . . ?
C3 C32A H32C 109.5 . . ?
H32A C32A H32C 109.5 . . ?
H32B C32A H32C 109.5 . . ?
C3 C33A H33A 109.5 . . ?
C3 C33A H33B 109.5 . . ?
H33A C33A H33B 109.5 . . ?
C3 C33A H33C 109.5 . . ?
H33A C33A H33C 109.5 . . ?
H33B C33A H33C 109.5 . . ?
C3 C31B H31D 109.5 . . ?
C3 C31B H31E 109.5 . . ?
H31D C31B H31E 109.5 . . ?
C3 C31B H31F 109.5 . . ?
H31D C31B H31F 109.5 . . ?
H31E C31B H31F 109.5 . . ?
C3 C32B H32D 109.5 . . ?
C3 C32B H32E 109.5 . . ?
H32D C32B H32E 109.5 . . ?
C3 C32B H32F 109.5 . . ?
H32D C32B H32F 109.5 . . ?
H32E C32B H32F 109.5 . . ?
C3 C33B H33D 109.5 . . ?
C3 C33B H33E 109.5 . . ?
H33D C33B H33E 109.5 . . ?
C3 C33B H33F 109.5 . . ?
H33D C33B H33F 109.5 . . ?
H33E C33B H33F 109.5 . . ?
N1 C5 C51 106.97(15) . . ?
N1 C5 C51 106.97(15) . 4_565 ?
C51 C5 C51 111.9(3) . 4_565 ?
N1 C5 C52 107.0(2) . . ?
C51 C5 C52 111.81(16) . . ?
C51 C5 C52 111.81(16) 4_565 . ?
C5 C51 H51A 109.5 . . ?
C5 C51 H51B 109.5 . . ?
H51A C51 H51B 109.5 . . ?
C5 C51 H51C 109.5 . . ?
H51A C51 H51C 109.5 . . ?
H51B C51 H51C 109.5 . . ?
C5 C52 H52A 109.5 . . ?
C5 C52 H52B 109.5 . . ?
H52A C52 H52B 109.5 . . ?
C5 C52 H52C 109.5 . . ?
H52A C52 H52C 109.5 . . ?
H52B C52 H52C 109.5 . . ?
_diffrn_measured_fraction_theta_max
_diffrn_reflns_theta_full
_diffrn_measured_fraction_theta_full
_refine_diff_density_max
_refine_diff_density_min
_refine_diff_density_rms
0.999
26.00
0.999
0.497
-0.458
0.053
140
CIF File for tBu3Ga·C≡NtBu
_audit_creation_method
_chemical_name_systematic
;
?
;
_chemical_name_common
_chemical_melting_point
_chemical_formula_moiety
_chemical_formula_sum
SHELXL-97
_chemical_formula_weight
324.19
?
?
'C17 H36 Ga N'
'C17 H36 Ga N'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Ga' 'Ga' 0.2307 1.6083
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
_symmetry_space_group_name_H-M
monoclinic
P2(1)/m
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z'
'-x, -y, -z'
'x, -y-1/2, z'
_cell_length_a
_cell_length_b
_cell_length_c
_cell_angle_alpha
_cell_angle_beta
_cell_angle_gamma
_cell_volume
_cell_formula_units_Z
_cell_measurement_temperature
_cell_measurement_reflns_used
_cell_measurement_theta_min
_cell_measurement_theta_max
8.3397(2)
12.2280(2)
10.5604(2)
90.00
110.8900(10)
90.00
1006.14(3)
2
-133
6873
2.614
28.292
141
_exptl_crystal_description
_exptl_crystal_colour
_exptl_crystal_size_max
_exptl_crystal_size_mid
_exptl_crystal_size_min
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn
_exptl_crystal_density_method
_exptl_crystal_F_000
_exptl_absorpt_coefficient_mu
_exptl_absorpt_correction_type ?
_exptl_absorpt_correction_T_min
_exptl_absorpt_correction_T_max
_exptl_absorpt_process_details ?
rectangle brick
Colorless
.25
.25
.20
1.070
'not measured'
352
1.359
0.790
1.000
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
_diffrn_radiation_wavelength
_diffrn_radiation_type
_diffrn_radiation_source
_diffrn_radiation_monochromator
_diffrn_measurement_device_type
_diffrn_measurement_method
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
?
_diffrn_reflns_number
_diffrn_reflns_av_R_equivalents
_diffrn_reflns_av_sigmaI/netI
_diffrn_reflns_limit_h_min
_diffrn_reflns_limit_h_max
_diffrn_reflns_limit_k_min
_diffrn_reflns_limit_k_max
_diffrn_reflns_limit_l_min
_diffrn_reflns_limit_l_max
_diffrn_reflns_theta_min
_diffrn_reflns_theta_max
_reflns_number_total
_reflns_number_gt
_reflns_threshold_expression
-133
0.71073
MoK\a
'fine-focus sealed tube'
graphite
'Bruker platform with 6k CCD'
'omega scans'
_computing_data_collection
_computing_cell_refinement
_computing_data_reduction
_computing_structure_solution
_computing_structure_refinement
'Smart 5.630'
'Saintplus 5.45'
'Saintplus 5.45'
'SHELXS-97 (Sheldrick, 1990)'
'SHELXL-97 (Sheldrick, 1997)'
15239
0.0231
0.0150
-11
11
-14
16
-14
14
2.06
28.29
2620
2536
>2sigma(I)
142
_computing_molecular_graphics ?
_computing_publication_material ?
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0378P)^2^+0.8329P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary
difmap
_atom_sites_solution_hydrogens
geom
_refine_ls_hydrogen_treatment
mixed
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
2620
_refine_ls_number_parameters
91
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.0345
_refine_ls_R_factor_gt
0.0333
_refine_ls_wR_factor_ref
0.0832
_refine_ls_wR_factor_gt
0.0824
_refine_ls_goodness_of_fit_ref
1.053
_refine_ls_restrained_S_all
1.053
_refine_ls_shift/su_max
0.000
_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ga1 Ga 0.00003(3) 0.2500 0.26268(2) 0.02351(9) Uani 1 2 d S . .
143
N1 N -0.3245(3) 0.2500 -0.0304(2) 0.0308(4) Uani 1 2 d S . .
C1 C -0.2060(3) 0.2500 0.0668(3) 0.0341(5) Uani 1 2 d S . .
C2 C -0.1444(3) 0.2500 0.3827(3) 0.0372(6) Uani 1 2 d S . .
C21 C -0.0277(5) 0.2776(3) 0.5279(4) 0.0407(9) Uiso 0.50 1 d P A 1
H21A H -0.0955 0.2780 0.5870 0.061 Uiso 0.50 1 calc PR A 1
H21B H 0.0236 0.3499 0.5294 0.061 Uiso 0.50 1 calc PR A 1
H21C H 0.0633 0.2227 0.5601 0.061 Uiso 0.50 1 calc PR A 1
C22 C -0.2916(6) 0.3276(4) 0.3370(5) 0.0531(11) Uiso 0.50 1 d P A 1
H22A H -0.3556 0.3236 0.3987 0.080 Uiso 0.50 1 calc PR A 1
H22B H -0.3676 0.3082 0.2451 0.080 Uiso 0.50 1 calc PR A 1
H22C H -0.2486 0.4022 0.3370 0.080 Uiso 0.50 1 calc PR A 1
C23 C -0.2233(7) 0.1322(4) 0.3852(6) 0.0548(11) Uiso 0.50 1 d P A 1
H23A H -0.2925 0.1337 0.4432 0.082 Uiso 0.50 1 calc PR A 1
H23B H -0.1302 0.0789 0.4210 0.082 Uiso 0.50 1 calc PR A 1
H23C H -0.2959 0.1112 0.2930 0.082 Uiso 0.50 1 calc PR A 1
C3 C 0.1213(2) 0.10796(16) 0.25264(19) 0.0367(4) Uani 1 1 d . . .
C31A C 0.0009(7) 0.0139(5) 0.1925(6) 0.0485(12) Uiso 0.45 1 d P A 1
H31A H 0.0678 -0.0515 0.1902 0.073 Uiso 0.45 1 calc PR A 1
H31B H -0.0741 0.0327 0.1001 0.073 Uiso 0.45 1 calc PR A 1
H31C H -0.0690 -0.0005 0.2481 0.073 Uiso 0.45 1 calc PR A 1
C32A C 0.2394(6) 0.0731(4) 0.4002(5) 0.0405(10) Uiso 0.45 1 d P A 1
H32A H 0.2985 0.0047 0.3960 0.061 Uiso 0.45 1 calc PR A 1
H32B H 0.1687 0.0625 0.4561 0.061 Uiso 0.45 1 calc PR A 1
H32C H 0.3244 0.1305 0.4402 0.061 Uiso 0.45 1 calc PR A 1
C33A C 0.2357(8) 0.1200(5) 0.1659(6) 0.0517(12) Uiso 0.45 1 d P A 1
H33A H 0.2917 0.0500 0.1634 0.078 Uiso 0.45 1 calc PR A 1
H33B H 0.3233 0.1760 0.2059 0.078 Uiso 0.45 1 calc PR A 1
H33C H 0.1647 0.1416 0.0735 0.078 Uiso 0.45 1 calc PR A 1
C31B C 0.0042(5) 0.0089(4) 0.2499(5) 0.0518(11) Uiso 0.55 1 d P A 3
H31D H 0.0639 -0.0590 0.2446 0.078 Uiso 0.55 1 calc PR A 3
H31E H -0.1021 0.0145 0.1707 0.078 Uiso 0.55 1 calc PR A 3
H31F H -0.0234 0.0085 0.3327 0.078 Uiso 0.55 1 calc PR A 3
C32B C 0.2864(5) 0.0998(4) 0.3758(4) 0.0440(8) Uiso 0.55 1 d P A 3
H32D H 0.3457 0.0315 0.3713 0.066 Uiso 0.55 1 calc PR A 3
H32E H 0.2589 0.1005 0.4586 0.066 Uiso 0.55 1 calc PR A 3
H32F H 0.3608 0.1620 0.3766 0.066 Uiso 0.55 1 calc PR A 3
C33B C 0.1664(7) 0.1024(5) 0.1254(5) 0.0592(12) Uiso 0.55 1 d P A 3
H33D H 0.2245 0.0331 0.1238 0.089 Uiso 0.55 1 calc PR A 3
H33E H 0.2426 0.1634 0.1252 0.089 Uiso 0.55 1 calc PR A 3
H33F H 0.0612 0.1073 0.0452 0.089 Uiso 0.55 1 calc PR A 3
C5 C -0.4792(3) 0.2500 -0.1526(2) 0.0334(5) Uani 1 2 d S . .
C51 C -0.5784(3) 0.1470(2) -0.1486(3) 0.0586(6) Uani 1 1 d . . .
H51A H -0.6150 0.1497 -0.0702 0.088 Uiso 1 1 calc R . .
H51B H -0.5049 0.0830 -0.1412 0.088 Uiso 1 1 calc R . .
H51C H -0.6796 0.1418 -0.2319 0.088 Uiso 1 1 calc R . .
C52 C -0.4200(5) 0.2500 -0.2731(3) 0.0519(8) Uani 1 2 d S . .
H52A H -0.3576 0.3179 -0.2733 0.078 Uiso 0.50 1 calc PR . .
H52B H -0.5200 0.2449 -0.3572 0.078 Uiso 0.50 1 calc PR . .
H52C H -0.3442 0.1873 -0.2664 0.078 Uiso 0.50 1 calc PR . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
144
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Ga1 0.02019(13) 0.02801(15) 0.01968(13) 0.000 0.00387(9) 0.000
N1 0.0264(10) 0.0382(11) 0.0236(9) 0.000 0.0038(8) 0.000
C1 0.0302(12) 0.0400(14) 0.0286(12) 0.000 0.0061(10) 0.000
C2 0.0277(12) 0.0552(17) 0.0292(12) 0.000 0.0108(10) 0.000
C3 0.0357(9) 0.0349(9) 0.0337(9) -0.0063(7) 0.0052(7) 0.0051(7)
C5 0.0261(11) 0.0391(13) 0.0256(11) 0.000 -0.0021(9) 0.000
C51 0.0409(11) 0.0617(15) 0.0590(14) 0.0049(12) 0.0006(10) -0.0185(11)
C52 0.0587(19) 0.066(2) 0.0251(12) 0.000 0.0080(12) 0.000
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ga1 C3 2.0315(19) 4_565 ?
Ga1 C3 2.0315(19) . ?
Ga1 C2 2.036(3) . ?
Ga1 C1 2.167(2) . ?
N1 C1 1.143(3) . ?
N1 C5 1.464(3) . ?
C2 C22 1.489(5) 4_565 ?
C2 C22 1.489(5) . ?
C2 C21 1.533(4) . ?
C2 C21 1.533(4) 4_565 ?
C2 C23 1.588(5) . ?
C2 C23 1.588(5) 4_565 ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?
C22 H22A 0.9800 . ?
C22 H22B 0.9800 . ?
C22 H22C 0.9800 . ?
C23 H23A 0.9800 . ?
C23 H23B 0.9800 . ?
C23 H23C 0.9800 . ?
C3 C31A 1.509(6) . ?
C3 C33B 1.521(5) . ?
145
C3 C32B 1.523(4) . ?
C3 C33A 1.547(6) . ?
C3 C31B 1.550(5) . ?
C3 C32A 1.577(5) . ?
C31A H31A 0.9800 . ?
C31A H31B 0.9800 . ?
C31A H31C 0.9800 . ?
C32A H32A 0.9800 . ?
C32A H32B 0.9800 . ?
C32A H32C 0.9800 . ?
C33A H33A 0.9800 . ?
C33A H33B 0.9800 . ?
C33A H33C 0.9800 . ?
C31B H31D 0.9800 . ?
C31B H31E 0.9800 . ?
C31B H31F 0.9800 . ?
C32B H32D 0.9800 . ?
C32B H32E 0.9800 . ?
C32B H32F 0.9800 . ?
C33B H33D 0.9800 . ?
C33B H33E 0.9800 . ?
C33B H33F 0.9800 . ?
C5 C51 1.516(3) . ?
C5 C51 1.516(3) 4_565 ?
C5 C52 1.520(4) . ?
C51 H51A 0.9800 . ?
C51 H51B 0.9800 . ?
C51 H51C 0.9800 . ?
C52 H52A 0.9800 . ?
C52 H52B 0.9800 . ?
C52 H52C 0.9800 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C3 Ga1 C3 117.51(12) 4_565 . ?
C3 Ga1 C2 116.65(6) 4_565 . ?
C3 Ga1 C2 116.65(6) . . ?
C3 Ga1 C1 100.96(6) 4_565 . ?
C3 Ga1 C1 100.96(6) . . ?
C2 Ga1 C1 98.65(10) . . ?
C1 N1 C5 178.4(3) . . ?
N1 C1 Ga1 173.9(2) . . ?
C22 C2 C22 79.2(4) 4_565 . ?
C22 C2 C21 128.4(3) 4_565 . ?
C22 C2 C21 109.9(3) . . ?
C22 C2 C21 109.9(3) 4_565 4_565 ?
C22 C2 C21 128.4(3) . 4_565 ?
146
C21 C2 C21 25.5(3) . 4_565 ?
C22 C2 C23 29.4(2) 4_565 . ?
C22 C2 C23 106.6(4) . . ?
C21 C2 C23 107.6(3) . . ?
C21 C2 C23 84.4(3) 4_565 . ?
C22 C2 C23 106.6(4) 4_565 4_565 ?
C22 C2 C23 29.4(2) . 4_565 ?
C21 C2 C23 84.4(3) . 4_565 ?
C21 C2 C23 107.6(3) 4_565 4_565 ?
C23 C2 C23 130.3(4) . 4_565 ?
C22 C2 Ga1 113.6(2) 4_565 . ?
C22 C2 Ga1 113.6(2) . . ?
C21 C2 Ga1 108.5(2) . . ?
C21 C2 Ga1 108.5(2) 4_565 . ?
C23 C2 Ga1 110.6(2) . . ?
C23 C2 Ga1 110.6(2) 4_565 . ?
C2 C21 H21A 109.5 . . ?
C2 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C2 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C2 C22 H22A 109.5 . . ?
C2 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
C2 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
C2 C23 H23A 109.5 . . ?
C2 C23 H23B 109.5 . . ?
H23A C23 H23B 109.5 . . ?
C2 C23 H23C 109.5 . . ?
H23A C23 H23C 109.5 . . ?
H23B C23 H23C 109.5 . . ?
C31A C3 C33B 86.1(3) . . ?
C31A C3 C32B 124.9(3) . . ?
C33B C3 C32B 108.5(3) . . ?
C31A C3 C33A 106.3(3) . . ?
C33B C3 C33A 23.4(3) . . ?
C32B C3 C33A 87.2(3) . . ?
C31A C3 C31B 22.6(2) . . ?
C33B C3 C31B 107.6(3) . . ?
C32B C3 C31B 109.7(3) . . ?
C33A C3 C31B 125.5(3) . . ?
C31A C3 C32A 107.3(3) . . ?
C33B C3 C32A 126.7(3) . . ?
C32B C3 C32A 23.4(2) . . ?
C33A C3 C32A 108.1(3) . . ?
C31B C3 C32A 88.5(3) . . ?
C31A C3 Ga1 113.9(2) . . ?
C33B C3 Ga1 111.6(2) . . ?
C32B C3 Ga1 109.09(19) . . ?
C33A C3 Ga1 111.9(3) . . ?
147
C31B C3 Ga1 110.3(2) . . ?
C32A C3 Ga1 109.1(2) . . ?
C3 C31A H31A 109.5 . . ?
C3 C31A H31B 109.5 . . ?
H31A C31A H31B 109.5 . . ?
C3 C31A H31C 109.5 . . ?
H31A C31A H31C 109.5 . . ?
H31B C31A H31C 109.5 . . ?
C3 C32A H32A 109.5 . . ?
C3 C32A H32B 109.5 . . ?
H32A C32A H32B 109.5 . . ?
C3 C32A H32C 109.5 . . ?
H32A C32A H32C 109.5 . . ?
H32B C32A H32C 109.5 . . ?
C3 C33A H33A 109.5 . . ?
C3 C33A H33B 109.5 . . ?
H33A C33A H33B 109.5 . . ?
C3 C33A H33C 109.5 . . ?
H33A C33A H33C 109.5 . . ?
H33B C33A H33C 109.5 . . ?
C3 C31B H31D 109.5 . . ?
C3 C31B H31E 109.5 . . ?
H31D C31B H31E 109.5 . . ?
C3 C31B H31F 109.5 . . ?
H31D C31B H31F 109.5 . . ?
H31E C31B H31F 109.5 . . ?
C3 C32B H32D 109.5 . . ?
C3 C32B H32E 109.5 . . ?
H32D C32B H32E 109.5 . . ?
C3 C32B H32F 109.5 . . ?
H32D C32B H32F 109.5 . . ?
H32E C32B H32F 109.5 . . ?
C3 C33B H33D 109.5 . . ?
C3 C33B H33E 109.5 . . ?
H33D C33B H33E 109.5 . . ?
C3 C33B H33F 109.5 . . ?
H33D C33B H33F 109.5 . . ?
H33E C33B H33F 109.5 . . ?
N1 C5 C51 107.09(15) . . ?
N1 C5 C51 107.09(15) . 4_565 ?
C51 C5 C51 112.3(3) . 4_565 ?
N1 C5 C52 106.9(2) . . ?
C51 C5 C52 111.52(17) . . ?
C51 C5 C52 111.52(17) 4_565 . ?
C5 C51 H51A 109.5 . . ?
C5 C51 H51B 109.5 . . ?
H51A C51 H51B 109.5 . . ?
C5 C51 H51C 109.5 . . ?
H51A C51 H51C 109.5 . . ?
H51B C51 H51C 109.5 . . ?
C5 C52 H52A 109.5 . . ?
C5 C52 H52B 109.5 . . ?
H52A C52 H52B 109.5 . . ?
148
C5 C52 H52C 109.5 . . ?
H52A C52 H52C 109.5 . . ?
H52B C52 H52C 109.5 . . ?
_diffrn_measured_fraction_theta_max
_diffrn_reflns_theta_full
_diffrn_measured_fraction_theta_full
_refine_diff_density_max
_refine_diff_density_min
_refine_diff_density_rms
1.000
26.00
1.000
0.560
-0.586
0.060
149
CIF File for Me3Ga·C≡NtBu
_audit_creation_method
_chemical_name_systematic
;
?
;
_chemical_name_common
_chemical_melting_point
_chemical_formula_moiety
_chemical_formula_sum
SHELXL-97
?
?
_chemical_formula_weight
'C8 H18 Ga N'
'C8 H18 Ga N'
197.95
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Ga' 'Ga' 0.2307 1.6083
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
_symmetry_space_group_name_H-M
orthorhombic
Pnma
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'-x, y+1/2, -z'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'-x-1/2, y-1/2, z-1/2'
'x, -y-1/2, z'
_cell_length_a
_cell_length_b
_cell_length_c
_cell_angle_alpha
_cell_angle_beta
_cell_angle_gamma
_cell_volume
_cell_formula_units_Z
_cell_measurement_temperature
_cell_measurement_reflns_used
_cell_measurement_theta_min
_cell_measurement_theta_max
13.5497(4)
9.6064(3)
8.6082(2)
90.00
90.00
90.00
1120.48(5)
4
-133
4.60
70.92
150
_exptl_crystal_description
_exptl_crystal_colour
_exptl_crystal_size_max
_exptl_crystal_size_mid
_exptl_crystal_size_min
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn
_exptl_crystal_density_method
_exptl_crystal_F_000
_exptl_absorpt_coefficient_mu
_exptl_absorpt_correction_type
_exptl_absorpt_correction_T_min
_exptl_absorpt_correction_T_max
_exptl_absorpt_process_details ?
cube
colorless
.25
.25
.25
1.173
'not measured'
416
2.400
multi-scan
0.808
1.000
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
_diffrn_radiation_wavelength
_diffrn_radiation_type
_diffrn_radiation_source
_diffrn_radiation_monochromator
_diffrn_measurement_device_type
_diffrn_measurement_method
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
?
_diffrn_reflns_number
_diffrn_reflns_av_R_equivalents
_diffrn_reflns_av_sigmaI/netI
_diffrn_reflns_limit_h_min
_diffrn_reflns_limit_h_max
_diffrn_reflns_limit_k_min
_diffrn_reflns_limit_k_max
_diffrn_reflns_limit_l_min
_diffrn_reflns_limit_l_max
_diffrn_reflns_theta_min
_diffrn_reflns_theta_max
_reflns_number_total
_reflns_number_gt
_reflns_threshold_expression
-133
0.71073
MoK\a
'fine-focus sealed tube'
graphite
'Bruker platform with 6k CCD'
'omega scans'
_computing_data_collection
_computing_cell_refinement
_computing_data_reduction
_computing_structure_solution
_computing_structure_refinement
_computing_molecular_graphics ?
_computing_publication_material ?
'Smart 5.630'
'Saintplus 5.45'
'Saintplus 5.45'
'SHELXS-97 (Sheldrick, 1990)'
'SHELXL-97 (Sheldrick, 1997)'
4952
0.0145
0.0198
-8
21
-15
8
-7
13
2.80
35.46
2353
1759
>2sigma(I)
151
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0728P)^2^+0.3159P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary
difmap
_atom_sites_solution_hydrogens
geom
_refine_ls_hydrogen_treatment
mixed
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
2353
_refine_ls_number_parameters
89
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.0508
_refine_ls_R_factor_gt
0.0366
_refine_ls_wR_factor_ref
0.1242
_refine_ls_wR_factor_gt
0.1133
_refine_ls_goodness_of_fit_ref
1.033
_refine_ls_restrained_S_all
1.033
_refine_ls_shift/su_max
0.009
_refine_ls_shift/su_mean
0.001
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ga1 Ga 0.255359(18) 0.7500 0.75643(3) 0.02796(11) Uani 1 2 d S . .
N1 N 0.09850(15) 0.7500 0.4612(2) 0.0325(4) Uani 1 2 d S . .
C1 C 0.03163(18) 0.7500 0.3267(2) 0.0331(5) Uani 1 2 d S . .
C4 C 0.15171(19) 0.7500 0.5638(3) 0.0370(5) Uani 1 2 d S . .
C5 C 0.3821(2) 0.7500 0.6407(4) 0.0417(6) Uani 1 2 d S . .
C6 C 0.21654(16) 0.5740(2) 0.8609(2) 0.0421(4) Uani 1 1 d . . .
H6C H 0.1440(18) 0.575(2) 0.900(3) 0.047(6) Uiso 1 1 d . . .
H6B H 0.225(2) 0.488(4) 0.780(3) 0.057(8) Uiso 1 1 d . . .
152
H6A H 0.243(2) 0.582(5) 0.966(5) 0.114(14) Uiso 1 1 d . . .
H5B H 0.3892(19) 0.831(3) 0.584(3) 0.064(8) Uiso 1 1 d . . .
H5A H 0.438(4) 0.7500 0.710(5) 0.069(11) Uiso 1 2 d S . .
C21 C -0.0683(8) 0.8022(14) 0.3743(12) 0.0336(16) Uiso 0.20 1 d P . 1
C22 C 0.0851(5) 0.8180(8) 0.1932(8) 0.0237(13) Uiso 0.20 1 d P . 1
C23 C 0.0317(6) 0.5863(8) 0.2668(9) 0.0203(11) Uiso 0.20 1 d P . 1
C31 C -0.0762(8) 0.7500 0.3876(11) 0.050(2) Uiso 0.40 2 d SP . 2
C32 C 0.0578(7) 0.8712(10) 0.2251(9) 0.0681(18) Uiso 0.40 1 d P . 2
C41 C 0.1135(18) 0.7500 0.178(3) 0.074(5) Uiso 0.20 2 d SP A 3
C42 C -0.0510(19) 0.859(3) 0.369(3) 0.051(5) Uiso 0.10 1 d P . 3
C43 C 0.0067(12) 0.5876(19) 0.310(2) 0.027(3) Uiso 0.10 1 d P . 3
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Ga1 0.02899(15) 0.03207(17) 0.02284(15) 0.000 -0.00168(8) 0.000
N1 0.0342(9) 0.0375(10) 0.0259(8) 0.000 -0.0016(7) 0.000
C1 0.0285(10) 0.0461(13) 0.0247(9) 0.000 -0.0040(7) 0.000
C4 0.0399(12) 0.0417(13) 0.0293(10) 0.000 -0.0015(9) 0.000
C5 0.0392(13) 0.0416(14) 0.0442(14) 0.000 0.0110(11) 0.000
C6 0.0427(10) 0.0430(10) 0.0406(9) 0.0081(8) -0.0006(8) -0.0069(9)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ga1 C5 1.985(3) . ?
Ga1 C6 1.986(2) . ?
Ga1 C6 1.986(2) 8_575 ?
Ga1 C4 2.173(2) . ?
N1 C4 1.140(3) . ?
N1 C1 1.470(3) . ?
C1 C32 1.498(8) . ?
C1 C32 1.498(8) 8_575 ?
C1 C21 1.501(11) 8_575 ?
C1 C21 1.501(11) . ?
C1 C22 1.507(7) . ?
C1 C22 1.507(7) 8_575 ?
C1 C31 1.553(11) . ?
153
C1 C42 1.58(2) 8_575 ?
C1 C42 1.58(2) . ?
C1 C43 1.603(18) 8_575 ?
C1 C43 1.603(18) . ?
C5 H5B 0.92(3) . ?
C5 H5A 0.96(5) . ?
C6 H6C 1.04(2) . ?
C6 H6B 1.09(3) . ?
C6 H6A 0.98(4) . ?
C21 C21 1.00(3) 8_575 ?
C21 C23 1.959(14) 8_575 ?
C22 C22 1.307(16) 8_575 ?
C22 C23 1.330(11) 8_575 ?
C23 C22 1.330(11) 8_575 ?
C23 C21 1.959(14) 8_575 ?
C42 C43 1.06(3) 8_575 ?
C43 C42 1.06(3) 8_575 ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C5 Ga1 C6 117.14(7) . . ?
C5 Ga1 C6 117.15(7) . 8_575 ?
C6 Ga1 C6 116.74(13) . 8_575 ?
C5 Ga1 C4 100.14(11) . . ?
C6 Ga1 C4 100.03(7) . . ?
C6 Ga1 C4 100.03(7) 8_575 . ?
C4 N1 C1 178.8(2) . . ?
N1 C1 C32 108.3(3) . . ?
N1 C1 C32 108.3(3) . 8_575 ?
C32 C1 C32 102.0(8) . 8_575 ?
N1 C1 C21 109.9(4) . 8_575 ?
C32 C1 C21 129.3(6) . 8_575 ?
C32 C1 C21 96.5(6) 8_575 8_575 ?
N1 C1 C21 109.9(4) . . ?
C32 C1 C21 96.5(6) . . ?
C32 C1 C21 129.3(6) 8_575 . ?
C21 C1 C21 39.1(10) 8_575 . ?
N1 C1 C22 107.7(3) . . ?
C32 C1 C22 26.4(4) . . ?
C32 C1 C22 77.2(6) 8_575 . ?
C21 C1 C22 141.9(5) 8_575 . ?
C21 C1 C22 119.8(6) . . ?
N1 C1 C22 107.7(3) . 8_575 ?
C32 C1 C22 77.2(6) . 8_575 ?
C32 C1 C22 26.4(4) 8_575 8_575 ?
C21 C1 C22 119.8(6) 8_575 8_575 ?
C21 C1 C22 141.9(5) . 8_575 ?
C22 C1 C22 51.4(6) . 8_575 ?
N1 C1 C31 108.3(4) . . ?
C32 C1 C31 114.8(5) . . ?
154
C32 C1 C31 114.8(5) 8_575 . ?
C21 C1 C31 19.7(5) 8_575 . ?
C21 C1 C31 19.7(5) . . ?
C22 C1 C31 135.2(4) . . ?
C22 C1 C31 135.2(4) 8_575 . ?
N1 C1 C42 104.9(9) . 8_575 ?
C32 C1 C42 145.0(10) . 8_575 ?
C32 C1 C42 77.6(10) 8_575 8_575 ?
C21 C1 C42 22.2(9) 8_575 8_575 ?
C21 C1 C42 61.3(14) . 8_575 ?
C22 C1 C42 143.6(9) . 8_575 ?
C22 C1 C42 103.1(10) 8_575 8_575 ?
C31 C1 C42 41.8(10) . 8_575 ?
N1 C1 C42 104.9(9) . . ?
C32 C1 C42 77.6(10) . . ?
C32 C1 C42 145.0(10) 8_575 . ?
C21 C1 C42 61.3(14) 8_575 . ?
C21 C1 C42 22.2(9) . . ?
C22 C1 C42 103.1(10) . . ?
C22 C1 C42 143.6(9) 8_575 . ?
C31 C1 C42 41.8(10) . . ?
C42 C1 C42 83(2) 8_575 . ?
N1 C1 C43 101.6(6) . 8_575 ?
C32 C1 C43 40.6(7) . 8_575 ?
C32 C1 C43 138.9(9) 8_575 8_575 ?
C21 C1 C43 99.2(9) 8_575 8_575 ?
C21 C1 C43 60.6(8) . 8_575 ?
C22 C1 C43 67.0(8) . 8_575 ?
C22 C1 C43 117.0(8) 8_575 8_575 ?
C31 C1 C43 80.4(7) . 8_575 ?
C42 C1 C43 121.3(13) 8_575 8_575 ?
C42 C1 C43 39.0(11) . 8_575 ?
N1 C1 C43 101.6(6) . . ?
C32 C1 C43 138.9(9) . . ?
C32 C1 C43 40.6(7) 8_575 . ?
C21 C1 C43 60.6(8) 8_575 . ?
C21 C1 C43 99.2(9) . . ?
C22 C1 C43 117.0(8) . . ?
C22 C1 C43 67.0(8) 8_575 . ?
C31 C1 C43 80.4(7) . . ?
C42 C1 C43 39.0(11) 8_575 . ?
C42 C1 C43 121.3(13) . . ?
C43 C1 C43 153.5(11) 8_575 . ?
N1 C4 Ga1 178.9(2) . . ?
Ga1 C5 H5B 110.8(16) . . ?
Ga1 C5 H5A 112(2) . . ?
H5B C5 H5A 104(2) . . ?
Ga1 C6 H6C 112.7(13) . . ?
Ga1 C6 H6B 109.6(17) . . ?
H6C C6 H6B 108(2) . . ?
Ga1 C6 H6A 105(3) . . ?
H6C C6 H6A 93(2) . . ?
H6B C6 H6A 128(3) . . ?
C21 C21 C1 70.5(5) 8_575 . ?
C21 C21 C23 123.1(4) 8_575 8_575 ?
C1 C21 C23 55.2(4) . 8_575 ?
155
C22 C22 C23 133.7(5) 8_575 8_575 ?
C22 C22 C1 64.3(3) 8_575 . ?
C23 C22 C1 71.0(5) 8_575 . ?
C22 C23 C1 59.5(4) 8_575 . ?
C22 C23 C21 102.9(6) 8_575 8_575 ?
C1 C23 C21 48.2(4) . 8_575 ?
C43 C42 C1 71.8(16) 8_575 . ?
C42 C43 C1 69.1(17) 8_575 . ?
_diffrn_measured_fraction_theta_max
_diffrn_reflns_theta_full
_diffrn_measured_fraction_theta_full
_refine_diff_density_max
_refine_diff_density_min
_refine_diff_density_rms
0.882
26.00
0.966
0.533
-0.552
0.101
156
CIF File for Me3Al·C≡N(2,6-Me2C6H3)
_audit_creation_method
_chemical_name_systematic
;
?
;
_chemical_name_common
_chemical_melting_point
_chemical_formula_moiety
_chemical_formula_sum
SHELXL-97
?
?
'C12 H18 Al N'
'C12 H18 Al N'
_chemical_formula_weight
203.25
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Al' 'Al' 0.0645 0.0514
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
_symmetry_space_group_name_H-M
'triclinic'
' P-1'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
_cell_length_a
_cell_length_b
_cell_length_c
_cell_angle_alpha
_cell_angle_beta
_cell_angle_gamma
_cell_volume
_cell_formula_units_Z
_cell_measurement_temperature
_cell_measurement_reflns_used
_cell_measurement_theta_min
_cell_measurement_theta_max
7.3776(4)
10.6143(6)
17.2858(10)
92.011(2)
94.854(2)
91.323(2)
1347.47(13)
4
-133
5254
1.18
28.15
_exptl_crystal_description
_exptl_crystal_colour
_exptl_crystal_size_max
_exptl_crystal_size_mid
_exptl_crystal_size_min
_exptl_crystal_density_meas
'jagged square'
'colorless'
.25
.25
.25
?
157
_exptl_crystal_density_diffrn
_exptl_crystal_density_method
_exptl_crystal_F_000
_exptl_absorpt_coefficient_mu
_exptl_absorpt_correction_type
_exptl_absorpt_correction_T_min
_exptl_absorpt_correction_T_max
_exptl_absorpt_process_details
1.002
'not measured'
440
0.118
multi-scan
0.793
1.000
'sadabs (Sheldrick, 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
_diffrn_radiation_wavelength
_diffrn_radiation_type
_diffrn_radiation_source
_diffrn_radiation_monochromator
_diffrn_measurement_device_type
_diffrn_measurement_method
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
?
_diffrn_reflns_number
_diffrn_reflns_av_R_equivalents
_diffrn_reflns_av_sigmaI/netI
_diffrn_reflns_limit_h_min
_diffrn_reflns_limit_h_max
_diffrn_reflns_limit_k_min
_diffrn_reflns_limit_k_max
_diffrn_reflns_limit_l_min
_diffrn_reflns_limit_l_max
_diffrn_reflns_theta_min
_diffrn_reflns_theta_max
_reflns_number_total
_reflns_number_gt
_reflns_threshold_expression
-133
0.71073
MoK\a
'fine-focus sealed tube'
graphite
'Bruker platform with 6k CCD'
'10 scans'
_computing_data_collection
_computing_cell_refinement
_computing_data_reduction
_computing_structure_solution
_computing_structure_refinement
_computing_molecular_graphics ?
_computing_publication_material ?
'Smart 5.630'
'Saintplus 5.45'
'Saintplus 5.45'
'SHELXS-97 (Sheldrick, 1990)'
'SHELXL-97 (Sheldrick, 1997)'
16421
0.0437
0.0395
-9
9
-13
13
-21
21
1.18
26.00
5254
4712
>2sigma(I)
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
158
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0950P)^2^+0.4048P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary
difmap
_atom_sites_solution_hydrogens
difmap
_refine_ls_hydrogen_treatment
refall
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
5254
_refine_ls_number_parameters
337
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.0627
_refine_ls_R_factor_gt
0.0574
_refine_ls_wR_factor_ref
0.1624
_refine_ls_wR_factor_gt
0.1576
_refine_ls_goodness_of_fit_ref
1.113
_refine_ls_restrained_S_all
1.113
_refine_ls_shift/su_max
0.001
_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Al1 Al 0.29672(8) 0.90140(5) 0.35899(3) 0.03594(18) Uani 1 1 d . . .
Al2 Al 0.27221(7) 1.45138(5) 1.12509(3) 0.02826(17) Uani 1 1 d . . .
N1A N 0.2533(2) 1.21107(14) 1.00127(9) 0.0312(3) Uani 1 1 d . . .
C10 C 0.2051(2) 0.56223(17) 0.59031(10) 0.0287(4) Uani 1 1 d . . .
N1 N 0.26422(19) 0.66484(15) 0.47289(9) 0.0314(3) Uani 1 1 d . . .
C5A C 0.2466(2) 1.10589(17) 0.94953(10) 0.0290(4) Uani 1 1 d . . .
C1 C 0.2823(2) 0.75410(19) 0.43811(11) 0.0350(4) Uani 1 1 d . . .
C6 C 0.2630(2) 0.43873(18) 0.47164(11) 0.0323(4) Uani 1 1 d . . .
C7A C 0.2322(3) 1.0206(2) 0.82072(12) 0.0469(5) Uani 1 1 d . . .
C1A C 0.2592(3) 1.29556(17) 1.04493(11) 0.0342(4) Uani 1 1 d . . .
C12 C 0.1873(3) 0.6877(2) 0.63101(13) 0.0391(4) Uani 1 1 d . . .
C5 C 0.2432(2) 0.55280(17) 0.51243(10) 0.0279(4) Uani 1 1 d . . .
C9 C 0.1865(2) 0.45030(19) 0.62788(11) 0.0342(4) Uani 1 1 d . . .
C6A C 0.2385(3) 1.12792(19) 0.87010(11) 0.0357(4) Uani 1 1 d . . .
C10A C 0.2487(3) 0.98682(18) 0.98104(11) 0.0343(4) Uani 1 1 d . . .
159
C8 C 0.2059(3) 0.33502(19) 0.58938(13) 0.0391(4) Uani 1 1 d . . .
C3A C 0.4996(3) 1.4210(2) 1.18864(13) 0.0457(5) Uani 1 1 d . . .
H3X H 0.5213 1.4883 1.2288 0.069 Uiso 1 1 calc R . .
H3Y H 0.6010 1.4198 1.1555 0.069 Uiso 1 1 calc R . .
H3Z H 0.4898 1.3396 1.2133 0.069 Uiso 1 1 calc R . .
C2A C 0.2697(4) 1.5917(2) 1.05326(13) 0.0491(5) Uani 1 1 d . . .
H2X H 0.2750 1.6721 1.0831 0.074 Uiso 1 1 calc R . .
H2Y H 0.1577 1.5861 1.0184 0.074 Uiso 1 1 calc R . .
H2Z H 0.3752 1.5866 1.0225 0.074 Uiso 1 1 calc R . .
C12A C 0.2574(4) 0.9719(2) 1.06779(13) 0.0443(5) Uani 1 1 d . . .
C4A C 0.0485(3) 1.4227(2) 1.17718(13) 0.0458(5) Uani 1 1 d . . .
H4X H 0.0358 1.4913 1.2157 0.069 Uiso 1 1 calc R . .
H4Y H 0.0551 1.3422 1.2032 0.069 Uiso 1 1 calc R . .
HZ H -0.0569 1.4204 1.1386 0.069 Uiso 1 1 calc R . .
C7 C 0.2435(3) 0.32950(19) 0.51240(13) 0.0387(4) Uani 1 1 d . . .
C8A C 0.2344(4) 0.9016(2) 0.84960(14) 0.0513(6) Uani 1 1 d . . .
C9A C 0.2422(3) 0.8844(2) 0.92862(14) 0.0458(5) Uani 1 1 d . . .
C11 C 0.3029(3) 0.4352(3) 0.38755(12) 0.0446(5) Uani 1 1 d . . .
C11A C 0.2353(4) 1.2593(2) 0.84089(15) 0.0521(6) Uani 1 1 d . . .
H11A H 0.410(4) 0.489(3) 0.3813(15) 0.054(7) Uiso 1 1 d . . .
H9 H 0.164(3) 0.453(2) 0.6826(14) 0.041(6) Uiso 1 1 d . . .
H11B H 0.318(4) 0.348(3) 0.3689(18) 0.070(8) Uiso 1 1 d . . .
H8 H 0.191(3) 0.261(3) 0.6157(15) 0.049(6) Uiso 1 1 d . . .
H7 H 0.256(3) 0.248(3) 0.4904(16) 0.058(7) Uiso 1 1 d . . .
H9X H 0.244(4) 0.804(3) 0.9446(17) 0.073(9) Uiso 1 1 d . . .
H12A H 0.289(4) 0.734(3) 0.6342(17) 0.065(8) Uiso 1 1 d . . .
H12B H 0.101(5) 0.735(3) 0.604(2) 0.081(10) Uiso 1 1 d . . .
H11C H 0.201(4) 0.467(3) 0.3567(17) 0.063(8) Uiso 1 1 d . . .
H12Z H 0.364(4) 1.006(3) 1.0918(16) 0.058(7) Uiso 1 1 d . . .
H12X H 0.149(4) 1.015(3) 1.0887(17) 0.066(8) Uiso 1 1 d . . .
H12Y H 0.237(5) 0.897(4) 1.079(2) 0.089(11) Uiso 1 1 d . . .
H11X H 0.338(5) 1.306(3) 0.8596(19) 0.080(10) Uiso 1 1 d . . .
H12C H 0.149(4) 0.678(3) 0.684(2) 0.082(10) Uiso 1 1 d . . .
H8X H 0.232(3) 0.828(3) 0.8164(16) 0.061(8) Uiso 1 1 d . . .
H11Z H 0.129(4) 1.301(3) 0.8605(19) 0.078(9) Uiso 1 1 d . . .
C2 C 0.5281(3) 0.9936(3) 0.38761(18) 0.0622(7) Uani 1 1 d . . .
H2A H 0.5408 1.0631 0.3525 0.093 Uiso 1 1 calc R . .
H2B H 0.6293 0.9362 0.3835 0.093 Uiso 1 1 calc R . .
H2C H 0.5296 1.0274 0.4411 0.093 Uiso 1 1 calc R . .
C3 C 0.0820(3) 1.0002(3) 0.37837(19) 0.0627(7) Uani 1 1 d . . .
H3A H 0.0756 1.0720 0.3442 0.094 Uiso 1 1 calc R . .
H3B H 0.0915 1.0309 0.4327 0.094 Uiso 1 1 calc R . .
H3C H -0.0280 0.9468 0.3678 0.094 Uiso 1 1 calc R . .
H11Y H 0.221(4) 1.255(3) 0.785(2) 0.088(10) Uiso 1 1 d . . .
C4 C 0.2851(8) 0.7931(3) 0.26441(18) 0.0855(12) Uani 1 1 d . . .
H7X H 0.226(3) 1.034(2) 0.7662(16) 0.050(7) Uiso 1 1 d . . .
H4A H 0.173(5) 0.735(4) 0.257(2) 0.094(12) Uiso 1 1 d . . .
H4B H 0.370(5) 0.727(4) 0.265(2) 0.101(13) Uiso 1 1 d . . .
H4C H 0.290(8) 0.828(6) 0.222(4) 0.18(2) Uiso 1 1 d . . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
160
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Al1 0.0445(3) 0.0311(3) 0.0328(3) 0.0069(2) 0.0048(2) -0.0004(2)
Al2 0.0329(3) 0.0255(3) 0.0265(3) -0.0018(2) 0.0042(2) 0.0018(2)
N1A 0.0337(8) 0.0275(8) 0.0326(8) 0.0006(7) 0.0039(6) 0.0011(6)
C10 0.0230(8) 0.0331(9) 0.0297(9) 0.0031(7) -0.0003(6) -0.0001(6)
N1 0.0250(7) 0.0394(9) 0.0299(8) 0.0075(7) -0.0001(6) -0.0010(6)
C5A 0.0319(8) 0.0268(9) 0.0280(9) -0.0037(7) 0.0027(7) 0.0017(7)
C1 0.0323(9) 0.0407(11) 0.0321(9) 0.0061(8) 0.0019(7) -0.0013(8)
C6 0.0218(8) 0.0417(10) 0.0330(9) -0.0009(8) 0.0009(7) 0.0024(7)
C7A 0.0574(13) 0.0538(13) 0.0283(10) -0.0062(9) -0.0001(9) 0.0004(10)
C1A 0.0411(10) 0.0275(9) 0.0342(9) 0.0002(8) 0.0051(8) 0.0009(7)
C12 0.0435(11) 0.0364(11) 0.0375(11) 0.0007(8) 0.0039(9) 0.0009(9)
C5 0.0206(7) 0.0323(9) 0.0307(9) 0.0076(7) -0.0002(6) -0.0012(6)
C9 0.0288(9) 0.0407(11) 0.0337(10) 0.0085(8) 0.0039(7) 0.0001(7)
C6A 0.0369(9) 0.0395(10) 0.0303(9) 0.0010(8) 0.0006(7) 0.0013(8)
C10A 0.0407(10) 0.0293(9) 0.0329(9) 0.0015(7) 0.0024(7) 0.0034(7)
C8 0.0351(10) 0.0321(10) 0.0505(12) 0.0124(9) 0.0020(8) 0.0003(8)
C3A 0.0374(10) 0.0552(13) 0.0441(11) 0.0011(10) -0.0005(8) 0.0047(9)
C2A 0.0711(15) 0.0328(11) 0.0432(12) 0.0047(9) 0.0034(10) -0.0001(10)
C12A 0.0608(14) 0.0373(12) 0.0355(11) 0.0087(9) 0.0054(10) 0.0007(10)
C4A 0.0387(10) 0.0596(14) 0.0397(11) -0.0029(10) 0.0089(8) 0.0004(9)
C7 0.0335(10) 0.0322(10) 0.0497(12) -0.0029(9) 0.0008(8) 0.0040(7)
C8A 0.0690(15) 0.0397(12) 0.0435(12) -0.0173(10) 0.0025(10) -0.0009(10)
C9A 0.0638(14) 0.0255(10) 0.0480(12) -0.0037(9) 0.0045(10) 0.0025(9)
C11 0.0360(11) 0.0620(15) 0.0356(11) -0.0061(10) 0.0046(8) 0.0053(10)
C11A 0.0682(16) 0.0474(13) 0.0410(12) 0.0139(10) 0.0011(11) 0.0015(12)
C2 0.0508(13) 0.0538(15) 0.0836(19) 0.0084(13) 0.0164(13) -0.0115(11)
C3 0.0494(13) 0.0511(14) 0.088(2) 0.0109(13) 0.0035(13) 0.0082(11)
C4 0.164(4) 0.0534(17) 0.0394(15) -0.0036(13) 0.0130(18) -0.005(2)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Al1 C4 1.960(3) . ?
Al1 C3 1.965(3) . ?
Al1 C2 1.965(3) . ?
Al1 C1 2.120(2) . ?
Al2 C3A 1.965(2) . ?
Al2 C4A 1.969(2) . ?
Al2 C2A 1.972(2) . ?
Al2 C1A 2.1153(19) . ?
N1A C1A 1.149(2) . ?
161
N1A C5A 1.403(2) . ?
C10 C9 1.383(3) . ?
C10 C5 1.399(2) . ?
C10 C12 1.498(3) . ?
N1 C1 1.151(3) . ?
N1 C5 1.404(2) . ?
C5A C10A 1.394(3) . ?
C5A C6A 1.397(3) . ?
C6 C7 1.388(3) . ?
C6 C5 1.396(3) . ?
C6 C11 1.507(3) . ?
C7A C8A 1.374(4) . ?
C7A C6A 1.397(3) . ?
C7A H7X 0.95(3) . ?
C12 H12A 0.88(3) . ?
C12 H12B 0.92(4) . ?
C12 H12C 0.99(3) . ?
C9 C8 1.388(3) . ?
C9 H9 0.97(2) . ?
C6A C11A 1.500(3) . ?
C10A C9A 1.388(3) . ?
C10A C12A 1.510(3) . ?
C8 C7 1.382(3) . ?
C8 H8 0.93(3) . ?
C3A H3X 0.9800 . ?
C3A H3Y 0.9800 . ?
C3A H3Z 0.9800 . ?
C2A H2X 0.9800 . ?
C2A H2Y 0.9800 . ?
C2A H2Z 0.9800 . ?
C12A H12Z 0.92(3) . ?
C12A H12X 1.02(3) . ?
C12A H12Y 0.84(4) . ?
C4A H4X 0.9800 . ?
C4A H4Y 0.9800 . ?
C4A HZ 0.9800 . ?
C7 H7 0.95(3) . ?
C8A C9A 1.381(3) . ?
C8A H8X 0.95(3) . ?
C9A H9X 0.90(3) . ?
C11 H11A 0.98(3) . ?
C11 H11B 0.98(3) . ?
C11 H11C 0.96(3) . ?
C11A H11X 0.93(3) . ?
C11A H11Z 0.99(3) . ?
C11A H11Y 0.96(4) . ?
C2 H2A 0.9800 . ?
C2 H2B 0.9800 . ?
C2 H2C 0.9800 . ?
C3 H3A 0.9800 . ?
C3 H3B 0.9800 . ?
C3 H3C 0.9800 . ?
C4 H4A 1.01(4) . ?
C4 H4B 0.95(4) . ?
C4 H4C 0.83(6) . ?
162
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C4 Al1 C3 117.87(19) . . ?
C4 Al1 C2 116.47(18) . . ?
C3 Al1 C2 113.34(12) . . ?
C4 Al1 C1 96.56(12) . . ?
C3 Al1 C1 102.65(10) . . ?
C2 Al1 C1 106.51(10) . . ?
C3A Al2 C4A 115.00(10) . . ?
C3A Al2 C2A 118.12(11) . . ?
C4A Al2 C2A 116.24(11) . . ?
C3A Al2 C1A 101.55(9) . . ?
C4A Al2 C1A 101.06(9) . . ?
C2A Al2 C1A 100.37(9) . . ?
C1A N1A C5A 178.56(19) . . ?
C9 C10 C5 116.76(17) . . ?
C9 C10 C12 121.82(17) . . ?
C5 C10 C12 121.42(17) . . ?
C1 N1 C5 177.54(18) . . ?
C10A C5A C6A 124.64(17) . . ?
C10A C5A N1A 117.64(16) . . ?
C6A C5A N1A 117.72(17) . . ?
N1 C1 Al1 171.06(16) . . ?
C7 C6 C5 116.66(17) . . ?
C7 C6 C11 122.01(18) . . ?
C5 C6 C11 121.33(19) . . ?
C8A C7A C6A 121.3(2) . . ?
C8A C7A H7X 121.6(15) . . ?
C6A C7A H7X 117.2(15) . . ?
N1A C1A Al2 179.57(17) . . ?
C10 C12 H12A 112.8(19) . . ?
C10 C12 H12B 111(2) . . ?
H12A C12 H12B 106(3) . . ?
C10 C12 H12C 111(2) . . ?
H12A C12 H12C 109(3) . . ?
H12B C12 H12C 107(3) . . ?
C6 C5 C10 124.03(17) . . ?
C6 C5 N1 117.88(16) . . ?
C10 C5 N1 118.09(16) . . ?
C10 C9 C8 120.91(18) . . ?
C10 C9 H9 119.1(14) . . ?
C8 C9 H9 120.0(14) . . ?
C7A C6A C5A 115.80(19) . . ?
C7A C6A C11A 122.9(2) . . ?
C5A C6A C11A 121.30(19) . . ?
C9A C10A C5A 116.48(18) . . ?
C9A C10A C12A 122.46(19) . . ?
C5A C10A C12A 121.05(17) . . ?
C7 C8 C9 120.67(19) . . ?
C7 C8 H8 120.3(16) . . ?
163
C9 C8 H8 119.1(16) . . ?
Al2 C3A H3X 109.5 . . ?
Al2 C3A H3Y 109.5 . . ?
H3X C3A H3Y 109.5 . . ?
Al2 C3A H3Z 109.5 . . ?
H3X C3A H3Z 109.5 . . ?
H3Y C3A H3Z 109.5 . . ?
Al2 C2A H2X 109.5 . . ?
Al2 C2A H2Y 109.5 . . ?
H2X C2A H2Y 109.5 . . ?
Al2 C2A H2Z 109.5 . . ?
H2X C2A H2Z 109.5 . . ?
H2Y C2A H2Z 109.5 . . ?
C10A C12A H12Z 111.0(17) . . ?
C10A C12A H12X 108.7(17) . . ?
H12Z C12A H12X 110(2) . . ?
C10A C12A H12Y 112(2) . . ?
H12Z C12A H12Y 113(3) . . ?
H12X C12A H12Y 101(3) . . ?
Al2 C4A H4X 109.5 . . ?
Al2 C4A H4Y 109.5 . . ?
H4X C4A H4Y 109.5 . . ?
Al2 C4A HZ 109.5 . . ?
H4X C4A HZ 109.5 . . ?
H4Y C4A HZ 109.5 . . ?
C8 C7 C6 120.98(18) . . ?
C8 C7 H7 115.6(17) . . ?
C6 C7 H7 123.4(17) . . ?
C7A C8A C9A 120.93(19) . . ?
C7A C8A H8X 121.8(17) . . ?
C9A C8A H8X 117.2(17) . . ?
C8A C9A C10A 120.9(2) . . ?
C8A C9A H9X 117(2) . . ?
C10A C9A H9X 122(2) . . ?
C6 C11 H11A 109.6(15) . . ?
C6 C11 H11B 110.4(18) . . ?
H11A C11 H11B 112(2) . . ?
C6 C11 H11C 109.2(16) . . ?
H11A C11 H11C 109(2) . . ?
H11B C11 H11C 107(2) . . ?
C6A C11A H11X 112(2) . . ?
C6A C11A H11Z 107.6(19) . . ?
H11X C11A H11Z 107(3) . . ?
C6A C11A H11Y 109(2) . . ?
H11X C11A H11Y 112(3) . . ?
H11Z C11A H11Y 109(3) . . ?
Al1 C2 H2A 109.5 . . ?
Al1 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
Al1 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
Al1 C3 H3A 109.5 . . ?
Al1 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
Al1 C3 H3C 109.5 . . ?
164
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
Al1 C4 H4A 114(2) . . ?
Al1 C4 H4B 115(2) . . ?
H4A C4 H4B 95(3) . . ?
Al1 C4 H4C 118(4) . . ?
H4A C4 H4C 105(4) . . ?
H4B C4 H4C 107(5) . . ?
_diffrn_measured_fraction_theta_max
_diffrn_reflns_theta_full
_diffrn_measured_fraction_theta_full
_refine_diff_density_max
_refine_diff_density_min
_refine_diff_density_rms
0.995
26.00
0.995
0.707
-0.200
0.077
165
CIF File for Me3Ga·C≡N(2,6-Me2C6H3)
data_sad
_audit_creation_method
_chemical_name_systematic
;
?
;
_chemical_name_common
_chemical_melting_point
_chemical_formula_moiety
_chemical_formula_sum
SHELXL-97
?
?
_chemical_formula_weight
'C12 H18 Ga N'
'C12 H18 Ga N'
245.99
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Ga' 'Ga' 0.2307 1.6083
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
_symmetry_space_group_name_H-M
'triclinic'
'P -1'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
_cell_length_a
_cell_length_b
_cell_length_c
_cell_angle_alpha
_cell_angle_beta
_cell_angle_gamma
_cell_volume
_cell_formula_units_Z
_cell_measurement_temperature
_cell_measurement_reflns_used
_cell_measurement_theta_min
_cell_measurement_theta_max
7.3706(2)
10.6485(3)
17.2629(4)
92.170(1)
95.034(1)
91.303(1)
1348.24(6)
4
–133
7642
2.2
28.28
_exptl_crystal_description
_exptl_crystal_colour
_exptl_crystal_size_max
_exptl_crystal_size_mid
'cube'
'colorless'
.20
.20
166
_exptl_crystal_size_min
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn
_exptl_crystal_density_method
_exptl_crystal_F_000
_exptl_absorpt_coefficient_mu
_exptl_absorpt_correction_type
_exptl_absorpt_correction_T_min
_exptl_absorpt_correction_T_max
_exptl_absorpt_process_details
.20
1.212
'not measured'
512
2.008
multi-scan
0.773
1.000
'sadabs (Sheldrick, 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
_diffrn_radiation_wavelength
_diffrn_radiation_type
_diffrn_radiation_source
_diffrn_radiation_monochromator
_diffrn_measurement_device_type
_diffrn_measurement_method
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
?
_diffrn_reflns_number
_diffrn_reflns_av_R_equivalents
_diffrn_reflns_av_sigmaI/netI
_diffrn_reflns_limit_h_min
_diffrn_reflns_limit_h_max
_diffrn_reflns_limit_k_min
_diffrn_reflns_limit_k_max
_diffrn_reflns_limit_l_min
_diffrn_reflns_limit_l_max
_diffrn_reflns_theta_min
_diffrn_reflns_theta_max
_reflns_number_total
_reflns_number_gt
_reflns_threshold_expression
140(2)
0.71073
MoK\a
'fine-focus sealed tube'
graphite
'Bruker platform with 6k CCD'
'omega scans'
_computing_data_collection
_computing_cell_refinement
_computing_data_reduction
_computing_structure_solution
_computing_structure_refinement
_computing_molecular_graphics ?
_computing_publication_material ?
'Smart 5.630'
'Saintplus 5.45'
'Saintplus 5.45'
'SHELXS-97 (Sheldrick, 1990)'
'SHELXL-97 (Sheldrick, 1997)'
18897
0.0233
0.0241
-9
9
-14
14
-23
23
1.19
28.28
6685
6198
>2sigma(I)
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
167
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0270P)^2^+0.3433P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary
difmap
_atom_sites_solution_hydrogens
difmap
_refine_ls_hydrogen_treatment
mixed
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
6685
_refine_ls_number_parameters
337
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.0277
_refine_ls_R_factor_gt
0.0252
_refine_ls_wR_factor_ref
0.0657
_refine_ls_wR_factor_gt
0.0645
_refine_ls_goodness_of_fit_ref
1.106
_refine_ls_restrained_S_all
1.106
_refine_ls_shift/su_max
0.004
_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ga1 Ga 0.29876(2) 0.903565(15) 0.357615(9) 0.03526(5) Uani 1 1 d . . .
Ga1A Ga 0.27281(2) 1.455668(14) 1.125988(8) 0.02782(5) Uani 1 1 d . . .
N1 N 0.26577(15) 0.66463(12) 0.47332(7) 0.0312(2) Uani 1 1 d . . .
N1A N 0.25384(16) 1.21072(11) 1.00077(7) 0.0306(2) Uani 1 1 d . . .
C1 C 0.2852(2) 0.75422(16) 0.43960(9) 0.0361(3) Uani 1 1 d . . .
C1A C 0.2604(2) 1.29528(14) 1.04401(9) 0.0362(3) Uani 1 1 d . . .
C2 C 0.5339(3) 0.9931(2) 0.38803(14) 0.0615(5) Uani 1 1 d . . .
H2A H 0.5488 1.0629 0.3535 0.092 Uiso 1 1 calc R . .
H2B H 0.6338 0.9348 0.3837 0.092 Uiso 1 1 calc R . .
H2C H 0.5356 1.0260 0.4419 0.092 Uiso 1 1 calc R . .
C2A C 0.2697(3) 1.59378(16) 1.05229(10) 0.0494(4) Uani 1 1 d . . .
H2X H 0.2750 1.6748 1.0814 0.074 Uiso 1 1 calc R . .
H2Y H 0.1574 1.5872 1.0173 0.074 Uiso 1 1 calc R . .
168
H2Z H 0.3752 1.5878 1.0217 0.074 Uiso 1 1 calc R . .
C3 C 0.0830(3) 1.0009(2) 0.37930(15) 0.0625(5) Uani 1 1 d . . .
H3A H 0.0743 1.0731 0.3457 0.094 Uiso 1 1 calc R . .
H3B H 0.0945 1.0307 0.4340 0.094 Uiso 1 1 calc R . .
H3C H -0.0269 0.9472 0.3690 0.094 Uiso 1 1 calc R . .
C3A C 0.5024(2) 1.42309(19) 1.18900(10) 0.0462(4) Uani 1 1 d . . .
H3X H 0.5262 1.4898 1.2296 0.069 Uiso 1 1 calc R . .
H3Y H 0.6030 1.4215 1.1554 0.069 Uiso 1 1 calc R . .
H3Z H 0.4920 1.3418 1.2133 0.069 Uiso 1 1 calc R . .
C4 C 0.2838(6) 0.7920(3) 0.26303(14) 0.0841(10) Uani 1 1 d . . .
C4A C 0.0464(2) 1.42457(19) 1.17679(10) 0.0466(4) Uani 1 1 d . . .
H4X H 0.0316 1.4924 1.2155 0.070 Uiso 1 1 calc R . .
H4Y H 0.0536 1.3441 1.2025 0.070 Uiso 1 1 calc R . .
H4Z H -0.0582 1.4218 1.1375 0.070 Uiso 1 1 calc R . .
C5 C 0.24328(17) 0.55262(13) 0.51218(8) 0.0269(3) Uani 1 1 d . . .
C5A C 0.24708(19) 1.10562(13) 0.94911(8) 0.0282(3) Uani 1 1 d . . .
C6 C 0.26323(18) 0.43930(15) 0.47123(8) 0.0321(3) Uani 1 1 d . . .
C6A C 0.2388(2) 1.12636(15) 0.86942(8) 0.0353(3) Uani 1 1 d . . .
C7 C 0.2427(2) 0.32989(15) 0.51168(10) 0.0390(3) Uani 1 1 d . . .
C7A C 0.2325(3) 1.01999(19) 0.82019(9) 0.0468(4) Uani 1 1 d . . .
C8 C 0.2040(2) 0.33522(15) 0.58887(10) 0.0387(3) Uani 1 1 d . . .
C8A C 0.2349(3) 0.90086(18) 0.84929(11) 0.0525(5) Uani 1 1 d . . .
C9 C 0.18445(19) 0.44933(15) 0.62750(9) 0.0330(3) Uani 1 1 d . . .
C9A C 0.2424(3) 0.88429(16) 0.92861(11) 0.0474(4) Uani 1 1 d . . .
C10 C 0.20414(17) 0.56215(13) 0.59017(8) 0.0279(3) Uani 1 1 d . . .
C10A C 0.2489(2) 0.98695(14) 0.98073(8) 0.0346(3) Uani 1 1 d . . .
C11 C 0.3037(2) 0.4360(2) 0.38736(10) 0.0450(4) Uani 1 1 d . . .
C11A C 0.2361(3) 1.2574(2) 0.84023(12) 0.0524(5) Uani 1 1 d . . .
C12 C 0.1868(2) 0.68632(16) 0.63142(10) 0.0380(3) Uani 1 1 d . . .
C12A C 0.2580(3) 0.97274(18) 1.06751(10) 0.0449(4) Uani 1 1 d . . .
H4A H 0.172(4) 0.738(3) 0.2609(18) 0.104(11) Uiso 1 1 d . . .
H4B H 0.386(5) 0.734(3) 0.2661(18) 0.108(12) Uiso 1 1 d . . .
H4C H 0.294(5) 0.836(4) 0.220(2) 0.140(14) Uiso 1 1 d . . .
H7 H 0.256(3) 0.254(2) 0.4868(12) 0.053(6) Uiso 1 1 d . . .
H7X H 0.227(3) 1.033(2) 0.7672(13) 0.058(6) Uiso 1 1 d . . .
H8 H 0.188(3) 0.2604(19) 0.6153(11) 0.046(5) Uiso 1 1 d . . .
H8X H 0.234(3) 0.830(2) 0.8150(14) 0.065(7) Uiso 1 1 d . . .
H9 H 0.156(3) 0.4553(18) 0.6806(11) 0.040(5) Uiso 1 1 d . . .
H9X H 0.244(3) 0.802(2) 0.9480(13) 0.062(6) Uiso 1 1 d . . .
H11A H 0.407(3) 0.486(2) 0.3801(12) 0.053(6) Uiso 1 1 d . . .
H11B H 0.320(3) 0.352(3) 0.3690(14) 0.070(7) Uiso 1 1 d . . .
H11C H 0.215(3) 0.469(2) 0.3557(13) 0.054(6) Uiso 1 1 d . . .
H11X H 0.345(4) 1.301(3) 0.8576(15) 0.080(8) Uiso 1 1 d . . .
H11Y H 0.230(3) 1.255(2) 0.7872(15) 0.072(7) Uiso 1 1 d . . .
H11Z H 0.139(4) 1.304(2) 0.8582(14) 0.069(7) Uiso 1 1 d . . .
H12A H 0.300(3) 0.734(2) 0.6337(13) 0.063(6) Uiso 1 1 d . . .
H12B H 0.106(3) 0.737(2) 0.6050(14) 0.069(7) Uiso 1 1 d . . .
H12C H 0.146(3) 0.679(2) 0.6824(15) 0.077(8) Uiso 1 1 d . . .
H12X H 0.159(3) 1.017(2) 1.0895(13) 0.061(6) Uiso 1 1 d . . .
H12Y H 0.255(3) 0.891(3) 1.0813(14) 0.073(7) Uiso 1 1 d . . .
H12Z H 0.368(3) 1.012(2) 1.0918(13) 0.062(6) Uiso 1 1 d . . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
169
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Ga1 0.04183(10) 0.03197(9) 0.03240(9) 0.00622(6) 0.00429(7) -0.00150(7)
Ga1A 0.03010(8) 0.02695(8) 0.02643(8) -0.00146(6) 0.00363(6) 0.00084(6)
N1 0.0227(5) 0.0406(7) 0.0301(6) 0.0085(5) 0.0002(4) -0.0034(5)
N1A 0.0338(6) 0.0266(6) 0.0314(6) -0.0012(5) 0.0037(5) 0.0001(5)
C1 0.0296(7) 0.0445(8) 0.0341(7) 0.0073(6) 0.0009(6) -0.0035(6)
C1A 0.0423(8) 0.0306(7) 0.0360(7) -0.0006(6) 0.0060(6) 0.0004(6)
C2 0.0466(10) 0.0573(12) 0.0822(15) 0.0094(10) 0.0161(10) -0.0136(9)
C2A 0.0702(12) 0.0342(8) 0.0433(9) 0.0068(7) 0.0008(8) -0.0005(8)
C3 0.0466(10) 0.0504(11) 0.0902(16) 0.0062(10) 0.0019(10) 0.0078(9)
C3A 0.0322(8) 0.0588(11) 0.0469(9) 0.0039(8) -0.0007(7) 0.0027(7)
C4 0.156(3) 0.0575(14) 0.0380(11) -0.0041(9) 0.0103(14) -0.0046(18)
C4A 0.0343(8) 0.0658(11) 0.0404(8) -0.0024(8) 0.0094(6) 0.0003(8)
C5 0.0184(5) 0.0331(7) 0.0291(6) 0.0072(5) -0.0003(5) -0.0021(5)
C5A 0.0305(6) 0.0261(6) 0.0275(6) -0.0028(5) 0.0016(5) 0.0002(5)
C6 0.0202(6) 0.0426(8) 0.0329(7) -0.0008(6) 0.0003(5) 0.0012(5)
C6A 0.0373(7) 0.0393(8) 0.0287(7) 0.0028(6) 0.0001(6) 0.0001(6)
C7 0.0317(7) 0.0339(8) 0.0504(9) -0.0036(7) -0.0013(6) 0.0039(6)
C7A 0.0567(10) 0.0552(10) 0.0271(7) -0.0058(7) 0.0006(7) -0.0020(8)
C8 0.0342(7) 0.0330(7) 0.0490(9) 0.0113(7) 0.0008(6) -0.0011(6)
C8A 0.0687(12) 0.0423(9) 0.0444(9) -0.0193(8) 0.0035(8) -0.0011(8)
C9 0.0279(7) 0.0399(8) 0.0317(7) 0.0096(6) 0.0026(5) -0.0007(6)
C9A 0.0663(12) 0.0270(7) 0.0485(9) -0.0020(7) 0.0042(8) 0.0010(7)
C10 0.0208(6) 0.0339(7) 0.0288(6) 0.0041(5) 0.0005(5) -0.0007(5)
C10A 0.0409(8) 0.0301(7) 0.0326(7) 0.0009(5) 0.0025(6) 0.0012(6)
C11 0.0329(8) 0.0678(12) 0.0341(8) -0.0059(8) 0.0041(6) 0.0046(8)
C11A 0.0662(13) 0.0496(11) 0.0421(10) 0.0181(8) 0.0021(9) 0.0012(10)
C12 0.0411(8) 0.0371(8) 0.0357(8) -0.0008(6) 0.0034(6) -0.0006(7)
C12A 0.0622(11) 0.0380(9) 0.0353(8) 0.0091(7) 0.0053(8) 0.0030(8)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ga1 C3 1.973(2) . ?
Ga1 C4 1.976(2) . ?
Ga1 C2 1.979(2) . ?
Ga1 C1 2.1749(15) . ?
Ga1A C3A 1.9746(16) . ?
Ga1A C4A 1.9795(16) . ?
Ga1A C2A 1.9799(17) . ?
170
Ga1A C1A 2.1715(15) . ?
N1 C1 1.149(2) . ?
N1 C5 1.4040(17) . ?
N1A C1A 1.1450(19) . ?
N1A C5A 1.4015(17) . ?
C2 H2A 0.9800 . ?
C2 H2B 0.9800 . ?
C2 H2C 0.9800 . ?
C2A H2X 0.9800 . ?
C2A H2Y 0.9800 . ?
C2A H2Z 0.9800 . ?
C3 H3A 0.9800 . ?
C3 H3B 0.9800 . ?
C3 H3C 0.9800 . ?
C3A H3X 0.9800 . ?
C3A H3Y 0.9800 . ?
C3A H3Z 0.9800 . ?
C4 H4A 0.99(3) . ?
C4 H4B 0.98(3) . ?
C4 H4C 0.89(4) . ?
C4A H4X 0.9800 . ?
C4A H4Y 0.9800 . ?
C4A H4Z 0.9800 . ?
C5 C6 1.393(2) . ?
C5 C10 1.4020(18) . ?
C5A C10A 1.395(2) . ?
C5A C6A 1.3977(19) . ?
C6 C7 1.393(2) . ?
C6 C11 1.503(2) . ?
C6A C7A 1.387(2) . ?
C6A C11A 1.501(2) . ?
C7 C8 1.386(2) . ?
C7 H7 0.92(2) . ?
C7A C8A 1.382(3) . ?
C7A H7X 0.93(2) . ?
C8 C9 1.380(2) . ?
C8 H8 0.94(2) . ?
C8A C9A 1.384(3) . ?
C8A H8X 0.94(2) . ?
C9 C10 1.395(2) . ?
C9 H9 0.959(19) . ?
C9A C10A 1.386(2) . ?
C9A H9X 0.95(2) . ?
C10 C12 1.491(2) . ?
C10A C12A 1.507(2) . ?
C11 H11A 0.94(2) . ?
C11 H11B 0.95(3) . ?
C11 H11C 0.90(2) . ?
C11A H11X 0.94(3) . ?
C11A H11Y 0.91(3) . ?
C11A H11Z 0.95(3) . ?
C12 H12A 0.97(2) . ?
C12 H12B 0.92(2) . ?
C12 H12C 0.96(3) . ?
C12A H12X 0.97(2) . ?
C12A H12Y 0.91(3) . ?
171
C12A H12Z 0.96(2) . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C3 Ga1 C4 118.35(15) . . ?
C3 Ga1 C2 114.13(10) . . ?
C4 Ga1 C2 117.32(15) . . ?
C3 Ga1 C1 101.39(8) . . ?
C4 Ga1 C1 96.06(9) . . ?
C2 Ga1 C1 104.96(8) . . ?
C3A Ga1A C4A 115.81(8) . . ?
C3A Ga1A C2A 118.67(8) . . ?
C4A Ga1A C2A 116.66(9) . . ?
C3A Ga1A C1A 100.29(7) . . ?
C4A Ga1A C1A 100.04(7) . . ?
C2A Ga1A C1A 99.69(7) . . ?
C1 N1 C5 177.98(16) . . ?
C1A N1A C5A 178.81(15) . . ?
N1 C1 Ga1 169.51(14) . . ?
N1A C1A Ga1A 179.98(18) . . ?
Ga1 C2 H2A 109.5 . . ?
Ga1 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
Ga1 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
Ga1A C2A H2X 109.5 . . ?
Ga1A C2A H2Y 109.5 . . ?
H2X C2A H2Y 109.5 . . ?
Ga1A C2A H2Z 109.5 . . ?
H2X C2A H2Z 109.5 . . ?
H2Y C2A H2Z 109.5 . . ?
Ga1 C3 H3A 109.5 . . ?
Ga1 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
Ga1 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
Ga1A C3A H3X 109.5 . . ?
Ga1A C3A H3Y 109.5 . . ?
H3X C3A H3Y 109.5 . . ?
Ga1A C3A H3Z 109.5 . . ?
H3X C3A H3Z 109.5 . . ?
H3Y C3A H3Z 109.5 . . ?
Ga1 C4 H4A 109.4(19) . . ?
Ga1 C4 H4B 109.8(19) . . ?
H4A C4 H4B 106(3) . . ?
Ga1 C4 H4C 111(2) . . ?
H4A C4 H4C 114(3) . . ?
H4B C4 H4C 107(3) . . ?
172
Ga1A C4A H4X 109.5 . . ?
Ga1A C4A H4Y 109.5 . . ?
H4X C4A H4Y 109.5 . . ?
Ga1A C4A H4Z 109.5 . . ?
H4X C4A H4Z 109.5 . . ?
H4Y C4A H4Z 109.5 . . ?
C6 C5 C10 124.15(13) . . ?
C6 C5 N1 118.07(12) . . ?
C10 C5 N1 117.78(13) . . ?
C10A C5A C6A 124.28(13) . . ?
C10A C5A N1A 117.71(12) . . ?
C6A C5A N1A 118.01(13) . . ?
C5 C6 C7 116.71(13) . . ?
C5 C6 C11 121.34(15) . . ?
C7 C6 C11 121.95(16) . . ?
C7A C6A C5A 116.28(14) . . ?
C7A C6A C11A 122.86(15) . . ?
C5A C6A C11A 120.86(15) . . ?
C8 C7 C6 120.94(15) . . ?
C8 C7 H7 119.9(13) . . ?
C6 C7 H7 119.2(13) . . ?
C8A C7A C6A 121.16(15) . . ?
C8A C7A H7X 122.3(14) . . ?
C6A C7A H7X 116.5(14) . . ?
C9 C8 C7 120.71(14) . . ?
C9 C8 H8 119.2(12) . . ?
C7 C8 H8 120.1(12) . . ?
C7A C8A C9A 120.80(16) . . ?
C7A C8A H8X 119.7(14) . . ?
C9A C8A H8X 119.4(14) . . ?
C8 C9 C10 121.00(14) . . ?
C8 C9 H9 122.2(11) . . ?
C10 C9 H9 116.8(11) . . ?
C8A C9A C10A 120.72(16) . . ?
C8A C9A H9X 120.2(14) . . ?
C10A C9A H9X 119.1(14) . . ?
C9 C10 C5 116.48(13) . . ?
C9 C10 C12 121.72(13) . . ?
C5 C10 C12 121.80(13) . . ?
C9A C10A C5A 116.77(14) . . ?
C9A C10A C12A 122.27(15) . . ?
C5A C10A C12A 120.96(14) . . ?
C6 C11 H11A 111.4(13) . . ?
C6 C11 H11B 110.7(15) . . ?
H11A C11 H11B 110.0(19) . . ?
C6 C11 H11C 113.1(14) . . ?
H11A C11 H11C 103.7(18) . . ?
H11B C11 H11C 108(2) . . ?
C6A C11A H11X 110.1(17) . . ?
C6A C11A H11Y 110.4(16) . . ?
H11X C11A H11Y 106(2) . . ?
C6A C11A H11Z 112.4(15) . . ?
H11X C11A H11Z 107(2) . . ?
H11Y C11A H11Z 110(2) . . ?
C10 C12 H12A 110.6(14) . . ?
C10 C12 H12B 112.8(15) . . ?
173
H12A C12 H12B 103(2) . . ?
C10 C12 H12C 112.8(16) . . ?
H12A C12 H12C 111(2) . . ?
H12B C12 H12C 106(2) . . ?
C10A C12A H12X 110.6(13) . . ?
C10A C12A H12Y 113.1(16) . . ?
H12X C12A H12Y 109(2) . . ?
C10A C12A H12Z 109.8(14) . . ?
H12X C12A H12Z 105.6(19) . . ?
H12Y C12A H12Z 108(2) . . ?
_diffrn_measured_fraction_theta_max
_diffrn_reflns_theta_full
_diffrn_measured_fraction_theta_full
_refine_diff_density_max
_refine_diff_density_min
_refine_diff_density_rms
0.999
26.00
0.999
0.317
-0.318
0.068
174
CIF File For tBu3Al·C≡N(2,6-Me2C6H3)
_audit_creation_method
_chemical_name_systematic
;
?
;
_chemical_name_common
_chemical_melting_point
_chemical_formula_moiety
_chemical_formula_sum
_chemical_formula_weight
SHELXL-97
?
?
'C21 H36 Al N'
'C21 H36 Al N'
329.49
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Al' 'Al' 0.0645 0.0514
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
_symmetry_space_group_name_H-M
triclinic
P-1
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
_cell_length_a
_cell_length_b
_cell_length_c
_cell_angle_alpha
_cell_angle_beta
_cell_angle_gamma
_cell_volume
_cell_formula_units_Z
_cell_measurement_temperature
_cell_measurement_reflns_used
_cell_measurement_theta_min
_cell_measurement_theta_max
_exptl_crystal_description
_exptl_crystal_colour
_exptl_crystal_size_max
_exptl_crystal_size_mid
_exptl_crystal_size_min
8.8875(2)
11.8471(2)
11.9501(2)
64.0690(10)
87.1090(10)
72.3300(10)
1073.19(4)
2
-133
?
2.412
33.126
rectangle
colorless
.30
.25
.20
175
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn
_exptl_crystal_density_method
_exptl_crystal_F_000
_exptl_absorpt_coefficient_mu
_exptl_absorpt_correction_type multi-scan
_exptl_absorpt_correction_T_min
_exptl_absorpt_correction_T_max
_exptl_absorpt_process_details
1.020
'not measured'
364
0.096
0.850
1.000
'sadabs (Sheldrick, 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
_diffrn_radiation_wavelength
_diffrn_radiation_type
_diffrn_radiation_source
_diffrn_radiation_monochromator
_diffrn_measurement_device_type
_diffrn_measurement_method
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
?
_diffrn_reflns_number
_diffrn_reflns_av_R_equivalents
_diffrn_reflns_av_sigmaI/netI
_diffrn_reflns_limit_h_min
_diffrn_reflns_limit_h_max
_diffrn_reflns_limit_k_min
_diffrn_reflns_limit_k_max
_diffrn_reflns_limit_l_min
_diffrn_reflns_limit_l_max
_diffrn_reflns_theta_min
_diffrn_reflns_theta_max
_reflns_number_total
_reflns_number_gt
_reflns_threshold_expression
-133
0.71073
MoK\a
'fine-focus sealed tube'
'graphite'
'Bruker platform with 6k CCD'
'omega scans'
_computing_data_collection
_computing_cell_refinement
_computing_data_reduction
_computing_structure_solution
_computing_structure_refinement
_computing_molecular_graphics ?
_computing_publication_material ?
'Smart 5.630 '
'Saintplus 5.45 '
'Saintplus 5.45'
'SHELXS-97 (Sheldrick, 1990)'
'SHELXL-97 (Sheldrick, 1997)'
19702
0.0279
0.0393
-13
13
-18
17
-18
17
1.90
33.32
7553
6228
>2sigma(I)
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
176
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0484P)^2^+0.3523P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary
difmap
_atom_sites_solution_hydrogens
geom
_refine_ls_hydrogen_treatment
mixed
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
7553
_refine_ls_number_parameters
352
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.0649
_refine_ls_R_factor_gt
0.0496
_refine_ls_wR_factor_ref
0.1168
_refine_ls_wR_factor_gt
0.1116
_refine_ls_goodness_of_fit_ref
1.054
_refine_ls_restrained_S_all
1.054
_refine_ls_shift/su_max
0.000
_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Al1 Al 0.32802(3) 0.36488(3) 0.29567(3) 0.01258(8) Uani 1 1 d . . .
N1 N 0.26508(10) 0.20834(8) 0.58684(8) 0.01617(16) Uani 1 1 d . . .
C1 C 0.28888(12) 0.26710(10) 0.48560(9) 0.01742(19) Uani 1 1 d . . .
C2 C 0.55528(12) 0.36134(10) 0.30840(9) 0.01779(19) Uani 1 1 d . . .
C3 C 0.28838(14) 0.24101(11) 0.23388(10) 0.0213(2) Uani 1 1 d . . .
C4 C 0.15820(13) 0.54205(10) 0.24281(10) 0.0198(2) Uani 1 1 d . . .
C5 C 0.23843(12) 0.13055(9) 0.70972(9) 0.01460(17) Uani 1 1 d . . .
C6 C 0.32176(12) 0.12769(10) 0.80787(9) 0.01544(18) Uani 1 1 d . . .
C7 C 0.29630(13) 0.04660(10) 0.92859(9) 0.01887(19) Uani 1 1 d . . .
C8 C 0.19506(14) -0.02834(11) 0.94842(10) 0.0210(2) Uani 1 1 d . . .
C9 C 0.11243(13) -0.02064(11) 0.84836(10) 0.0200(2) Uani 1 1 d . . .
C10 C 0.13050(12) 0.06094(10) 0.72559(9) 0.01648(18) Uani 1 1 d . . .
C11 C 0.43207(14) 0.20864(11) 0.78321(11) 0.0211(2) Uani 1 1 d . . .
C12 C 0.03724(15) 0.07644(12) 0.61554(11) 0.0227(2) Uani 1 1 d . . .
177
C21 C 0.67484(15) 0.22523(13) 0.33931(14) 0.0313(3) Uani 1 1 d . . .
C22 C 0.58900(15) 0.40023(14) 0.40946(11) 0.0270(2) Uani 1 1 d . . .
C23 C 0.58980(14) 0.46013(13) 0.18224(11) 0.0243(2) Uani 1 1 d . . .
C31 C 0.3488(2) 0.27262(17) 0.10406(14) 0.0408(4) Uani 1 1 d . . .
C32 C 0.37309(19) 0.09459(12) 0.32063(14) 0.0329(3) Uani 1 1 d . . .
C33 C 0.11131(18) 0.25731(15) 0.22126(13) 0.0319(3) Uani 1 1 d . . .
C41 C 0.12465(18) 0.61395(13) 0.09973(12) 0.0332(3) Uani 1 1 d . . .
C42 C 0.00163(15) 0.52692(14) 0.29878(15) 0.0327(3) Uani 1 1 d . . .
C43 C 0.20601(17) 0.63346(13) 0.28379(14) 0.0311(3) Uani 1 1 d . . .
H8 H 0.1821(18) -0.0848(15) 1.0322(14) 0.027(4) Uiso 1 1 d . . .
H7 H 0.3501(17) 0.0423(14) 0.9987(13) 0.022(3) Uiso 1 1 d . . .
H9 H 0.0449(18) -0.0731(15) 0.8644(14) 0.027(4) Uiso 1 1 d . . .
H11A H 0.4688(19) 0.2052(15) 0.8596(15) 0.032(4) Uiso 1 1 d . . .
H11B H 0.524(2) 0.1760(17) 0.7460(16) 0.039(4) Uiso 1 1 d . . .
H11C H 0.3794(19) 0.3003(16) 0.7260(15) 0.031(4) Uiso 1 1 d . . .
H12A H 0.105(2) 0.0546(17) 0.5577(16) 0.039(4) Uiso 1 1 d . . .
H12B H -0.028(2) 0.1649(17) 0.5686(15) 0.035(4) Uiso 1 1 d . . .
H12C H -0.025(2) 0.0175(18) 0.6431(17) 0.044(5) Uiso 1 1 d . . .
H21A H 0.6675(19) 0.1957(16) 0.2776(15) 0.032(4) Uiso 1 1 d . . .
H21B H 0.659(2) 0.1582(18) 0.4203(17) 0.043(5) Uiso 1 1 d . . .
H21C H 0.786(2) 0.2281(19) 0.3457(18) 0.053(5) Uiso 1 1 d . . .
H22A H 0.575(2) 0.3377(16) 0.4919(15) 0.035(4) Uiso 1 1 d . . .
H22B H 0.518(2) 0.4889(17) 0.3979(15) 0.036(4) Uiso 1 1 d . . .
H22C H 0.698(2) 0.4031(18) 0.4137(16) 0.044(5) Uiso 1 1 d . . .
H23A H 0.5746(19) 0.4404(16) 0.1122(15) 0.032(4) Uiso 1 1 d . . .
H23B H 0.521(2) 0.5516(17) 0.1575(15) 0.034(4) Uiso 1 1 d . . .
H23C H 0.701(2) 0.4598(17) 0.1859(15) 0.037(4) Uiso 1 1 d . . .
H31A H 0.300(2) 0.365(2) 0.0426(18) 0.049(5) Uiso 1 1 d . . .
H31B H 0.466(3) 0.2555(19) 0.1063(18) 0.054(6) Uiso 1 1 d . . .
H31C H 0.323(2) 0.220(2) 0.0688(19) 0.058(6) Uiso 1 1 d . . .
H32A H 0.332(2) 0.0672(16) 0.4050(16) 0.037(4) Uiso 1 1 d . . .
H32B H 0.350(2) 0.0393(19) 0.2899(17) 0.048(5) Uiso 1 1 d . . .
H32C H 0.492(2) 0.0705(18) 0.3318(17) 0.050(5) Uiso 1 1 d . . .
H33A H 0.051(2) 0.3443(17) 0.1616(16) 0.035(4) Uiso 1 1 d . . .
H33B H 0.0657(19) 0.2363(16) 0.3018(16) 0.033(4) Uiso 1 1 d . . .
H33C H 0.099(2) 0.1956(18) 0.1894(17) 0.049(5) Uiso 1 1 d . . .
H41A H 0.222(2) 0.5978(17) 0.3730(17) 0.037(4) Uiso 1 1 d . . .
H41B H 0.089(2) 0.5639(18) 0.0683(17) 0.045(5) Uiso 1 1 d . . .
H41C H 0.040(2) 0.7025(19) 0.0719(17) 0.047(5) Uiso 1 1 d . . .
H42A H -0.039(2) 0.4737(18) 0.2746(17) 0.044(5) Uiso 1 1 d . . .
H42B H -0.080(2) 0.6128(18) 0.2675(17) 0.045(5) Uiso 1 1 d . . .
H42C H 0.010(2) 0.4872(18) 0.3928(17) 0.046(5) Uiso 1 1 d . . .
H43A H 0.225(2) 0.6323(17) 0.0566(16) 0.038(4) Uiso 1 1 d . . .
H43B H 0.116(2) 0.7181(18) 0.2557(17) 0.045(5) Uiso 1 1 d . . .
H43C H 0.304(2) 0.6542(17) 0.2485(15) 0.038(4) Uiso 1 1 d . . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Al1 0.01408(14) 0.01212(14) 0.01144(13) -0.00460(10) 0.00223(10) -0.00510(10)
N1 0.0169(4) 0.0155(4) 0.0156(4) -0.0063(3) 0.0027(3) -0.0053(3)
178
C1 0.0176(4) 0.0172(4) 0.0177(4) -0.0073(4) 0.0020(3) -0.0064(4)
C2 0.0164(4) 0.0193(5) 0.0163(4) -0.0062(4) 0.0031(3) -0.0063(4)
C3 0.0317(6) 0.0208(5) 0.0184(4) -0.0109(4) 0.0084(4) -0.0150(4)
C4 0.0186(5) 0.0162(5) 0.0209(5) -0.0060(4) 0.0003(4) -0.0038(4)
C5 0.0159(4) 0.0128(4) 0.0134(4) -0.0047(3) 0.0036(3) -0.0042(3)
C6 0.0157(4) 0.0138(4) 0.0158(4) -0.0061(3) 0.0029(3) -0.0041(3)
C7 0.0216(5) 0.0186(5) 0.0145(4) -0.0064(4) 0.0022(4) -0.0053(4)
C8 0.0254(5) 0.0192(5) 0.0151(4) -0.0042(4) 0.0060(4) -0.0087(4)
C9 0.0223(5) 0.0186(5) 0.0202(5) -0.0073(4) 0.0070(4) -0.0107(4)
C10 0.0181(4) 0.0154(4) 0.0170(4) -0.0077(3) 0.0038(3) -0.0061(3)
C11 0.0224(5) 0.0203(5) 0.0213(5) -0.0073(4) 0.0016(4) -0.0105(4)
C12 0.0256(5) 0.0251(5) 0.0202(5) -0.0100(4) 0.0009(4) -0.0113(4)
C21 0.0181(5) 0.0267(6) 0.0394(7) -0.0101(5) 0.0048(5) -0.0014(4)
C22 0.0262(6) 0.0394(7) 0.0202(5) -0.0123(5) 0.0009(4) -0.0180(5)
C23 0.0239(5) 0.0305(6) 0.0201(5) -0.0086(4) 0.0070(4) -0.0156(5)
C31 0.0743(12) 0.0465(9) 0.0282(6) -0.0277(6) 0.0266(7) -0.0407(8)
C32 0.0443(8) 0.0185(5) 0.0408(7) -0.0160(5) 0.0145(6) -0.0135(5)
C33 0.0387(7) 0.0358(7) 0.0294(6) -0.0126(5) -0.0008(5) -0.0247(6)
C41 0.0371(7) 0.0238(6) 0.0241(6) -0.0008(5) -0.0077(5) -0.0031(5)
C42 0.0178(5) 0.0275(6) 0.0446(8) -0.0127(6) 0.0049(5) -0.0016(5)
C43 0.0334(7) 0.0217(6) 0.0419(7) -0.0194(5) 0.0050(5) -0.0060(5)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Al1 C2 2.0196(11) . ?
Al1 C4 2.0239(11) . ?
Al1 C3 2.0274(11) . ?
Al1 C1 2.1166(11) . ?
N1 C1 1.1489(13) . ?
N1 C5 1.4056(12) . ?
C2 C21 1.5311(16) . ?
C2 C23 1.5378(15) . ?
C2 C22 1.5385(16) . ?
C3 C33 1.5332(18) . ?
C3 C32 1.5374(17) . ?
C3 C31 1.5379(17) . ?
C4 C43 1.5353(17) . ?
C4 C41 1.5366(16) . ?
C4 C42 1.5390(17) . ?
C5 C10 1.4004(14) . ?
C5 C6 1.4011(14) . ?
C6 C7 1.3937(14) . ?
179
C6 C11 1.5041(14) . ?
C7 C8 1.3905(15) . ?
C7 H7 0.960(14) . ?
C8 C9 1.3891(15) . ?
C8 H8 0.956(15) . ?
C9 C10 1.3938(14) . ?
C9 H9 0.946(16) . ?
C10 C12 1.5021(15) . ?
C11 H11A 0.965(16) . ?
C11 H11B 0.970(18) . ?
C11 H11C 0.969(16) . ?
C12 H12A 0.965(18) . ?
C12 H12B 0.948(17) . ?
C12 H12C 0.957(19) . ?
C21 H21A 0.956(17) . ?
C21 H21B 0.985(18) . ?
C21 H21C 1.01(2) . ?
C22 H22A 0.970(16) . ?
C22 H22B 0.999(17) . ?
C22 H22C 0.984(19) . ?
C23 H23A 0.987(16) . ?
C23 H23B 0.985(17) . ?
C23 H23C 0.993(17) . ?
C31 H31A 0.982(19) . ?
C31 H31B 1.00(2) . ?
C31 H31C 0.97(2) . ?
C32 H32A 1.001(17) . ?
C32 H32B 0.95(2) . ?
C32 H32C 1.01(2) . ?
C33 H33A 0.958(17) . ?
C33 H33B 0.982(17) . ?
C33 H33C 0.995(19) . ?
C41 H41B 0.958(19) . ?
C41 H41C 1.009(19) . ?
C41 H43A 1.039(18) . ?
C42 H42A 0.959(19) . ?
C42 H42B 0.973(19) . ?
C42 H42C 1.007(18) . ?
C43 H41A 0.959(18) . ?
C43 H43B 1.002(19) . ?
C43 H43C 0.996(18) . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C2 Al1 C4 116.93(5) . . ?
C2 Al1 C3 116.39(5) . . ?
C4 Al1 C3 116.63(5) . . ?
C2 Al1 C1 102.22(4) . . ?
C4 Al1 C1 100.62(4) . . ?
C3 Al1 C1 99.18(4) . . ?
180
C1 N1 C5 177.04(10) . . ?
N1 C1 Al1 175.59(9) . . ?
C21 C2 C23 107.65(10) . . ?
C21 C2 C22 106.86(10) . . ?
C23 C2 C22 107.97(9) . . ?
C21 C2 Al1 112.83(8) . . ?
C23 C2 Al1 108.96(7) . . ?
C22 C2 Al1 112.36(7) . . ?
C33 C3 C32 107.01(10) . . ?
C33 C3 C31 107.85(11) . . ?
C32 C3 C31 108.11(11) . . ?
C33 C3 Al1 111.88(8) . . ?
C32 C3 Al1 112.91(8) . . ?
C31 C3 Al1 108.89(8) . . ?
C43 C4 C41 107.29(10) . . ?
C43 C4 C42 106.72(10) . . ?
C41 C4 C42 108.03(10) . . ?
C43 C4 Al1 112.65(8) . . ?
C41 C4 Al1 110.18(8) . . ?
C42 C4 Al1 111.74(8) . . ?
C10 C5 C6 124.49(9) . . ?
C10 C5 N1 117.67(9) . . ?
C6 C5 N1 117.84(9) . . ?
C7 C6 C5 116.45(9) . . ?
C7 C6 C11 122.19(9) . . ?
C5 C6 C11 121.36(9) . . ?
C8 C7 C6 120.86(10) . . ?
C8 C7 H7 119.8(9) . . ?
C6 C7 H7 119.3(9) . . ?
C9 C8 C7 120.78(9) . . ?
C9 C8 H8 120.2(9) . . ?
C7 C8 H8 119.0(9) . . ?
C8 C9 C10 120.90(10) . . ?
C8 C9 H9 119.1(9) . . ?
C10 C9 H9 120.0(9) . . ?
C9 C10 C5 116.44(9) . . ?
C9 C10 C12 122.23(10) . . ?
C5 C10 C12 121.32(9) . . ?
C6 C11 H11A 111.1(10) . . ?
C6 C11 H11B 110.7(10) . . ?
H11A C11 H11B 107.9(14) . . ?
C6 C11 H11C 110.8(9) . . ?
H11A C11 H11C 108.4(13) . . ?
H11B C11 H11C 107.8(14) . . ?
C10 C12 H12A 111.8(10) . . ?
C10 C12 H12B 111.8(10) . . ?
H12A C12 H12B 105.7(14) . . ?
C10 C12 H12C 110.0(11) . . ?
H12A C12 H12C 106.7(14) . . ?
H12B C12 H12C 110.6(14) . . ?
C2 C21 H21A 112.7(10) . . ?
C2 C21 H21B 110.9(10) . . ?
H21A C21 H21B 107.6(14) . . ?
C2 C21 H21C 109.9(11) . . ?
H21A C21 H21C 108.0(14) . . ?
H21B C21 H21C 107.6(15) . . ?
181
C2 C22 H22A 111.2(10) . . ?
C2 C22 H22B 114.0(9) . . ?
H22A C22 H22B 106.0(13) . . ?
C2 C22 H22C 113.1(10) . . ?
H22A C22 H22C 106.5(14) . . ?
H22B C22 H22C 105.6(14) . . ?
C2 C23 H23A 113.3(9) . . ?
C2 C23 H23B 112.8(9) . . ?
H23A C23 H23B 105.7(13) . . ?
C2 C23 H23C 110.6(10) . . ?
H23A C23 H23C 106.9(13) . . ?
H23B C23 H23C 107.2(13) . . ?
C3 C31 H31A 113.3(11) . . ?
C3 C31 H31B 112.6(11) . . ?
H31A C31 H31B 106.6(16) . . ?
C3 C31 H31C 110.7(12) . . ?
H31A C31 H31C 105.1(16) . . ?
H31B C31 H31C 108.1(16) . . ?
C3 C32 H32A 111.3(9) . . ?
C3 C32 H32B 110.7(11) . . ?
H32A C32 H32B 104.1(14) . . ?
C3 C32 H32C 114.3(11) . . ?
H32A C32 H32C 108.7(14) . . ?
H32B C32 H32C 107.2(16) . . ?
C3 C33 H33A 112.4(10) . . ?
C3 C33 H33B 112.0(10) . . ?
H33A C33 H33B 109.3(14) . . ?
C3 C33 H33C 108.5(11) . . ?
H33A C33 H33C 106.3(14) . . ?
H33B C33 H33C 108.1(14) . . ?
C4 C41 H41B 111.5(11) . . ?
C4 C41 H41C 111.2(10) . . ?
H41B C41 H41C 107.4(15) . . ?
C4 C41 H43A 111.6(9) . . ?
H41B C41 H43A 108.3(15) . . ?
H41C C41 H43A 106.7(14) . . ?
C4 C42 H42A 112.0(11) . . ?
C4 C42 H42B 110.1(11) . . ?
H42A C42 H42B 105.8(15) . . ?
C4 C42 H42C 113.8(10) . . ?
H42A C42 H42C 107.4(15) . . ?
H42B C42 H42C 107.3(15) . . ?
C4 C43 H41A 112.3(10) . . ?
C4 C43 H43B 108.0(10) . . ?
H41A C43 H43B 106.0(14) . . ?
C4 C43 H43C 113.5(10) . . ?
H41A C43 H43C 108.0(14) . . ?
H43B C43 H43C 108.7(14) . . ?
_diffrn_measured_fraction_theta_max
_diffrn_reflns_theta_full
_diffrn_measured_fraction_theta_full
_refine_diff_density_max
_refine_diff_density_min
_refine_diff_density_rms
0.909
26.00
1.000
0.536
-0.190
0.053
182
CIF File For tBu3Ga·C≡N(2,6-Me2C6H3)
_audit_creation_method
_chemical_name_systematic
;
?
;
_chemical_name_common
_chemical_melting_point
_chemical_formula_moiety
_chemical_formula_sum
SHELXL-97
?
?
'C21 H36 Ga N'
'C21 H36 Ga N'
_chemical_formula_weight
372.23
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Ga' 'Ga' 0.2307 1.6083
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
_symmetry_space_group_name_H-M
triclinic
P-1
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
_cell_length_a
_cell_length_b
_cell_length_c
_cell_angle_alpha
_cell_angle_beta
_cell_angle_gamma
_cell_volume
_cell_formula_units_Z
_cell_measurement_temperature
_cell_measurement_reflns_used
_cell_measurement_theta_min
_cell_measurement_theta_max
_exptl_crystal_description
_exptl_crystal_colour
_exptl_crystal_size_max
_exptl_crystal_size_mid
_exptl_crystal_size_min
_exptl_crystal_density_meas
8.9135(2)
11.8766(2)
11.9732(3)
64.1920(10)
87.1740(10)
72.3710(10)
1082.45(4)
2
-133
?
1.90
28.29
rectangle
colorless
.35
.30
.25
?
183
_exptl_crystal_density_diffrn
_exptl_crystal_density_method
_exptl_crystal_F_000
_exptl_absorpt_coefficient_mu
_exptl_absorpt_correction_type
_exptl_absorpt_correction_T_min
_exptl_absorpt_correction_T_max
_exptl_absorpt_process_details
1.142
'not measured'
400
1.272
multi-scan
0.858
1.000
'sadabs (Sheldrick, 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
_diffrn_radiation_wavelength
_diffrn_radiation_type
_diffrn_radiation_source
_diffrn_radiation_monochromator
_diffrn_measurement_device_type
_diffrn_measurement_method
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
?
_diffrn_reflns_number
_diffrn_reflns_av_R_equivalents
_diffrn_reflns_av_sigmaI/netI
_diffrn_reflns_limit_h_min
_diffrn_reflns_limit_h_max
_diffrn_reflns_limit_k_min
_diffrn_reflns_limit_k_max
_diffrn_reflns_limit_l_min
_diffrn_reflns_limit_l_max
_diffrn_reflns_theta_min
_diffrn_reflns_theta_max
_reflns_number_total
_reflns_number_gt
_reflns_threshold_expression
-133
0.71073
MoK\a
'fine-focus sealed tube'
'graphite'
'Bruker platform with 6k CCD'
'omega scans'
_computing_data_collection
_computing_cell_refinement
_computing_data_reduction
_computing_structure_solution
_computing_structure_refinement
_computing_molecular_graphics ?
_computing_publication_material ?
'Smart 5.630 '
'Saintplus 5.45 '
'Saintplus 5.45'
'SHELXS-97 (Sheldrick, 1990)'
'SHELXL-97 (Sheldrick, 1997)'
15412
0.0199
0.0218
-11
11
-15
15
-15
15
1.90
28.29
5367
5143
>2sigma(I)
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
184
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0262P)^2^+0.3121P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary
difmap
_atom_sites_solution_hydrogens
geom
_refine_ls_hydrogen_treatment
mixed
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
5367
_refine_ls_number_parameters
352
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.0245
_refine_ls_R_factor_gt
0.0231
_refine_ls_wR_factor_ref
0.0602
_refine_ls_wR_factor_gt
0.0595
_refine_ls_goodness_of_fit_ref
1.103
_refine_ls_restrained_S_all
1.103
_refine_ls_shift/su_max
0.002
_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ga1 Ga 0.327132(14) 0.366666(11) 0.291640(11) 0.01961(5) Uani 1 1 d . . .
N1 N 0.26427(12) 0.20768(10) 0.58634(10) 0.0247(2) Uani 1 1 d . . .
C1 C 0.28780(15) 0.26679(13) 0.48568(12) 0.0271(2) Uani 1 1 d . . .
C2 C 0.55544(15) 0.36069(13) 0.30740(12) 0.0273(2) Uani 1 1 d . . .
C3 C 0.28465(19) 0.24242(14) 0.23068(13) 0.0331(3) Uani 1 1 d . . .
C4 C 0.15720(16) 0.54369(13) 0.24269(13) 0.0312(3) Uani 1 1 d . . .
C5 C 0.23814(14) 0.13038(11) 0.70892(11) 0.0223(2) Uani 1 1 d . . .
C6 C 0.32143(14) 0.12736(12) 0.80668(12) 0.0240(2) Uani 1 1 d . . .
C7 C 0.29622(16) 0.04718(13) 0.92702(12) 0.0283(3) Uani 1 1 d . . .
C8 C 0.19480(17) -0.02707(14) 0.94724(13) 0.0312(3) Uani 1 1 d . . .
C9 C 0.11236(17) -0.01933(13) 0.84748(13) 0.0303(3) Uani 1 1 d . . .
C10 C 0.13016(15) 0.06130(12) 0.72537(12) 0.0253(2) Uani 1 1 d . . .
C11 C 0.43184(18) 0.20775(15) 0.78200(14) 0.0322(3) Uani 1 1 d . . .
C12 C 0.03687(19) 0.07596(16) 0.61581(14) 0.0343(3) Uani 1 1 d . . .
C21 C 0.6719(2) 0.22473(18) 0.3387(2) 0.0482(4) Uani 1 1 d . . .
185
C22 C 0.5876(2) 0.3989(2) 0.40883(15) 0.0416(4) Uani 1 1 d . . .
C23 C 0.59009(19) 0.45941(17) 0.18252(14) 0.0374(3) Uani 1 1 d . . .
C31 C 0.3438(4) 0.2745(2) 0.1016(2) 0.0614(6) Uani 1 1 d . . .
C32 C 0.3686(3) 0.09736(16) 0.3179(2) 0.0494(4) Uani 1 1 d . . .
C33 C 0.1074(2) 0.26036(19) 0.22001(18) 0.0466(4) Uani 1 1 d . . .
C41 C 0.1246(3) 0.61563(18) 0.10065(18) 0.0513(4) Uani 1 1 d . . .
C42 C 0.0021(2) 0.52708(19) 0.2996(2) 0.0494(4) Uani 1 1 d . . .
C43 C 0.2072(2) 0.63166(17) 0.2861(2) 0.0480(4) Uani 1 1 d . . .
H8 H 0.181(2) -0.0817(17) 1.0302(17) 0.037(4) Uiso 1 1 d . . .
H7 H 0.3497(19) 0.0439(16) 0.9940(15) 0.029(4) Uiso 1 1 d . . .
H9 H 0.047(2) -0.0700(17) 0.8617(16) 0.035(4) Uiso 1 1 d . . .
H11B H 0.519(2) 0.1778(19) 0.7427(18) 0.047(5) Uiso 1 1 d . . .
H23A H 0.579(2) 0.4340(18) 0.1146(18) 0.043(5) Uiso 1 1 d . . .
H11A H 0.470(2) 0.2040(19) 0.8570(18) 0.045(5) Uiso 1 1 d . . .
H22C H 0.702(2) 0.3970(19) 0.4109(18) 0.048(5) Uiso 1 1 d . . .
H23B H 0.521(2) 0.553(2) 0.1598(18) 0.050(5) Uiso 1 1 d . . .
H11C H 0.383(2) 0.298(2) 0.7251(18) 0.045(5) Uiso 1 1 d . . .
H22A H 0.577(2) 0.333(2) 0.489(2) 0.057(6) Uiso 1 1 d . . .
H22B H 0.519(2) 0.488(2) 0.3956(19) 0.053(6) Uiso 1 1 d . . .
H23C H 0.704(3) 0.459(2) 0.183(2) 0.061(6) Uiso 1 1 d . . .
H21A H 0.661(2) 0.2006(18) 0.2739(17) 0.036(4) Uiso 1 1 d . . .
H21B H 0.652(2) 0.162(2) 0.420(2) 0.050(5) Uiso 1 1 d . . .
H12B H -0.026(2) 0.162(2) 0.5694(18) 0.045(5) Uiso 1 1 d . . .
H12A H 0.105(2) 0.056(2) 0.5567(19) 0.050(5) Uiso 1 1 d . . .
H12C H -0.028(3) 0.022(2) 0.644(2) 0.058(6) Uiso 1 1 d . . .
H32A H 0.329(3) 0.073(2) 0.399(2) 0.060(6) Uiso 1 1 d . . .
H32C H 0.484(3) 0.072(2) 0.329(2) 0.062(6) Uiso 1 1 d . . .
H21C H 0.788(3) 0.225(2) 0.347(2) 0.064(6) Uiso 1 1 d . . .
H32B H 0.340(3) 0.046(2) 0.283(2) 0.069(7) Uiso 1 1 d . . .
H41A H 0.217(2) 0.593(2) 0.374(2) 0.046(5) Uiso 1 1 d . . .
H42A H -0.039(3) 0.479(2) 0.270(2) 0.061(6) Uiso 1 1 d . . .
H43A H 0.224(3) 0.633(2) 0.063(2) 0.061(6) Uiso 1 1 d . . .
H31A H 0.295(3) 0.364(2) 0.041(2) 0.063(7) Uiso 1 1 d . . .
H42B H -0.075(3) 0.607(2) 0.272(2) 0.066(7) Uiso 1 1 d . . .
H43C H 0.309(3) 0.648(2) 0.254(2) 0.056(6) Uiso 1 1 d . . .
H31B H 0.455(3) 0.257(2) 0.103(2) 0.065(7) Uiso 1 1 d . . .
H42C H 0.015(3) 0.485(2) 0.394(2) 0.074(7) Uiso 1 1 d . . .
H41B H 0.083(3) 0.565(2) 0.068(2) 0.068(7) Uiso 1 1 d . . .
H31C H 0.317(3) 0.224(2) 0.068(2) 0.075(7) Uiso 1 1 d . . .
H43B H 0.118(3) 0.714(2) 0.263(2) 0.069(7) Uiso 1 1 d . . .
H41C H 0.042(3) 0.703(3) 0.075(2) 0.074(7) Uiso 1 1 d . . .
H33A H 0.045(2) 0.350(2) 0.1593(19) 0.048(5) Uiso 1 1 d . . .
H33B H 0.063(2) 0.236(2) 0.303(2) 0.055(6) Uiso 1 1 d . . .
H33C H 0.095(3) 0.202(2) 0.188(2) 0.063(6) Uiso 1 1 d . . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Ga1 0.02077(7) 0.01769(7) 0.02020(7) -0.00744(5) 0.00300(5) -0.00734(5)
N1 0.0257(5) 0.0223(5) 0.0248(5) -0.0094(4) 0.0049(4) -0.0079(4)
C1 0.0273(6) 0.0264(6) 0.0281(6) -0.0114(5) 0.0043(5) -0.0105(5)
186
C2 0.0232(6) 0.0306(6) 0.0258(6) -0.0090(5) 0.0036(4) -0.0109(5)
C3 0.0474(8) 0.0316(7) 0.0327(7) -0.0192(6) 0.0137(6) -0.0228(6)
C4 0.0284(6) 0.0238(6) 0.0362(7) -0.0108(5) -0.0003(5) -0.0044(5)
C5 0.0238(5) 0.0178(5) 0.0228(5) -0.0082(4) 0.0060(4) -0.0051(4)
C6 0.0237(5) 0.0197(5) 0.0276(6) -0.0104(5) 0.0042(4) -0.0058(4)
C7 0.0312(6) 0.0274(6) 0.0251(6) -0.0116(5) 0.0029(5) -0.0076(5)
C8 0.0366(7) 0.0284(6) 0.0246(6) -0.0076(5) 0.0091(5) -0.0121(5)
C9 0.0337(7) 0.0272(6) 0.0325(7) -0.0123(5) 0.0099(5) -0.0154(5)
C10 0.0278(6) 0.0222(5) 0.0276(6) -0.0124(5) 0.0063(5) -0.0086(5)
C11 0.0327(7) 0.0308(7) 0.0348(7) -0.0122(6) 0.0024(6) -0.0155(6)
C12 0.0384(8) 0.0354(7) 0.0337(7) -0.0156(6) 0.0028(6) -0.0169(6)
C21 0.0274(7) 0.0420(9) 0.0626(11) -0.0176(9) 0.0056(7) -0.0027(7)
C22 0.0388(8) 0.0594(11) 0.0337(8) -0.0198(8) 0.0026(6) -0.0258(8)
C23 0.0358(8) 0.0481(9) 0.0318(7) -0.0139(7) 0.0094(6) -0.0245(7)
C31 0.1082(19) 0.0695(14) 0.0468(11) -0.0431(11) 0.0392(12) -0.0602(14)
C32 0.0611(11) 0.0278(7) 0.0667(12) -0.0259(8) 0.0211(9) -0.0183(8)
C33 0.0569(10) 0.0506(10) 0.0462(9) -0.0214(8) 0.0003(8) -0.0347(9)
C41 0.0559(11) 0.0351(8) 0.0406(9) -0.0019(7) -0.0121(8) -0.0041(8)
C42 0.0284(8) 0.0413(9) 0.0695(13) -0.0222(9) 0.0073(8) -0.0029(7)
C43 0.0496(10) 0.0322(8) 0.0667(12) -0.0294(8) 0.0045(9) -0.0073(7)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ga1 C2 2.0299(12) . ?
Ga1 C4 2.0356(13) . ?
Ga1 C3 2.0389(13) . ?
Ga1 C1 2.1679(13) . ?
N1 C1 1.1475(17) . ?
N1 C5 1.4049(15) . ?
C2 C21 1.524(2) . ?
C2 C23 1.5340(19) . ?
C2 C22 1.535(2) . ?
C3 C31 1.530(2) . ?
C3 C32 1.532(2) . ?
C3 C33 1.533(2) . ?
C4 C43 1.529(2) . ?
C4 C41 1.530(2) . ?
C4 C42 1.539(2) . ?
C5 C6 1.3984(17) . ?
C5 C10 1.3990(17) . ?
C6 C7 1.3915(18) . ?
C6 C11 1.5041(18) . ?
187
C7 C8 1.3889(19) . ?
C7 H7 0.934(16) . ?
C8 C9 1.388(2) . ?
C8 H8 0.948(18) . ?
C9 C10 1.3892(18) . ?
C9 H9 0.921(18) . ?
C10 C12 1.5045(19) . ?
C11 H11B 0.94(2) . ?
C11 H11A 0.954(19) . ?
C11 H11C 0.96(2) . ?
C12 H12B 0.92(2) . ?
C12 H12A 0.97(2) . ?
C12 H12C 0.93(2) . ?
C21 H21A 0.955(18) . ?
C21 H21B 0.99(2) . ?
C21 H21C 1.05(2) . ?
C22 H22C 1.01(2) . ?
C22 H22A 0.96(2) . ?
C22 H22B 0.99(2) . ?
C23 H23A 1.000(19) . ?
C23 H23B 1.01(2) . ?
C23 H23C 1.01(2) . ?
C31 H31A 0.96(2) . ?
C31 H31B 0.95(2) . ?
C31 H31C 0.94(3) . ?
C32 H32A 0.97(2) . ?
C32 H32C 0.98(2) . ?
C32 H32B 0.97(2) . ?
C33 H33A 0.99(2) . ?
C33 H33B 1.00(2) . ?
C33 H33C 0.96(2) . ?
C41 H43A 1.01(2) . ?
C41 H41B 1.00(2) . ?
C41 H41C 1.00(3) . ?
C42 H42A 0.94(2) . ?
C42 H42B 0.91(2) . ?
C42 H42C 1.02(2) . ?
C43 H41A 0.94(2) . ?
C43 H43C 1.01(2) . ?
C43 H43B 0.99(2) . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C2 Ga1 C4 117.31(5) . . ?
C2 Ga1 C3 117.02(6) . . ?
C4 Ga1 C3 117.11(6) . . ?
C2 Ga1 C1 101.19(5) . . ?
C4 Ga1 C1 99.62(5) . . ?
C3 Ga1 C1 98.67(5) . . ?
C1 N1 C5 177.56(13) . . ?
188
N1 C1 Ga1 175.15(11) . . ?
C21 C2 C23 108.55(13) . . ?
C21 C2 C22 107.17(14) . . ?
C23 C2 C22 108.03(12) . . ?
C21 C2 Ga1 112.48(10) . . ?
C23 C2 Ga1 108.24(9) . . ?
C22 C2 Ga1 112.23(9) . . ?
C31 C3 C32 108.97(16) . . ?
C31 C3 C33 108.66(16) . . ?
C32 C3 C33 107.41(13) . . ?
C31 C3 Ga1 108.08(10) . . ?
C32 C3 Ga1 112.41(11) . . ?
C33 C3 Ga1 111.24(10) . . ?
C43 C4 C41 107.99(14) . . ?
C43 C4 C42 107.00(14) . . ?
C41 C4 C42 108.83(15) . . ?
C43 C4 Ga1 112.25(10) . . ?
C41 C4 Ga1 109.06(11) . . ?
C42 C4 Ga1 111.59(10) . . ?
C6 C5 C10 124.14(11) . . ?
C6 C5 N1 118.04(11) . . ?
C10 C5 N1 117.81(11) . . ?
C7 C6 C5 116.70(11) . . ?
C7 C6 C11 122.04(12) . . ?
C5 C6 C11 121.26(11) . . ?
C8 C7 C6 120.88(12) . . ?
C8 C7 H7 120.7(10) . . ?
C6 C7 H7 118.5(10) . . ?
C9 C8 C7 120.49(12) . . ?
C9 C8 H8 120.4(10) . . ?
C7 C8 H8 119.1(10) . . ?
C8 C9 C10 121.12(12) . . ?
C8 C9 H9 119.9(11) . . ?
C10 C9 H9 118.9(11) . . ?
C9 C10 C5 116.58(12) . . ?
C9 C10 C12 122.14(12) . . ?
C5 C10 C12 121.27(12) . . ?
C6 C11 H11B 110.4(12) . . ?
C6 C11 H11A 111.7(11) . . ?
H11B C11 H11A 109.1(16) . . ?
C6 C11 H11C 112.2(11) . . ?
H11B C11 H11C 104.9(16) . . ?
H11A C11 H11C 108.3(16) . . ?
C10 C12 H12B 112.1(12) . . ?
C10 C12 H12A 111.9(12) . . ?
H12B C12 H12A 104.1(16) . . ?
C10 C12 H12C 109.5(13) . . ?
H12B C12 H12C 108.3(17) . . ?
H12A C12 H12C 110.8(17) . . ?
C2 C21 H21A 109.5(11) . . ?
C2 C21 H21B 108.6(12) . . ?
H21A C21 H21B 112.4(16) . . ?
C2 C21 H21C 110.3(12) . . ?
H21A C21 H21C 108.9(16) . . ?
H21B C21 H21C 107.1(17) . . ?
C2 C22 H22C 108.9(11) . . ?
189
C2 C22 H22A 109.5(13) . . ?
H22C C22 H22A 105.6(16) . . ?
C2 C22 H22B 113.4(12) . . ?
H22C C22 H22B 108.4(16) . . ?
H22A C22 H22B 110.7(17) . . ?
C2 C23 H23A 110.9(11) . . ?
C2 C23 H23B 112.0(11) . . ?
H23A C23 H23B 110.9(15) . . ?
C2 C23 H23C 112.2(12) . . ?
H23A C23 H23C 103.5(16) . . ?
H23B C23 H23C 107.0(17) . . ?
C3 C31 H31A 113.7(14) . . ?
C3 C31 H31B 113.0(15) . . ?
H31A C31 H31B 108(2) . . ?
C3 C31 H31C 109.7(15) . . ?
H31A C31 H31C 104.3(19) . . ?
H31B C31 H31C 108(2) . . ?
C3 C32 H32A 110.8(13) . . ?
C3 C32 H32C 115.6(13) . . ?
H32A C32 H32C 108.4(18) . . ?
C3 C32 H32B 106.6(14) . . ?
H32A C32 H32B 106.4(19) . . ?
H32C C32 H32B 108.6(19) . . ?
C3 C33 H33A 112.7(12) . . ?
C3 C33 H33B 112.1(12) . . ?
H33A C33 H33B 110.8(17) . . ?
C3 C33 H33C 107.2(14) . . ?
H33A C33 H33C 106.1(17) . . ?
H33B C33 H33C 107.5(17) . . ?
C4 C41 H43A 109.3(12) . . ?
C4 C41 H41B 111.1(13) . . ?
H43A C41 H41B 112.7(18) . . ?
C4 C41 H41C 110.1(14) . . ?
H43A C41 H41C 107.1(19) . . ?
H41B C41 H41C 106.4(19) . . ?
C4 C42 H42A 110.4(14) . . ?
C4 C42 H42B 110.5(15) . . ?
H42A C42 H42B 103.5(19) . . ?
C4 C42 H42C 112.4(14) . . ?
H42A C42 H42C 111.1(19) . . ?
H42B C42 H42C 109(2) . . ?
C4 C43 H41A 108.6(12) . . ?
C4 C43 H43C 113.3(12) . . ?
H41A C43 H43C 110.3(17) . . ?
C4 C43 H43B 107.9(14) . . ?
H41A C43 H43B 103.2(18) . . ?
H43C C43 H43B 113.1(18) . . ?
_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full
26.00
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max 0.511
_refine_diff_density_min -0.297
_refine_diff_density_rms 0.046
190
CIF File For [3-methylindolyl(AlMe2)]2
_audit_creation_method
_chemical_name_systematic
;
?
;
_chemical_name_common
_chemical_melting_point
_chemical_formula_moiety
_chemical_formula_sum
SHELXL-97
?
?
_chemical_formula_weight
'C22 H28 Al2 N2'
'C22 H28 Al2 N2'
374.42
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Al' 'Al' 0.0645 0.0514
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
_symmetry_space_group_name_H-M
Monoclinic
P2(1)/c
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'
_cell_length_a
_cell_length_b
_cell_length_c
_cell_angle_alpha
_cell_angle_beta
_cell_angle_gamma
_cell_volume
_cell_formula_units_Z
_cell_measurement_temperature
_cell_measurement_reflns_used
_cell_measurement_theta_min
_cell_measurement_theta_max
7.9554(4)
18.7424(10)
14.6172(7)
90.00
104.9450(10)
90.00
2105.75(18)
4
-133
_exptl_crystal_description
_exptl_crystal_colour
_exptl_crystal_size_max
brick
colorless
.30
1.81
26.00
191
_exptl_crystal_size_mid
_exptl_crystal_size_min
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn
_exptl_crystal_density_method
_exptl_crystal_F_000
_exptl_absorpt_coefficient_mu
_exptl_absorpt_correction_type ?
_exptl_absorpt_correction_T_min
_exptl_absorpt_correction_T_max
_exptl_absorpt_process_details ?
.30
.25
1.181
'not measured'
800
0.146
0.895
1.00
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
_diffrn_radiation_wavelength
_diffrn_radiation_type
_diffrn_radiation_source
_diffrn_radiation_monochromator
_diffrn_measurement_device_type
_diffrn_measurement_method
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
?
_diffrn_reflns_number
_diffrn_reflns_av_R_equivalents
_diffrn_reflns_av_sigmaI/netI
_diffrn_reflns_limit_h_min
_diffrn_reflns_limit_h_max
_diffrn_reflns_limit_k_min
_diffrn_reflns_limit_k_max
_diffrn_reflns_limit_l_min
_diffrn_reflns_limit_l_max
_diffrn_reflns_theta_min
_diffrn_reflns_theta_max
_reflns_number_total
_reflns_number_gt
_reflns_threshold_expression
-133
0.71073
MoK\a
'fine-focus sealed tube'
'graphite'
'Bruker platform with 6k CCD'
'omega scans'
_computing_data_collection
_computing_cell_refinement
_computing_data_reduction
_computing_structure_solution
_computing_structure_refinement
_computing_molecular_graphics ?
_computing_publication_material ?
'Smart 5.630 '
'Saintplus 5.45 '
'Saintplus 5.45'
'SHELXS-97 (Sheldrick, 1990)'
'SHELXL-97 (Sheldrick, 1997)'
14293
0.0211
0.0262
-9
9
-20
23
-18
16
1.81
26.00
4133
3778
>2sigma(I)
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
192
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0887P)^2^+1.1754P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary
difmap
_atom_sites_solution_hydrogens
geom
_refine_ls_hydrogen_treatment
mixed
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
4133
_refine_ls_number_parameters
377
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.0597
_refine_ls_R_factor_gt
0.0556
_refine_ls_wR_factor_ref
0.1643
_refine_ls_wR_factor_gt
0.1614
_refine_ls_goodness_of_fit_ref
1.146
_refine_ls_restrained_S_all
1.146
_refine_ls_shift/su_max
0.080
_refine_ls_shift/su_mean
0.014
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Al1 Al 0.45089(9) 0.71324(3) 0.19894(4) 0.0303(2) Uani 1 1 d . . .
Al2 Al 0.51240(8) 0.64212(3) 0.03571(4) 0.0275(2) Uani 1 1 d . A .
C1 C 0.2174(4) 0.73838(15) 0.2065(2) 0.0536(7) Uani 1 1 d . A .
H1A H 0.2236 0.7615 0.2658 0.080 Uiso 1 1 calc R . .
H1B H 0.1482 0.6959 0.2019 0.080 Uiso 1 1 calc R . .
H1C H 0.1653 0.7701 0.1554 0.080 Uiso 1 1 calc R . .
C2 C 0.6490(4) 0.74076(15) 0.30206(18) 0.0559(7) Uani 1 1 d . A .
H2A H 0.6082 0.7637 0.3510 0.084 Uiso 1 1 calc R . .
H2B H 0.7218 0.7731 0.2787 0.084 Uiso 1 1 calc R . .
H2C H 0.7147 0.6990 0.3273 0.084 Uiso 1 1 calc R . .
C3 C 0.3260(4) 0.61290(16) -0.07178(19) 0.0544(7) Uani 1 1 d . . .
H3A H 0.3745 0.5903 -0.1181 0.082 Uiso 1 1 calc R A .
193
H3B H 0.2601 0.6540 -0.0993 0.082 Uiso 1 1 calc R . .
H3C H 0.2511 0.5799 -0.0511 0.082 Uiso 1 1 calc R . .
C4 C 0.7507(3) 0.62352(14) 0.03087(19) 0.0456(6) Uani 1 1 d . . .
H4A H 0.7501 0.5997 -0.0274 0.068 Uiso 1 1 calc R A .
H4B H 0.8070 0.5938 0.0833 0.068 Uiso 1 1 calc R . .
H4C H 0.8124 0.6678 0.0343 0.068 Uiso 1 1 calc R . .
C12 C 0.4887(3) 0.85151(10) -0.00152(14) 0.0263(4) Uani 1 1 d . . .
N1 N 0.5121(5) 0.74454(17) 0.0795(2) 0.0213(8) Uiso 0.56 1 d P A 3
C10 C 0.6769(7) 0.7781(2) 0.0935(3) 0.0248(9) Uani 0.56 1 d P A 3
H10A H 0.7796 0.7591 0.1311 0.030 Uiso 0.56 1 calc PR A 3
C11 C 0.6688(5) 0.84073(18) 0.0463(2) 0.0255(7) Uani 0.56 1 d P A 3
C13 C 0.4039(6) 0.9054(2) -0.0630(3) 0.0364(9) Uani 0.56 1 d P A 3
H13A H 0.4657 0.9438 -0.0782 0.044 Uiso 0.56 1 calc PR A 3
C14 C 0.2273(9) 0.9000(4) -0.1001(5) 0.0406(15) Uani 0.56 1 d P A 3
H14A H 0.1691 0.9350 -0.1414 0.049 Uiso 0.56 1 calc PR A 3
C15 C 0.1334(9) 0.8429(3) -0.0769(4) 0.0410(13) Uani 0.56 1 d P A 3
H15A H 0.0132 0.8416 -0.1012 0.049 Uiso 0.56 1 calc PR A 3
C16 C 0.2157(6) 0.7881(3) -0.0184(3) 0.0292(9) Uani 0.56 1 d P A 3
H16A H 0.1532 0.7495 -0.0042 0.035 Uiso 0.56 1 calc PR A 3
C17 C 0.3953(5) 0.79289(19) 0.0184(2) 0.0208(7) Uani 0.56 1 d P A 3
C18 C 0.8149(9) 0.8898(4) 0.0448(5) 0.0424(17) Uani 0.56 1 d P A 3
H18A H 0.9219 0.8699 0.0822 0.064 Uiso 0.56 1 calc PR A 3
H18B H 0.7949 0.9352 0.0703 0.064 Uiso 0.56 1 calc PR A 3
H18C H 0.8224 0.8958 -0.0193 0.064 Uiso 0.56 1 calc PR A 3
N1A N 0.4541(6) 0.7421(2) 0.0653(3) 0.0219(10) Uiso 0.44 1 d P A 1
C10A C 0.2934(10) 0.7699(3) 0.0073(4) 0.0286(11) Uani 0.44 1 d P A 1
H10D H 0.1883 0.7457 -0.0022 0.034 Uiso 0.44 1 calc PR A 1
C11A C 0.3065(7) 0.8325(3) -0.0312(3) 0.0334(11) Uani 0.44 1 d P A 1
C13A C 0.7593(11) 0.9133(4) 0.0215(6) 0.0368(18) Uani 0.44 1 d P A 1
H13D H 0.8244 0.9516 0.0092 0.044 Uiso 0.44 1 calc PR A 1
C14A C 0.5820(7) 0.9121(3) -0.0183(4) 0.0369(11) Uani 0.44 1 d P A 1
H14D H 0.5259 0.9499 -0.0550 0.044 Uiso 0.44 1 calc PR A 1
C15A C 0.8421(9) 0.8588(4) 0.0793(5) 0.0395(15) Uani 0.44 1 d P A 1
H15D H 0.9614 0.8615 0.1059 0.047 Uiso 0.44 1 calc PR A 1
C16A C 0.7500(9) 0.7994(3) 0.0986(4) 0.0310(12) Uani 0.44 1 d P A 1
H16D H 0.8064 0.7629 0.1378 0.037 Uiso 0.44 1 calc PR A 1
C17A C 0.5766(8) 0.7966(3) 0.0585(4) 0.0268(9) Uani 0.44 1 d P A 1
C18A C 0.1651(11) 0.8759(5) -0.0917(6) 0.042(2) Uani 0.44 1 d P A 1
H18D H 0.0564 0.8512 -0.1005 0.062 Uiso 0.44 1 calc PR A 1
H18E H 0.1887 0.8836 -0.1521 0.062 Uiso 0.44 1 calc PR A 1
H18F H 0.1586 0.9210 -0.0617 0.062 Uiso 0.44 1 calc PR A 1
C22 C 0.4443(3) 0.50332(10) 0.22984(14) 0.0266(4) Uani 1 1 d . . .
N2 N 0.4993(5) 0.61222(17) 0.1677(2) 0.0254(7) Uiso 0.56 1 d P A 1
C20 C 0.6585(7) 0.5830(3) 0.2263(3) 0.0275(9) Uani 0.56 1 d P A 1
H20A H 0.7655 0.6058 0.2362 0.033 Uiso 0.56 1 calc PR A 1
C21 C 0.6382(5) 0.5204(2) 0.2648(2) 0.0285(8) Uani 0.56 1 d P A 1
C23 C 0.3575(6) 0.44518(19) 0.2499(3) 0.0333(8) Uani 0.56 1 d P A 1
H23A H 0.4132 0.4085 0.2890 0.040 Uiso 0.56 1 calc PR A 1
C24 C 0.1797(7) 0.4447(3) 0.2079(4) 0.0386(10) Uani 0.56 1 d P A 1
H24A H 0.1129 0.4066 0.2193 0.046 Uiso 0.56 1 calc PR A 1
C25 C 0.0996(12) 0.5001(4) 0.1489(6) 0.0383(16) Uani 0.56 1 d P A 1
H25A H -0.0195 0.4983 0.1210 0.046 Uiso 0.56 1 calc PR A 1
C26 C 0.1965(6) 0.5582(3) 0.1315(3) 0.0312(10) Uani 0.56 1 d P A 1
H26A H 0.1436 0.5953 0.0924 0.037 Uiso 0.56 1 calc PR A 1
C27 C 0.3740(5) 0.55914(18) 0.1739(3) 0.0260(8) Uani 0.56 1 d P A 1
C28 C 0.7706(11) 0.4739(4) 0.3261(5) 0.0385(15) Uani 0.56 1 d P A 1
194
H28A H 0.8826 0.4964 0.3379 0.058 Uiso 0.56 1 calc PR A 1
H28B H 0.7739 0.4290 0.2951 0.058 Uiso 0.56 1 calc PR A 1
H28C H 0.7413 0.4661 0.3850 0.058 Uiso 0.56 1 calc PR A 1
N2A N 0.4359(6) 0.6116(2) 0.1501(3) 0.0215(9) Uiso 0.44 1 d P A 3
C20A C 0.2638(8) 0.5820(3) 0.1296(4) 0.0266(12) Uani 0.44 1 d P A 3
H20D H 0.1674 0.6041 0.0901 0.032 Uiso 0.44 1 calc PR A 3
C21A C 0.2554(6) 0.5200(3) 0.1723(3) 0.0260(9) Uani 0.44 1 d P A 3
C23A C 0.6778(8) 0.4459(3) 0.3285(3) 0.0301(10) Uani 0.44 1 d P A 3
H23D H 0.7263 0.4084 0.3684 0.036 Uiso 0.44 1 calc PR A 3
C24A C 0.5011(6) 0.4467(2) 0.2860(3) 0.0250(9) Uani 0.44 1 d P A 3
H24D H 0.4268 0.4108 0.2956 0.030 Uiso 0.44 1 calc PR A 3
C25A C 0.7836(12) 0.5011(4) 0.3116(6) 0.0299(16) Uani 0.44 1 d P A 3
H25D H 0.9024 0.4996 0.3404 0.036 Uiso 0.44 1 calc PR A 3
C26A C 0.7165(8) 0.5581(3) 0.2530(4) 0.0265(11) Uani 0.44 1 d P A 3
H26D H 0.7883 0.5943 0.2415 0.032 Uiso 0.44 1 calc PR A 3
C27A C 0.5375(6) 0.5593(2) 0.2117(3) 0.0192(8) Uani 0.44 1 d P A 3
C28A C 0.1033(15) 0.4746(5) 0.1701(8) 0.039(2) Uani 0.44 1 d P A 3
H28D H 0.0011 0.4960 0.1300 0.058 Uiso 0.44 1 calc PR A 3
H28E H 0.0890 0.4698 0.2331 0.058 Uiso 0.44 1 calc PR A 3
H28F H 0.1208 0.4283 0.1459 0.058 Uiso 0.44 1 calc PR A 3
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Al1 0.0504(4) 0.0184(3) 0.0257(3) 0.0018(2) 0.0162(3) 0.0018(2)
Al2 0.0398(4) 0.0195(3) 0.0253(3) -0.0004(2) 0.0122(3) 0.0004(2)
C1 0.0724(18) 0.0494(15) 0.0510(15) 0.0123(12) 0.0378(14) 0.0206(13)
C2 0.086(2) 0.0450(15) 0.0313(12) 0.0042(11) 0.0057(13) -0.0137(14)
C3 0.0593(16) 0.0553(17) 0.0455(15) -0.0130(13) 0.0080(12) -0.0161(13)
C4 0.0516(14) 0.0426(13) 0.0469(14) 0.0035(11) 0.0205(11) 0.0138(11)
C12 0.0396(11) 0.0210(9) 0.0216(9) 0.0010(7) 0.0137(8) 0.0041(8)
C10 0.020(2) 0.025(2) 0.029(2) -0.0038(17) 0.0050(19) 0.0013(19)
C11 0.0330(18) 0.0211(17) 0.0268(17) -0.0055(14) 0.0156(15) -0.0047(15)
C13 0.062(3) 0.0232(18) 0.0281(18) 0.0055(15) 0.0188(18) 0.0137(18)
C14 0.060(5) 0.038(3) 0.025(2) 0.008(2) 0.012(3) 0.028(3)
C15 0.037(3) 0.055(4) 0.030(3) 0.001(3) 0.006(2) 0.017(3)
C16 0.024(2) 0.036(2) 0.029(2) -0.0003(18) 0.0085(18) 0.0016(19)
C17 0.023(2) 0.0223(17) 0.0169(16) 0.0005(13) 0.0057(14) 0.0042(16)
C18 0.043(5) 0.036(5) 0.050(5) -0.002(3) 0.016(4) -0.012(3)
C10A 0.023(3) 0.033(3) 0.029(3) -0.003(2) 0.004(2) 0.004(3)
C11A 0.040(3) 0.035(3) 0.023(2) -0.003(2) 0.005(2) 0.011(2)
C13A 0.048(5) 0.026(4) 0.044(4) -0.003(3) 0.023(4) -0.009(3)
C14A 0.056(3) 0.023(2) 0.035(3) 0.003(2) 0.017(2) 0.000(2)
C15A 0.033(3) 0.038(4) 0.048(4) -0.005(3) 0.011(3) -0.004(3)
C16A 0.034(3) 0.028(3) 0.032(3) 0.002(2) 0.013(3) 0.002(3)
C17A 0.037(3) 0.022(2) 0.026(2) -0.0030(19) 0.017(2) 0.000(2)
C18A 0.040(6) 0.046(7) 0.034(4) 0.011(5) 0.003(4) 0.015(4)
C22 0.0377(11) 0.0216(9) 0.0236(9) -0.0023(8) 0.0132(8) 0.0014(8)
C20 0.028(3) 0.028(2) 0.025(2) -0.0025(17) 0.0034(17) 0.000(2)
C21 0.038(2) 0.0245(19) 0.0227(17) -0.0023(14) 0.0071(16) 0.0034(18)
C23 0.050(3) 0.0202(17) 0.0323(19) 0.0024(14) 0.0151(18) -0.0014(16)
195
C24 0.047(3) 0.030(2) 0.043(3) -0.0037(19) 0.020(2) -0.012(2)
C25 0.031(3) 0.047(5) 0.038(4) -0.002(3) 0.010(2) 0.000(3)
C26 0.028(3) 0.029(3) 0.034(2) 0.001(2) 0.005(2) 0.003(2)
C27 0.034(2) 0.0182(16) 0.0276(17) -0.0006(14) 0.0115(17) -0.0008(15)
C28 0.044(4) 0.033(4) 0.035(3) 0.008(3) 0.004(2) 0.004(4)
C20A 0.020(3) 0.027(3) 0.031(3) -0.001(2) 0.004(2) 0.001(2)
C21A 0.023(2) 0.029(3) 0.028(2) -0.002(2) 0.0087(18) -0.003(2)
C23A 0.044(3) 0.019(2) 0.029(2) 0.0050(19) 0.011(2) 0.008(2)
C24A 0.035(3) 0.017(2) 0.027(2) -0.0010(16) 0.0139(19) -0.0016(17)
C25A 0.029(3) 0.030(4) 0.030(4) 0.002(3) 0.006(2) -0.001(4)
C26A 0.025(3) 0.023(3) 0.029(3) 0.002(2) 0.004(2) -0.004(2)
C27A 0.025(2) 0.0142(19) 0.0183(19) 0.0000(15) 0.0050(17) 0.0000(17)
C28A 0.030(3) 0.041(6) 0.046(6) 0.006(4) 0.010(4) -0.003(5)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Al1 C1 1.947(3) . ?
Al1 C2 1.949(3) . ?
Al1 N2 2.008(3) . ?
Al1 N1 2.016(3) . ?
Al1 N2A 2.027(4) . ?
Al1 N1A 2.033(4) . ?
Al1 Al2 2.8828(8) . ?
Al2 C3 1.941(3) . ?
Al2 C4 1.946(2) . ?
Al2 N1A 2.004(4) . ?
Al2 N2A 2.004(4) . ?
Al2 N1 2.024(3) . ?
Al2 N2 2.037(3) . ?
C1 H1A 0.9600 . ?
C1 H1B 0.9600 . ?
C1 H1C 0.9600 . ?
C2 H2A 0.9600 . ?
C2 H2B 0.9600 . ?
C2 H2C 0.9600 . ?
C3 H3A 0.9600 . ?
C3 H3B 0.9600 . ?
C3 H3C 0.9600 . ?
C4 H4A 0.9600 . ?
C4 H4B 0.9600 . ?
C4 H4C 0.9600 . ?
C12 C17 1.399(5) . ?
196
C12 C13 1.404(4) . ?
C12 C14A 1.412(5) . ?
C12 C17A 1.415(6) . ?
C12 C11 1.438(4) . ?
C12 C11A 1.446(6) . ?
N1 C10 1.421(6) . ?
N1 C17 1.433(5) . ?
C10 C11 1.354(6) . ?
C10 H10A 0.9300 . ?
C11 C18 1.487(7) . ?
C13 C14 1.373(8) . ?
C13 H13A 0.9300 . ?
C14 C15 1.395(8) . ?
C14 H14A 0.9300 . ?
C15 C16 1.389(8) . ?
C15 H15A 0.9300 . ?
C16 C17 1.394(5) . ?
C16 H16A 0.9300 . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
N1A C17A 1.433(6) . ?
N1A C10A 1.438(8) . ?
C10A C11A 1.316(8) . ?
C10A H10D 0.9300 . ?
C11A C18A 1.483(9) . ?
C13A C15A 1.379(9) . ?
C13A C14A 1.381(10) . ?
C13A H13D 0.9300 . ?
C14A H14D 0.9300 . ?
C15A C16A 1.401(10) . ?
C15A H15D 0.9300 . ?
C16A C17A 1.353(8) . ?
C16A H16D 0.9300 . ?
C18A H18D 0.9600 . ?
C18A H18E 0.9600 . ?
C18A H18F 0.9600 . ?
C22 C24A 1.347(5) . ?
C22 C27A 1.349(5) . ?
C22 C27 1.356(4) . ?
C22 C23 1.362(4) . ?
C22 C21 1.528(5) . ?
C22 C21A 1.553(5) . ?
N2 C27 1.428(5) . ?
N2 C20 1.442(6) . ?
C20 C21 1.329(6) . ?
C20 H20A 0.9300 . ?
C21 C28 1.478(8) . ?
C23 C24 1.389(7) . ?
C23 H23A 0.9300 . ?
C24 C25 1.395(7) . ?
C24 H24A 0.9300 . ?
C25 C26 1.396(9) . ?
C25 H25A 0.9300 . ?
C26 C27 1.388(6) . ?
C26 H26A 0.9300 . ?
197
C28 H28A 0.9600 . ?
C28 H28B 0.9600 . ?
C28 H28C 0.9600 . ?
N2A C27A 1.432(6) . ?
N2A C20A 1.435(8) . ?
C20A C21A 1.330(8) . ?
C20A H20D 0.9300 . ?
C21A C28A 1.473(12) . ?
C23A C24A 1.383(8) . ?
C23A C25A 1.396(8) . ?
C23A H23D 0.9300 . ?
C24A H24D 0.9300 . ?
C25A C26A 1.388(10) . ?
C25A H25D 0.9300 . ?
C26A C27A 1.396(7) . ?
C26A H26D 0.9300 . ?
C28A H28D 0.9600 . ?
C28A H28E 0.9600 . ?
C28A H28F 0.9600 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C1 Al1 C2 119.04(14) . . ?
C1 Al1 N2 118.88(14) . . ?
C2 Al1 N2 105.14(15) . . ?
C1 Al1 N1 115.18(13) . . ?
C2 Al1 N1 105.36(14) . . ?
N2 Al1 N1 88.51(13) . . ?
C1 Al1 N2A 106.09(16) . . ?
C2 Al1 N2A 118.92(16) . . ?
N2 Al1 N2A 14.34(12) . . ?
N1 Al1 N2A 88.51(14) . . ?
C1 Al1 N1A 103.80(16) . . ?
C2 Al1 N1A 117.68(16) . . ?
N2 Al1 N1A 88.94(15) . . ?
N1 Al1 N1A 12.94(13) . . ?
N2A Al1 N1A 85.75(16) . . ?
C1 Al1 Al2 121.79(10) . . ?
C2 Al1 Al2 119.11(10) . . ?
N2 Al1 Al2 44.95(9) . . ?
N1 Al1 Al2 44.58(9) . . ?
N2A Al1 Al2 44.04(11) . . ?
N1A Al1 Al2 44.03(11) . . ?
C3 Al2 C4 117.91(13) . . ?
C3 Al2 N1A 105.53(17) . . ?
C4 Al2 N1A 117.19(16) . . ?
C3 Al2 N2A 105.18(16) . . ?
C4 Al2 N2A 119.16(15) . . ?
N1A Al2 N2A 87.11(16) . . ?
C3 Al2 N1 117.44(14) . . ?
198
C4 Al2 N1 105.20(14) . . ?
N1A Al2 N1 13.00(13) . . ?
N2A Al2 N1 88.91(14) . . ?
C3 Al2 N2 118.30(14) . . ?
C4 Al2 N2 105.85(13) . . ?
N1A Al2 N2 88.94(15) . . ?
N2A Al2 N2 14.29(12) . . ?
N1 Al2 N2 87.52(13) . . ?
C3 Al2 Al1 122.89(10) . . ?
C4 Al2 Al1 119.19(9) . . ?
N1A Al2 Al1 44.83(11) . . ?
N2A Al2 Al1 44.66(11) . . ?
N1 Al2 Al1 44.37(9) . . ?
N2 Al2 Al1 44.15(9) . . ?
Al1 C1 H1A 109.5 . . ?
Al1 C1 H1B 109.5 . . ?
H1A C1 H1B 109.5 . . ?
Al1 C1 H1C 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
Al1 C2 H2A 109.5 . . ?
Al1 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
Al1 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
Al2 C3 H3A 109.5 . . ?
Al2 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
Al2 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
Al2 C4 H4A 109.5 . . ?
Al2 C4 H4B 109.5 . . ?
H4A C4 H4B 109.5 . . ?
Al2 C4 H4C 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?
C17 C12 C13 120.4(3) . . ?
C17 C12 C14A 177.7(3) . . ?
C13 C12 C14A 59.8(3) . . ?
C17 C12 C17A 60.2(3) . . ?
C13 C12 C17A 178.4(3) . . ?
C14A C12 C17A 119.7(4) . . ?
C17 C12 C11 107.7(2) . . ?
C13 C12 C11 131.8(3) . . ?
C14A C12 C11 72.3(3) . . ?
C17A C12 C11 47.5(3) . . ?
C17 C12 C11A 47.4(3) . . ?
C13 C12 C11A 73.0(3) . . ?
C14A C12 C11A 132.6(3) . . ?
C17A C12 C11A 107.7(3) . . ?
C11 C12 C11A 155.1(3) . . ?
C10 N1 C17 103.6(3) . . ?
C10 N1 Al1 115.1(3) . . ?
C17 N1 Al1 117.5(2) . . ?
199
C10 N1 Al2 112.9(3) . . ?
C17 N1 Al2 117.1(3) . . ?
Al1 N1 Al2 91.05(13) . . ?
C11 C10 N1 112.9(4) . . ?
C11 C10 H10A 123.5 . . ?
N1 C10 H10A 123.5 . . ?
C10 C11 C12 106.3(3) . . ?
C10 C11 C18 127.5(5) . . ?
C12 C11 C18 126.2(4) . . ?
C14 C13 C12 118.2(4) . . ?
C14 C13 H13A 120.9 . . ?
C12 C13 H13A 120.9 . . ?
C13 C14 C15 121.3(6) . . ?
C13 C14 H14A 119.4 . . ?
C15 C14 H14A 119.4 . . ?
C16 C15 C14 121.3(7) . . ?
C16 C15 H15A 119.3 . . ?
C14 C15 H15A 119.3 . . ?
C15 C16 C17 117.6(4) . . ?
C15 C16 H16A 121.2 . . ?
C17 C16 H16A 121.2 . . ?
C16 C17 C12 121.1(3) . . ?
C16 C17 N1 129.4(4) . . ?
C12 C17 N1 109.4(3) . . ?
C11 C18 H18A 109.5 . . ?
C11 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C11 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
C17A N1A C10A 102.6(4) . . ?
C17A N1A Al2 116.9(3) . . ?
C10A N1A Al2 115.6(3) . . ?
C17A N1A Al1 115.7(3) . . ?
C10A N1A Al1 115.7(3) . . ?
Al2 N1A Al1 91.14(17) . . ?
C11A C10A N1A 114.8(6) . . ?
C11A C10A H10D 122.6 . . ?
N1A C10A H10D 122.6 . . ?
C10A C11A C12 106.0(5) . . ?
C10A C11A C18A 127.8(7) . . ?
C12 C11A C18A 126.2(6) . . ?
C15A C13A C14A 121.4(8) . . ?
C15A C13A H13D 119.3 . . ?
C14A C13A H13D 119.3 . . ?
C13A C14A C12 117.7(5) . . ?
C13A C14A H14D 121.1 . . ?
C12 C14A H14D 121.2 . . ?
C13A C15A C16A 121.3(8) . . ?
C13A C15A H15D 119.3 . . ?
C16A C15A H15D 119.3 . . ?
C17A C16A C15A 118.1(6) . . ?
C17A C16A H16D 121.0 . . ?
C15A C16A H16D 121.0 . . ?
C16A C17A C12 121.7(4) . . ?
C16A C17A N1A 129.3(5) . . ?
200
C12 C17A N1A 109.0(5) . . ?
C11A C18A H18D 109.5 . . ?
C11A C18A H18E 109.5 . . ?
H18D C18A H18E 109.5 . . ?
C11A C18A H18F 109.5 . . ?
H18D C18A H18F 109.5 . . ?
H18E C18A H18F 109.5 . . ?
C24A C22 C27A 128.1(3) . . ?
C24A C22 C27 175.3(3) . . ?
C27A C22 C27 56.3(3) . . ?
C24A C22 C23 49.2(3) . . ?
C27A C22 C23 177.3(3) . . ?
C27 C22 C23 126.4(3) . . ?
C24A C22 C21 79.1(3) . . ?
C27A C22 C21 49.1(2) . . ?
C27 C22 C21 105.3(3) . . ?
C23 C22 C21 128.3(3) . . ?
C24A C22 C21A 127.9(3) . . ?
C27A C22 C21A 104.0(3) . . ?
C27 C22 C21A 47.7(2) . . ?
C23 C22 C21A 78.7(3) . . ?
C21 C22 C21A 153.1(3) . . ?
C27 N2 C20 102.6(3) . . ?
C27 N2 Al1 117.6(2) . . ?
C20 N2 Al1 114.4(3) . . ?
C27 N2 Al2 117.3(3) . . ?
C20 N2 Al2 114.6(3) . . ?
Al1 N2 Al2 90.90(13) . . ?
C21 C20 N2 113.8(4) . . ?
C21 C20 H20A 123.1 . . ?
N2 C20 H20A 123.1 . . ?
C20 C21 C28 129.2(5) . . ?
C20 C21 C22 105.4(3) . . ?
C28 C21 C22 125.4(4) . . ?
C22 C23 C24 115.1(4) . . ?
C22 C23 H23A 122.4 . . ?
C24 C23 H23A 122.4 . . ?
C23 C24 C25 121.3(5) . . ?
C23 C24 H24A 119.3 . . ?
C25 C24 H24A 119.3 . . ?
C24 C25 C26 120.5(7) . . ?
C24 C25 H25A 119.8 . . ?
C26 C25 H25A 119.7 . . ?
C27 C26 C25 118.3(6) . . ?
C27 C26 H26A 120.8 . . ?
C25 C26 H26A 120.8 . . ?
C22 C27 C26 118.3(3) . . ?
C22 C27 N2 112.9(3) . . ?
C26 C27 N2 128.8(4) . . ?
C21 C28 H28A 109.5 . . ?
C21 C28 H28B 109.5 . . ?
H28A C28 H28B 109.5 . . ?
C21 C28 H28C 109.5 . . ?
H28A C28 H28C 109.5 . . ?
H28B C28 H28C 109.5 . . ?
C27A N2A C20A 102.7(4) . . ?
201
C27A N2A Al2 118.4(3) . . ?
C20A N2A Al2 114.5(3) . . ?
C27A N2A Al1 116.7(3) . . ?
C20A N2A Al1 113.8(3) . . ?
Al2 N2A Al1 91.31(16) . . ?
C21A C20A N2A 113.6(5) . . ?
C21A C20A H20D 123.2 . . ?
N2A C20A H20D 123.2 . . ?
C20A C21A C28A 129.5(6) . . ?
C20A C21A C22 105.7(4) . . ?
C28A C21A C22 124.8(5) . . ?
C24A C23A C25A 120.1(5) . . ?
C24A C23A H23D 119.9 . . ?
C25A C23A H23D 119.9 . . ?
C22 C24A C23A 115.1(4) . . ?
C22 C24A H24D 122.4 . . ?
C23A C24A H24D 122.4 . . ?
C26A C25A C23A 121.8(7) . . ?
C26A C25A H25D 119.1 . . ?
C23A C25A H25D 119.1 . . ?
C25A C26A C27A 117.8(6) . . ?
C25A C26A H26D 121.1 . . ?
C27A C26A H26D 121.1 . . ?
C22 C27A C26A 117.0(4) . . ?
C22 C27A N2A 114.0(4) . . ?
C26A C27A N2A 129.0(5) . . ?
C21A C28A H28D 109.5 . . ?
C21A C28A H28E 109.5 . . ?
H28D C28A H28E 109.5 . . ?
C21A C28A H28F 109.5 . . ?
H28D C28A H28F 109.5 . . ?
H28E C28A H28F 109.5 . . ?
_diffrn_measured_fraction_theta_max
_diffrn_reflns_theta_full
_diffrn_measured_fraction_theta_full
_refine_diff_density_max
_refine_diff_density_min
_refine_diff_density_rms
1.000
26.00
1.000
0.478
-0.425
0.068
202
CIF File For [{di(3-methylindolyl)phenylmethane}(AlMe2)2]
_audit_creation_method
_chemical_name_systematic
;
?
;
_chemical_name_common
_chemical_melting_point
_chemical_formula_moiety
_chemical_formula_sum
SHELXL-97
?
?
'C29 H32 Al2 N2'
'C29 H32 Al2 N2'
_chemical_formula_weight
462.53
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Al' 'Al' 0.0645 0.0514
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
_symmetry_space_group_name_H-M
'Triclinic'
'P -1'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
_cell_length_a
_cell_length_b
_cell_length_c
_cell_angle_alpha
_cell_angle_beta
_cell_angle_gamma
_cell_volume
_cell_formula_units_Z
_cell_measurement_temperature
_cell_measurement_reflns_used
_cell_measurement_theta_min
_cell_measurement_theta_max
11.9211(18)
12.4867(19)
18.489(3)
91.419(3)
107.696(3)
101.049(3)
2563.2(7)
4
-133
6800
2.206
28.336
_exptl_crystal_description
_exptl_crystal_colour
_exptl_crystal_size_max
_exptl_crystal_size_mid
_exptl_crystal_size_min
_exptl_crystal_density_meas
'rectangular Brick'
'Colorless'
.35
.35
.25
?
203
_exptl_crystal_density_diffrn
1.199
_exptl_crystal_density_method
'not measured'
_exptl_crystal_F_000
984
_exptl_absorpt_coefficient_mu
0.133
_exptl_absorpt_correction_type
multi-scan
_exptl_absorpt_correction_T_min
.800
_exptl_absorpt_correction_T_max
1.00
_exptl_absorpt_process_details 'sadabs (Sheldrick, 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
_diffrn_radiation_wavelength
_diffrn_radiation_type
_diffrn_radiation_source
_diffrn_radiation_monochromator
_diffrn_measurement_device_type
_diffrn_measurement_method
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
?
_diffrn_reflns_number
_diffrn_reflns_av_R_equivalents
_diffrn_reflns_av_sigmaI/netI
_diffrn_reflns_limit_h_min
_diffrn_reflns_limit_h_max
_diffrn_reflns_limit_k_min
_diffrn_reflns_limit_k_max
_diffrn_reflns_limit_l_min
_diffrn_reflns_limit_l_max
_diffrn_reflns_theta_min
_diffrn_reflns_theta_max
_reflns_number_total
_reflns_number_gt
_reflns_threshold_expression
-133
0.71073
MoK\a
'fine-focus sealed tube'
'graphite'
'Bruker platform with 4k CCD'
'omega scans'
_computing_data_collection
_computing_cell_refinement
_computing_data_reduction
_computing_structure_solution
_computing_structure_refinement
_computing_molecular_graphics ?
_computing_publication_material ?
'Smart 5.630 '
'Saintplus 5.45 '
'Saintplus 5.45'
'SHELXS-97 (Sheldrick, 1990)'
'SHELXL-97 (Sheldrick, 1997)'
19281
0.0234
0.0327
-14
14
-15
15
-17
22
1.16
26.00
10067
8574
>2sigma(I)
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
204
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0706P)^2^+2.3039P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary
difmap
_atom_sites_solution_hydrogens
diffmap
_refine_ls_hydrogen_treatment
refall
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
10067
_refine_ls_number_parameters
591
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.0645
_refine_ls_R_factor_gt
0.0547
_refine_ls_wR_factor_ref
0.1486
_refine_ls_wR_factor_gt
0.1422
_refine_ls_goodness_of_fit_ref
1.026
_refine_ls_restrained_S_all
1.026
_refine_ls_shift/su_max
0.000
_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Al1 Al 0.65780(6) 0.88497(5) 0.19976(4) 0.02694(15) Uani 1 1 d . . .
Al2 Al 0.41366(6) 0.77009(6) 0.13826(4) 0.03305(17) Uani 1 1 d . . .
Al2A Al 0.88450(6) 0.26276(6) 0.31488(4) 0.03072(16) Uani 1 1 d . . .
Al1A Al 1.13235(6) 0.36420(5) 0.35924(4) 0.02904(16) Uani 1 1 d . . .
N1 N 0.57115(17) 0.73139(14) 0.19347(10) 0.0283(4) Uani 1 1 d . . .
N2 N 0.49598(16) 0.90373(14) 0.20751(9) 0.0259(4) Uani 1 1 d . . .
N1A N 1.03638(16) 0.21171(15) 0.32305(10) 0.0271(4) Uani 1 1 d . . .
N2A N 0.98226(17) 0.39406(15) 0.28713(10) 0.0280(4) Uani 1 1 d . . .
C2 C 0.6920(3) 0.9268(2) 0.10629(14) 0.0439(6) Uani 1 1 d . . .
H2A H 0.7752 0.9681 0.1190 0.066 Uiso 1 1 calc R . .
H2B H 0.6368 0.9726 0.0800 0.066 Uiso 1 1 calc R . .
H2C H 0.6812 0.8608 0.0730 0.066 Uiso 1 1 calc R . .
C3 C 0.7884(2) 0.9375(2) 0.29540(13) 0.0353(5) Uani 1 1 d . . .
H3A H 0.8601 0.9755 0.2839 0.053 Uiso 1 1 calc R . .
H3B H 0.8072 0.8751 0.3244 0.053 Uiso 1 1 calc R . .
205
H3C H 0.7631 0.9882 0.3255 0.053 Uiso 1 1 calc R . .
C4 C 0.2762(3) 0.6716(3) 0.15265(19) 0.0656(9) Uani 1 1 d . . .
H4A H 0.2081 0.6610 0.1055 0.098 Uiso 1 1 calc R . .
H4B H 0.2540 0.7034 0.1940 0.098 Uiso 1 1 calc R . .
H4C H 0.2973 0.6009 0.1657 0.098 Uiso 1 1 calc R . .
C5 C 0.3903(3) 0.7973(2) 0.03112(14) 0.0511(7) Uani 1 1 d . . .
H5A H 0.3080 0.7625 0.0003 0.077 Uiso 1 1 calc R . .
H5B H 0.4478 0.7667 0.0131 0.077 Uiso 1 1 calc R . .
H5C H 0.4033 0.8764 0.0265 0.077 Uiso 1 1 calc R . .
C11 C 0.59722(19) 0.63831(17) 0.16132(12) 0.0279(4) Uani 1 1 d . . .
C12 C 0.6106(2) 0.62323(19) 0.08968(12) 0.0330(5) Uani 1 1 d . . .
H12A H 0.6027 0.6783 0.0550 0.040 Uiso 1 1 calc R . .
C13 C 0.6361(2) 0.5241(2) 0.07133(13) 0.0368(5) Uani 1 1 d . . .
H13A H 0.6464 0.5110 0.0232 0.044 Uiso 1 1 calc R . .
C14 C 0.6468(2) 0.4434(2) 0.12226(14) 0.0386(6) Uani 1 1 d . . .
H14A H 0.6647 0.3765 0.1082 0.046 Uiso 1 1 calc R . .
C15 C 0.6320(2) 0.45857(19) 0.19252(13) 0.0338(5) Uani 1 1 d . . .
H15A H 0.6392 0.4031 0.2269 0.041 Uiso 1 1 calc R . .
C16 C 0.60598(18) 0.55787(17) 0.21194(12) 0.0273(4) Uani 1 1 d . . .
C17 C 0.58612(19) 0.59920(17) 0.27981(12) 0.0273(4) Uani 1 1 d . . .
C18 C 0.56628(19) 0.70186(17) 0.26842(12) 0.0262(4) Uani 1 1 d . . .
C19 C 0.5945(2) 0.53343(19) 0.34714(13) 0.0351(5) Uani 1 1 d . . .
H19A H 0.5784 0.5748 0.3873 0.053 Uiso 1 1 calc R . .
H19B H 0.6755 0.5182 0.3664 0.053 Uiso 1 1 calc R . .
H19C H 0.5351 0.4642 0.3318 0.053 Uiso 1 1 calc R . .
C21 C 0.46378(18) 1.00748(17) 0.19723(12) 0.0263(4) Uani 1 1 d . . .
C22 C 0.4401(2) 1.06196(19) 0.13150(13) 0.0324(5) Uani 1 1 d . . .
H22A H 0.4397 1.0291 0.0845 0.039 Uiso 1 1 calc R . .
C23 C 0.4170(2) 1.1657(2) 0.13680(14) 0.0365(5) Uani 1 1 d . . .
H23A H 0.4012 1.2051 0.0928 0.044 Uiso 1 1 calc R . .
C24 C 0.4166(2) 1.2134(2) 0.20576(14) 0.0367(5) Uani 1 1 d . . .
H24A H 0.4010 1.2850 0.2079 0.044 Uiso 1 1 calc R . .
C25 C 0.4384(2) 1.15878(19) 0.27072(13) 0.0334(5) Uani 1 1 d . . .
H25A H 0.4373 1.1916 0.3173 0.040 Uiso 1 1 calc R . .
C26 C 0.46242(18) 1.05332(18) 0.26659(12) 0.0269(4) Uani 1 1 d . . .
C27 C 0.4933(2) 0.97713(18) 0.32293(12) 0.0288(5) Uani 1 1 d . . .
C28 C 0.51131(19) 0.88846(17) 0.28744(11) 0.0259(4) Uani 1 1 d . . .
C29 C 0.5087(2) 0.9998(2) 0.40602(13) 0.0383(5) Uani 1 1 d . . .
H29A H 0.5294 0.9364 0.4332 0.057 Uiso 1 1 calc R . .
H29B H 0.4333 1.0134 0.4116 0.057 Uiso 1 1 calc R . .
H29C H 0.5732 1.0644 0.4274 0.057 Uiso 1 1 calc R . .
C2A C 1.2749(2) 0.4029(2) 0.32807(17) 0.0470(6) Uani 1 1 d . . .
H2AA H 1.3424 0.4414 0.3713 0.070 Uiso 1 1 calc R . .
H2AB H 1.2598 0.4506 0.2864 0.070 Uiso 1 1 calc R . .
H2AC H 1.2947 0.3362 0.3107 0.070 Uiso 1 1 calc R . .
C3A C 1.1515(3) 0.4038(2) 0.46589(13) 0.0459(6) Uani 1 1 d . . .
H3AA H 1.2349 0.4414 0.4920 0.069 Uiso 1 1 calc R . .
H3AB H 1.1321 0.3374 0.4906 0.069 Uiso 1 1 calc R . .
H3AC H 1.0972 0.4525 0.4685 0.069 Uiso 1 1 calc R . .
C4A C 0.7451(2) 0.1951(2) 0.22868(16) 0.0440(6) Uani 1 1 d . . .
H4AA H 0.6754 0.1717 0.2464 0.066 Uiso 1 1 calc R . .
H4AB H 0.7624 0.1313 0.2055 0.066 Uiso 1 1 calc R . .
H4AC H 0.7275 0.2482 0.1909 0.066 Uiso 1 1 calc R . .
C5A C 0.8496(3) 0.2800(3) 0.41021(17) 0.0535(7) Uani 1 1 d . . .
H5AA H 0.7648 0.2475 0.4025 0.080 Uiso 1 1 calc R . .
H5AB H 0.8659 0.3581 0.4269 0.080 Uiso 1 1 calc R . .
206
H5AC H 0.9007 0.2430 0.4491 0.080 Uiso 1 1 calc R . .
C11A C 1.08216(18) 0.12815(17) 0.36650(12) 0.0273(4) Uani 1 1 d . . .
C12A C 1.0914(2) 0.11033(19) 0.44188(13) 0.0328(5) Uani 1 1 d . . .
H12B H 1.0658 0.1571 0.4721 0.039 Uiso 1 1 calc R . .
C13A C 1.1391(2) 0.0223(2) 0.47124(14) 0.0388(5) Uani 1 1 d . . .
H13B H 1.1461 0.0082 0.5225 0.047 Uiso 1 1 calc R . .
C14A C 1.1773(2) -0.0461(2) 0.42704(15) 0.0407(6) Uani 1 1 d . . .
H14B H 1.2102 -0.1059 0.4487 0.049 Uiso 1 1 calc R . .
C15A C 1.1681(2) -0.02822(19) 0.35248(14) 0.0363(5) Uani 1 1 d . . .
H15B H 1.1945 -0.0750 0.3227 0.044 Uiso 1 1 calc R . .
C16A C 1.11925(18) 0.06007(18) 0.32128(12) 0.0285(4) Uani 1 1 d . . .
C17A C 1.09315(19) 0.09876(18) 0.24573(12) 0.0291(5) Uani 1 1 d . . .
C18A C 1.04437(19) 0.18819(17) 0.24774(12) 0.0273(4) Uani 1 1 d . B .
C19A C 1.1155(2) 0.0398(2) 0.18125(14) 0.0387(5) Uani 1 1 d . . .
H19D H 1.0924 0.0784 0.1352 0.058 Uiso 1 1 calc R . .
H19E H 1.0676 -0.0352 0.1717 0.058 Uiso 1 1 calc R . .
H19F H 1.2012 0.0379 0.1948 0.058 Uiso 1 1 calc R . .
C21A C 0.96451(19) 0.50282(18) 0.28989(12) 0.0275(4) Uani 1 1 d . . .
C22A C 0.9546(2) 0.5651(2) 0.35037(13) 0.0345(5) Uani 1 1 d . . .
H22B H 0.9572 0.5356 0.3976 0.041 Uiso 1 1 calc R . .
C23A C 0.9408(2) 0.6714(2) 0.33920(14) 0.0417(6) Uani 1 1 d . . .
H23B H 0.9334 0.7156 0.3794 0.050 Uiso 1 1 calc R . .
C24A C 0.9375(2) 0.7150(2) 0.27003(16) 0.0443(6) Uani 1 1 d . . .
H24B H 0.9293 0.7888 0.2643 0.053 Uiso 1 1 calc R . .
C25A C 0.9460(2) 0.6534(2) 0.21011(14) 0.0374(5) Uani 1 1 d . . .
H25B H 0.9432 0.6836 0.1631 0.045 Uiso 1 1 calc R . .
C26A C 0.95869(19) 0.54491(18) 0.21982(12) 0.0290(5) Uani 1 1 d . . .
C27A C 0.96740(19) 0.45940(18) 0.16928(12) 0.0288(5) Uani 1 1 d . . .
C28A C 0.98276(19) 0.37127(18) 0.20964(11) 0.0277(4) Uani 1 1 d . B .
C29A C 0.9540(2) 0.4734(2) 0.08658(13) 0.0385(6) Uani 1 1 d . . .
H29D H 0.9631 0.4064 0.0623 0.058 Uiso 1 1 calc R . .
H29E H 1.0159 0.5351 0.0828 0.058 Uiso 1 1 calc R . .
H29F H 0.8741 0.4878 0.0609 0.058 Uiso 1 1 calc R . .
C1 C 0.55542(19) 0.78965(18) 0.32361(12) 0.0276(4) Uani 1 1 d . A .
H1A H 0.6395 0.8192 0.3576 0.033 Uiso 1 1 calc R . .
C31 C 0.4846(2) 0.74550(18) 0.37702(13) 0.0346(5) Uani 1 1 d . . .
C32C C 0.3695(4) 0.7204(4) 0.3620(3) 0.0362(12) Uiso 0.64 1 d P A 1
H32A H 0.3208 0.7257 0.3115 0.043 Uiso 0.64 1 calc PR A 1
C33C C 0.3116(4) 0.6858(4) 0.4151(3) 0.0418(10) Uiso 0.64 1 d P A 1
H33A H 0.2263 0.6680 0.4011 0.050 Uiso 0.64 1 calc PR A 1
C34C C 0.3818(6) 0.6783(3) 0.4878(3) 0.0399(9) Uiso 0.64 1 d P A 1
H34A H 0.3437 0.6533 0.5243 0.048 Uiso 0.64 1 calc PR A 1
C35C C 0.5067(5) 0.7059(4) 0.5100(3) 0.0429(11) Uiso 0.64 1 d P A 1
H35A H 0.5536 0.6998 0.5609 0.051 Uiso 0.64 1 calc PR A 1
C36C C 0.5616(5) 0.7431(4) 0.4558(3) 0.0357(11) Uiso 0.64 1 d P A 1
H36A H 0.6466 0.7661 0.4695 0.043 Uiso 0.64 1 calc PR A 1
C32D C 0.3462(7) 0.7252(6) 0.3393(5) 0.0297(17) Uiso 0.36 1 d P A 3
H32C H 0.3113 0.7358 0.2872 0.036 Uiso 0.36 1 calc PR A 3
C33D C 0.2763(7) 0.6913(6) 0.3848(5) 0.0373(16) Uiso 0.36 1 d P A 3
H33B H 0.1910 0.6784 0.3646 0.045 Uiso 0.36 1 calc PR A 3
C34D C 0.3325(7) 0.6758(5) 0.4618(5) 0.0322(14) Uiso 0.36 1 d P A 3
H34B H 0.2823 0.6527 0.4922 0.039 Uiso 0.36 1 calc PR A 3
C35D C 0.4539(9) 0.6918(6) 0.4954(4) 0.0310(14) Uiso 0.36 1 d P A 3
H35B H 0.4897 0.6824 0.5476 0.037 Uiso 0.36 1 calc PR A 3
C36D C 0.5221(8) 0.7234(7) 0.4461(4) 0.0348(19) Uiso 0.36 1 d P A 3
H36B H 0.6065 0.7290 0.4671 0.042 Uiso 0.36 1 calc PR A 3
207
C1A C 0.9868(2) 0.25585(19) 0.18341(12) 0.0315(5) Uani 1 1 d . . .
C31A C 1.0505(4) 0.2630(3) 0.1201(2) 0.0245(10) Uiso 0.66 1 d P B 1
C32A C 1.1602(4) 0.3287(4) 0.1283(2) 0.0300(8) Uiso 0.66 1 d P B 1
H32D H 1.2025 0.3728 0.1748 0.036 Uiso 0.66 1 calc PR B 1
C33A C 1.2104(4) 0.3318(4) 0.0702(2) 0.0406(9) Uiso 0.66 1 d P B 1
H33C H 1.2869 0.3774 0.0767 0.049 Uiso 0.66 1 calc PR B 1
C34A C 1.1480(4) 0.2678(4) 0.0021(3) 0.0420(10) Uiso 0.66 1 d P B 1
H34C H 1.1836 0.2700 -0.0375 0.050 Uiso 0.66 1 calc PR B 1
C35A C 1.0346(5) 0.2001(4) -0.0101(2) 0.0412(9) Uiso 0.66 1 d P B 1
H35C H 0.9929 0.1560 -0.0566 0.049 Uiso 0.66 1 calc PR B 1
C36A C 0.9855(4) 0.2010(4) 0.0504(2) 0.0390(10) Uiso 0.66 1 d P B 1
H36C H 0.908(4) 0.150(4) 0.048(3) 0.047 Uiso 0.66 1 d P C 1
C31B C 1.0185(7) 0.2385(7) 0.1144(4) 0.0224(19) Uiso 0.34 1 d P B 3
C32B C 1.1302(8) 0.2939(7) 0.1136(5) 0.0348(19) Uiso 0.34 1 d P B 3
H32E H 1.1811 0.3379 0.1585 0.042 Uiso 0.34 1 calc PR B 3
C33B C 1.1733(7) 0.2901(7) 0.0526(5) 0.0343(16) Uiso 0.34 1 d P B 3
H33D H 1.2504 0.3300 0.0541 0.041 Uiso 0.34 1 calc PR B 3
C34B C 1.0996(9) 0.2270(7) -0.0079(4) 0.0276(13) Uiso 0.34 1 d P B 3
H34D H 1.1250 0.2229 -0.0517 0.033 Uiso 0.34 1 calc PR B 3
C35B C 0.9812(9) 0.1628(8) -0.0120(5) 0.046(2) Uiso 0.34 1 d P B 3
H35D H 0.9314 0.1169 -0.0562 0.056 Uiso 0.34 1 calc PR B 3
C36B C 0.9451(9) 0.1725(8) 0.0524(6) 0.039(2) Uiso 0.34 1 d P B 3
H36D H 0.8689 0.1327 0.0527 0.047 Uiso 0.34 1 calc PR B 3
H1 H 0.900(2) 0.216(2) 0.1631(15) 0.038(7) Uiso 1 1 d . . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Al1 0.0339(3) 0.0254(3) 0.0256(3) 0.0022(2) 0.0137(3) 0.0090(3)
Al2 0.0367(4) 0.0329(4) 0.0268(3) -0.0032(3) 0.0071(3) 0.0063(3)
Al2A 0.0314(4) 0.0309(4) 0.0339(4) 0.0034(3) 0.0150(3) 0.0083(3)
Al1A 0.0314(3) 0.0304(3) 0.0257(3) -0.0008(3) 0.0101(3) 0.0060(3)
N1 0.0387(10) 0.0248(9) 0.0247(9) 0.0008(7) 0.0129(8) 0.0098(8)
N2 0.0319(9) 0.0267(9) 0.0222(8) 0.0029(7) 0.0105(7) 0.0097(7)
N1A 0.0318(9) 0.0288(9) 0.0238(9) 0.0024(7) 0.0119(7) 0.0085(8)
N2A 0.0358(10) 0.0280(9) 0.0238(9) 0.0002(7) 0.0132(7) 0.0092(8)
C2 0.0614(17) 0.0414(14) 0.0388(13) 0.0069(11) 0.0298(12) 0.0113(12)
C3 0.0324(12) 0.0354(12) 0.0390(12) 0.0023(10) 0.0120(10) 0.0086(10)
C4 0.0459(17) 0.071(2) 0.0606(19) -0.0035(16) 0.0071(14) -0.0172(15)
C5 0.0683(19) 0.0565(17) 0.0268(12) -0.0032(11) 0.0056(12) 0.0251(15)
C11 0.0309(11) 0.0243(10) 0.0274(10) -0.0030(8) 0.0081(9) 0.0056(9)
C12 0.0430(13) 0.0306(12) 0.0268(11) -0.0006(9) 0.0112(9) 0.0110(10)
C13 0.0425(13) 0.0385(13) 0.0294(11) -0.0069(10) 0.0096(10) 0.0121(11)
C14 0.0441(14) 0.0320(12) 0.0384(13) -0.0080(10) 0.0079(10) 0.0143(11)
C15 0.0375(12) 0.0270(11) 0.0360(12) 0.0011(9) 0.0082(10) 0.0101(10)
C16 0.0250(10) 0.0253(11) 0.0286(10) -0.0018(8) 0.0058(8) 0.0029(8)
C17 0.0265(10) 0.0267(11) 0.0276(10) 0.0013(8) 0.0082(8) 0.0037(8)
C18 0.0283(11) 0.0272(11) 0.0245(10) 0.0016(8) 0.0109(8) 0.0047(8)
C19 0.0447(13) 0.0319(12) 0.0318(11) 0.0069(9) 0.0142(10) 0.0117(10)
C21 0.0236(10) 0.0285(11) 0.0272(10) 0.0008(8) 0.0073(8) 0.0078(8)
C22 0.0365(12) 0.0369(12) 0.0275(11) 0.0042(9) 0.0109(9) 0.0148(10)
208
C23 0.0407(13) 0.0391(13) 0.0354(12) 0.0118(10) 0.0127(10) 0.0196(11)
C24 0.0382(13) 0.0315(12) 0.0460(13) 0.0044(10) 0.0154(11) 0.0170(10)
C25 0.0363(12) 0.0323(12) 0.0353(12) -0.0004(9) 0.0137(10) 0.0124(10)
C26 0.0251(10) 0.0290(11) 0.0276(10) -0.0004(8) 0.0094(8) 0.0067(8)
C27 0.0322(11) 0.0310(11) 0.0257(10) 0.0012(9) 0.0117(9) 0.0081(9)
C28 0.0280(10) 0.0284(11) 0.0234(10) 0.0027(8) 0.0113(8) 0.0057(9)
C29 0.0548(15) 0.0370(13) 0.0271(11) -0.0007(10) 0.0164(10) 0.0139(11)
C2A 0.0358(13) 0.0496(16) 0.0562(16) 0.0002(13) 0.0191(12) 0.0035(12)
C3A 0.0585(17) 0.0476(15) 0.0267(12) -0.0044(11) 0.0065(11) 0.0121(13)
C4A 0.0336(13) 0.0347(13) 0.0596(16) 0.0038(12) 0.0088(11) 0.0071(10)
C5A 0.0587(18) 0.0635(19) 0.0561(17) 0.0119(14) 0.0389(15) 0.0201(15)
C11A 0.0235(10) 0.0268(11) 0.0308(11) 0.0019(9) 0.0094(8) 0.0020(8)
C12A 0.0330(12) 0.0359(12) 0.0307(11) 0.0051(9) 0.0127(9) 0.0052(10)
C13A 0.0405(13) 0.0409(14) 0.0335(12) 0.0111(10) 0.0100(10) 0.0070(11)
C14A 0.0418(14) 0.0367(13) 0.0447(14) 0.0122(11) 0.0110(11) 0.0140(11)
C15A 0.0359(12) 0.0316(12) 0.0428(13) 0.0031(10) 0.0122(10) 0.0104(10)
C16A 0.0237(10) 0.0270(11) 0.0331(11) 0.0005(9) 0.0084(8) 0.0026(8)
C17A 0.0300(11) 0.0274(11) 0.0299(11) -0.0013(9) 0.0111(9) 0.0037(9)
C18A 0.0309(11) 0.0277(11) 0.0242(10) -0.0010(8) 0.0111(8) 0.0046(9)
C19A 0.0499(15) 0.0330(12) 0.0386(13) -0.0026(10) 0.0185(11) 0.0147(11)
C21A 0.0259(10) 0.0277(11) 0.0289(10) -0.0016(8) 0.0087(8) 0.0059(9)
C22A 0.0381(12) 0.0366(13) 0.0309(11) -0.0021(9) 0.0120(10) 0.0112(10)
C23A 0.0484(15) 0.0392(14) 0.0396(13) -0.0075(11) 0.0126(11) 0.0176(11)
C24A 0.0520(15) 0.0319(13) 0.0522(15) 0.0018(11) 0.0146(12) 0.0192(11)
C25A 0.0434(14) 0.0342(13) 0.0387(13) 0.0084(10) 0.0139(10) 0.0156(11)
C26A 0.0255(10) 0.0306(11) 0.0312(11) 0.0021(9) 0.0083(8) 0.0074(9)
C27A 0.0297(11) 0.0333(12) 0.0254(10) 0.0037(9) 0.0095(8) 0.0095(9)
C28A 0.0308(11) 0.0315(11) 0.0233(10) -0.0004(8) 0.0110(8) 0.0088(9)
C29A 0.0496(14) 0.0450(14) 0.0271(11) 0.0100(10) 0.0134(10) 0.0213(12)
C1 0.0299(11) 0.0291(11) 0.0255(10) 0.0023(8) 0.0105(8) 0.0073(9)
C31 0.0513(14) 0.0277(11) 0.0374(12) 0.0069(9) 0.0279(11) 0.0148(10)
C1A 0.0332(12) 0.0358(12) 0.0271(11) -0.0018(9) 0.0091(9) 0.0122(10)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Al1 C2 1.954(2) . ?
Al1 C3 1.964(2) . ?
Al1 N1 1.9785(19) . ?
Al1 N2 2.0339(19) . ?
Al1 Al2 2.8510(10) . ?
Al2 C4 1.943(3) . ?
Al2 C5 1.963(3) . ?
209
Al2 N2 1.9722(19) . ?
Al2 N1 2.002(2) . ?
Al2A C5A 1.946(3) . ?
Al2A C4A 1.949(3) . ?
Al2A N2A 1.996(2) . ?
Al2A N1A 1.9971(19) . ?
Al2A Al1A 2.8368(10) . ?
Al1A C2A 1.936(3) . ?
Al1A C3A 1.954(2) . ?
Al1A N2A 1.9870(19) . ?
Al1A N1A 2.005(2) . ?
N1 C11 1.420(3) . ?
N1 C18 1.458(3) . ?
N2 C21 1.421(3) . ?
N2 C28 1.455(3) . ?
N1A C11A 1.423(3) . ?
N1A C18A 1.451(3) . ?
N2A C21A 1.416(3) . ?
N2A C28A 1.456(3) . ?
C2 H2A 0.9800 . ?
C2 H2B 0.9800 . ?
C2 H2C 0.9800 . ?
C3 H3A 0.9800 . ?
C3 H3B 0.9800 . ?
C3 H3C 0.9800 . ?
C4 H4A 0.9800 . ?
C4 H4B 0.9800 . ?
C4 H4C 0.9800 . ?
C5 H5A 0.9800 . ?
C5 H5B 0.9800 . ?
C5 H5C 0.9800 . ?
C11 C16 1.387(3) . ?
C11 C12 1.394(3) . ?
C12 C13 1.387(3) . ?
C12 H12A 0.9500 . ?
C13 C14 1.394(4) . ?
C13 H13A 0.9500 . ?
C14 C15 1.376(3) . ?
C14 H14A 0.9500 . ?
C15 C16 1.398(3) . ?
C15 H15A 0.9500 . ?
C16 C17 1.446(3) . ?
C17 C18 1.357(3) . ?
C17 C19 1.497(3) . ?
C18 C1 1.529(3) . ?
C19 H19A 0.9800 . ?
C19 H19B 0.9800 . ?
C19 H19C 0.9800 . ?
C21 C22 1.388(3) . ?
C21 C26 1.397(3) . ?
C22 C23 1.382(3) . ?
C22 H22A 0.9500 . ?
C23 C24 1.396(3) . ?
C23 H23A 0.9500 . ?
C24 C25 1.376(3) . ?
C24 H24A 0.9500 . ?
210
C25 C26 1.405(3) . ?
C25 H25A 0.9500 . ?
C26 C27 1.441(3) . ?
C27 C28 1.358(3) . ?
C27 C29 1.504(3) . ?
C28 C1 1.524(3) . ?
C29 H29A 0.9800 . ?
C29 H29B 0.9800 . ?
C29 H29C 0.9800 . ?
C2A H2AA 0.9800 . ?
C2A H2AB 0.9800 . ?
C2A H2AC 0.9800 . ?
C3A H3AA 0.9800 . ?
C3A H3AB 0.9800 . ?
C3A H3AC 0.9800 . ?
C4A H4AA 0.9800 . ?
C4A H4AB 0.9800 . ?
C4A H4AC 0.9800 . ?
C5A H5AA 0.9800 . ?
C5A H5AB 0.9800 . ?
C5A H5AC 0.9800 . ?
C11A C12A 1.391(3) . ?
C11A C16A 1.397(3) . ?
C12A C13A 1.381(3) . ?
C12A H12B 0.9500 . ?
C13A C14A 1.395(4) . ?
C13A H13B 0.9500 . ?
C14A C15A 1.377(4) . ?
C14A H14B 0.9500 . ?
C15A C16A 1.400(3) . ?
C15A H15B 0.9500 . ?
C16A C17A 1.452(3) . ?
C17A C18A 1.359(3) . ?
C17A C19A 1.503(3) . ?
C18A C1A 1.541(3) . ?
C19A H19D 0.9800 . ?
C19A H19E 0.9800 . ?
C19A H19F 0.9800 . ?
C21A C22A 1.394(3) . ?
C21A C26A 1.397(3) . ?
C22A C23A 1.381(3) . ?
C22A H22B 0.9500 . ?
C23A C24A 1.395(4) . ?
C23A H23B 0.9500 . ?
C24A C25A 1.373(4) . ?
C24A H24B 0.9500 . ?
C25A C26A 1.402(3) . ?
C25A H25B 0.9500 . ?
C26A C27A 1.441(3) . ?
C27A C28A 1.355(3) . ?
C27A C29A 1.506(3) . ?
C28A C1A 1.523(3) . ?
C29A H29D 0.9800 . ?
C29A H29E 0.9800 . ?
C29A H29F 0.9800 . ?
C1 C31 1.532(3) . ?
211
C1 H1A 1.0000 . ?
C31 C36D 1.275(8) . ?
C31 C32C 1.287(5) . ?
C31 C36C 1.472(5) . ?
C31 C32D 1.550(8) . ?
C32C C33C 1.393(7) . ?
C32C H32A 0.9500 . ?
C33C C34C 1.367(7) . ?
C33C H33A 0.9500 . ?
C34C C35C 1.389(7) . ?
C34C H34A 0.9500 . ?
C35C C36C 1.398(6) . ?
C35C H35A 0.9500 . ?
C36C H36A 0.9500 . ?
C32D C33D 1.374(11) . ?
C32D H32C 0.9500 . ?
C33D C34D 1.414(11) . ?
C33D H33B 0.9500 . ?
C34D C35D 1.363(11) . ?
C34D H34B 0.9500 . ?
C35D C36D 1.411(11) . ?
C35D H35B 0.9500 . ?
C36D H36B 0.9500 . ?
C1A C31B 1.458(7) . ?
C1A C31A 1.572(5) . ?
C1A H1 1.01(3) . ?
C31A C32A 1.367(7) . ?
C31A C36A 1.405(6) . ?
C32A C33A 1.376(6) . ?
C32A H32D 0.9500 . ?
C33A C34A 1.390(6) . ?
C33A H33C 0.9500 . ?
C34A C35A 1.400(7) . ?
C34A H34C 0.9500 . ?
C35A C36A 1.413(7) . ?
C35A H35C 0.9500 . ?
C36A H36C 1.00(5) . ?
C31B C36B 1.352(13) . ?
C31B C32B 1.383(12) . ?
C32B C33B 1.376(11) . ?
C32B H32E 0.9500 . ?
C33B C34B 1.319(12) . ?
C33B H33D 0.9500 . ?
C34B C35B 1.462(12) . ?
C34B H34D 0.9500 . ?
C35B C36B 1.392(14) . ?
C35B H35D 0.9500 . ?
C36B H36C 0.46(5) . ?
C36B H36D 0.9500 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
212
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C2 Al1 C3 115.97(12) . . ?
C2 Al1 N1 114.09(10) . . ?
C3 Al1 N1 115.52(9) . . ?
C2 Al1 N2 116.29(10) . . ?
C3 Al1 N2 111.55(9) . . ?
N1 Al1 N2 77.82(8) . . ?
C2 Al1 Al2 100.37(9) . . ?
C3 Al1 Al2 143.57(8) . . ?
N1 Al1 Al2 44.58(6) . . ?
N2 Al1 Al2 43.77(5) . . ?
C4 Al2 C5 112.74(14) . . ?
C4 Al2 N2 121.06(12) . . ?
C5 Al2 N2 111.96(11) . . ?
C4 Al2 N1 113.14(13) . . ?
C5 Al2 N1 115.20(11) . . ?
N2 Al2 N1 78.73(7) . . ?
C4 Al2 Al1 148.77(11) . . ?
C5 Al2 Al1 98.01(10) . . ?
N2 Al2 Al1 45.51(5) . . ?
N1 Al2 Al1 43.93(6) . . ?
C5A Al2A C4A 114.37(13) . . ?
C5A Al2A N2A 116.16(11) . . ?
C4A Al2A N2A 111.63(10) . . ?
C5A Al2A N1A 115.50(11) . . ?
C4A Al2A N1A 115.69(10) . . ?
N2A Al2A N1A 78.78(8) . . ?
C5A Al2A Al1A 101.18(10) . . ?
C4A Al2A Al1A 144.32(9) . . ?
N2A Al2A Al1A 44.46(6) . . ?
N1A Al2A Al1A 44.96(6) . . ?
C2A Al1A C3A 116.47(13) . . ?
C2A Al1A N2A 115.43(11) . . ?
C3A Al1A N2A 113.32(10) . . ?
C2A Al1A N1A 114.76(10) . . ?
C3A Al1A N1A 112.47(10) . . ?
N2A Al1A N1A 78.80(8) . . ?
C2A Al1A Al2A 146.43(9) . . ?
C3A Al1A Al2A 97.08(9) . . ?
N2A Al1A Al2A 44.70(6) . . ?
N1A Al1A Al2A 44.75(5) . . ?
C11 N1 C18 104.29(16) . . ?
C11 N1 Al1 126.05(15) . . ?
C18 N1 Al1 110.49(13) . . ?
C11 N1 Al2 116.08(14) . . ?
C18 N1 Al2 107.23(13) . . ?
Al1 N1 Al2 91.49(8) . . ?
C21 N2 C28 104.64(16) . . ?
C21 N2 Al2 124.65(14) . . ?
C28 N2 Al2 113.93(13) . . ?
C21 N2 Al1 119.30(14) . . ?
C28 N2 Al1 101.44(12) . . ?
Al2 N2 Al1 90.73(7) . . ?
C11A N1A C18A 104.96(16) . . ?
C11A N1A Al2A 128.07(14) . . ?
213
C18A N1A Al2A 110.28(13) . . ?
C11A N1A Al1A 115.01(13) . . ?
C18A N1A Al1A 106.31(13) . . ?
Al2A N1A Al1A 90.29(8) . . ?
C21A N2A C28A 104.55(17) . . ?
C21A N2A Al1A 117.15(14) . . ?
C28A N2A Al1A 108.59(13) . . ?
C21A N2A Al2A 126.51(14) . . ?
C28A N2A Al2A 108.05(13) . . ?
Al1A N2A Al2A 90.85(8) . . ?
Al1 C2 H2A 109.5 . . ?
Al1 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
Al1 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
Al1 C3 H3A 109.5 . . ?
Al1 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
Al1 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
Al2 C4 H4A 109.5 . . ?
Al2 C4 H4B 109.5 . . ?
H4A C4 H4B 109.5 . . ?
Al2 C4 H4C 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?
Al2 C5 H5A 109.5 . . ?
Al2 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
Al2 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
C16 C11 C12 122.2(2) . . ?
C16 C11 N1 109.86(18) . . ?
C12 C11 N1 127.9(2) . . ?
C13 C12 C11 116.9(2) . . ?
C13 C12 H12A 121.5 . . ?
C11 C12 H12A 121.5 . . ?
C12 C13 C14 121.2(2) . . ?
C12 C13 H13A 119.4 . . ?
C14 C13 H13A 119.4 . . ?
C15 C14 C13 121.4(2) . . ?
C15 C14 H14A 119.3 . . ?
C13 C14 H14A 119.3 . . ?
C14 C15 C16 118.2(2) . . ?
C14 C15 H15A 120.9 . . ?
C16 C15 H15A 120.9 . . ?
C11 C16 C15 120.0(2) . . ?
C11 C16 C17 108.07(18) . . ?
C15 C16 C17 131.9(2) . . ?
C18 C17 C16 106.96(19) . . ?
C18 C17 C19 131.6(2) . . ?
C16 C17 C19 121.41(19) . . ?
C17 C18 N1 110.81(18) . . ?
214
C17 C18 C1 130.23(19) . . ?
N1 C18 C1 118.51(17) . . ?
C17 C19 H19A 109.5 . . ?
C17 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C17 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C22 C21 C26 122.2(2) . . ?
C22 C21 N2 128.39(19) . . ?
C26 C21 N2 109.42(18) . . ?
C23 C22 C21 117.6(2) . . ?
C23 C22 H22A 121.2 . . ?
C21 C22 H22A 121.2 . . ?
C22 C23 C24 121.1(2) . . ?
C22 C23 H23A 119.5 . . ?
C24 C23 H23A 119.5 . . ?
C25 C24 C23 121.3(2) . . ?
C25 C24 H24A 119.4 . . ?
C23 C24 H24A 119.4 . . ?
C24 C25 C26 118.5(2) . . ?
C24 C25 H25A 120.7 . . ?
C26 C25 H25A 120.7 . . ?
C21 C26 C25 119.3(2) . . ?
C21 C26 C27 107.90(18) . . ?
C25 C26 C27 132.7(2) . . ?
C28 C27 C26 107.40(18) . . ?
C28 C27 C29 128.5(2) . . ?
C26 C27 C29 123.97(19) . . ?
C27 C28 N2 110.61(18) . . ?
C27 C28 C1 127.59(19) . . ?
N2 C28 C1 121.46(17) . . ?
C27 C29 H29A 109.5 . . ?
C27 C29 H29B 109.5 . . ?
H29A C29 H29B 109.5 . . ?
C27 C29 H29C 109.5 . . ?
H29A C29 H29C 109.5 . . ?
H29B C29 H29C 109.5 . . ?
Al1A C2A H2AA 109.5 . . ?
Al1A C2A H2AB 109.5 . . ?
H2AA C2A H2AB 109.5 . . ?
Al1A C2A H2AC 109.5 . . ?
H2AA C2A H2AC 109.5 . . ?
H2AB C2A H2AC 109.5 . . ?
Al1A C3A H3AA 109.5 . . ?
Al1A C3A H3AB 109.5 . . ?
H3AA C3A H3AB 109.5 . . ?
Al1A C3A H3AC 109.5 . . ?
H3AA C3A H3AC 109.5 . . ?
H3AB C3A H3AC 109.5 . . ?
Al2A C4A H4AA 109.5 . . ?
Al2A C4A H4AB 109.5 . . ?
H4AA C4A H4AB 109.5 . . ?
Al2A C4A H4AC 109.5 . . ?
H4AA C4A H4AC 109.5 . . ?
H4AB C4A H4AC 109.5 . . ?
215
Al2A C5A H5AA 109.5 . . ?
Al2A C5A H5AB 109.5 . . ?
H5AA C5A H5AB 109.5 . . ?
Al2A C5A H5AC 109.5 . . ?
H5AA C5A H5AC 109.5 . . ?
H5AB C5A H5AC 109.5 . . ?
C12A C11A C16A 121.8(2) . . ?
C12A C11A N1A 128.8(2) . . ?
C16A C11A N1A 109.39(18) . . ?
C13A C12A C11A 117.7(2) . . ?
C13A C12A H12B 121.2 . . ?
C11A C12A H12B 121.2 . . ?
C12A C13A C14A 121.3(2) . . ?
C12A C13A H13B 119.4 . . ?
C14A C13A H13B 119.4 . . ?
C15A C14A C13A 120.9(2) . . ?
C15A C14A H14B 119.5 . . ?
C13A C14A H14B 119.5 . . ?
C14A C15A C16A 118.9(2) . . ?
C14A C15A H15B 120.6 . . ?
C16A C15A H15B 120.6 . . ?
C11A C16A C15A 119.4(2) . . ?
C11A C16A C17A 107.71(18) . . ?
C15A C16A C17A 132.8(2) . . ?
C18A C17A C16A 107.21(18) . . ?
C18A C17A C19A 131.0(2) . . ?
C16A C17A C19A 121.7(2) . . ?
C17A C18A N1A 110.69(18) . . ?
C17A C18A C1A 130.83(19) . . ?
N1A C18A C1A 118.09(17) . . ?
C17A C19A H19D 109.5 . . ?
C17A C19A H19E 109.5 . . ?
H19D C19A H19E 109.5 . . ?
C17A C19A H19F 109.5 . . ?
H19D C19A H19F 109.5 . . ?
H19E C19A H19F 109.5 . . ?
C22A C21A C26A 121.7(2) . . ?
C22A C21A N2A 128.8(2) . . ?
C26A C21A N2A 109.55(18) . . ?
C23A C22A C21A 117.6(2) . . ?
C23A C22A H22B 121.2 . . ?
C21A C22A H22B 121.2 . . ?
C22A C23A C24A 121.3(2) . . ?
C22A C23A H23B 119.4 . . ?
C24A C23A H23B 119.4 . . ?
C25A C24A C23A 121.3(2) . . ?
C25A C24A H24B 119.4 . . ?
C23A C24A H24B 119.4 . . ?
C24A C25A C26A 118.5(2) . . ?
C24A C25A H25B 120.7 . . ?
C26A C25A H25B 120.7 . . ?
C21A C26A C25A 119.7(2) . . ?
C21A C26A C27A 107.84(19) . . ?
C25A C26A C27A 132.5(2) . . ?
C28A C27A C26A 107.24(18) . . ?
C28A C27A C29A 130.5(2) . . ?
216
C26A C27A C29A 122.2(2) . . ?
C27A C28A N2A 110.75(18) . . ?
C27A C28A C1A 129.87(19) . . ?
N2A C28A C1A 119.04(18) . . ?
C27A C29A H29D 109.5 . . ?
C27A C29A H29E 109.5 . . ?
H29D C29A H29E 109.5 . . ?
C27A C29A H29F 109.5 . . ?
H29D C29A H29F 109.5 . . ?
H29E C29A H29F 109.5 . . ?
C28 C1 C18 115.50(17) . . ?
C28 C1 C31 110.17(17) . . ?
C18 C1 C31 114.30(18) . . ?
C28 C1 H1A 105.3 . . ?
C18 C1 H1A 105.3 . . ?
C31 C1 H1A 105.3 . . ?
C36D C31 C32C 102.3(5) . . ?
C36D C31 C36C 17.7(4) . . ?
C32C C31 C36C 118.8(3) . . ?
C36D C31 C1 130.0(5) . . ?
C32C C31 C1 127.7(3) . . ?
C36C C31 C1 113.2(3) . . ?
C36D C31 C32D 116.6(5) . . ?
C32C C31 C32D 14.4(4) . . ?
C36C C31 C32D 133.0(4) . . ?
C1 C31 C32D 113.4(4) . . ?
C31 C32C C33C 124.3(5) . . ?
C31 C32C H32A 117.9 . . ?
C33C C32C H32A 117.9 . . ?
C34C C33C C32C 117.8(5) . . ?
C34C C33C H33A 121.1 . . ?
C32C C33C H33A 121.1 . . ?
C33C C34C C35C 122.3(5) . . ?
C33C C34C H34A 118.9 . . ?
C35C C34C H34A 118.9 . . ?
C34C C35C C36C 118.4(5) . . ?
C34C C35C H35A 120.8 . . ?
C36C C35C H35A 120.8 . . ?
C35C C36C C31 118.4(5) . . ?
C35C C36C H36A 120.8 . . ?
C31 C36C H36A 120.8 . . ?
C33D C32D C31 116.9(7) . . ?
C33D C32D H32C 121.6 . . ?
C31 C32D H32C 121.6 . . ?
C32D C33D C34D 119.4(8) . . ?
C32D C33D H33B 120.3 . . ?
C34D C33D H33B 120.3 . . ?
C35D C34D C33D 124.3(7) . . ?
C35D C34D H34B 117.9 . . ?
C33D C34D H34B 117.9 . . ?
C34D C35D C36D 114.5(7) . . ?
C34D C35D H35B 122.8 . . ?
C36D C35D H35B 122.8 . . ?
C31 C36D C35D 128.1(8) . . ?
C31 C36D H36B 115.9 . . ?
C35D C36D H36B 115.9 . . ?
217
C31B C1A C28A 119.1(4) . . ?
C31B C1A C18A 112.9(3) . . ?
C28A C1A C18A 114.88(18) . . ?
C31B C1A C31A 15.5(3) . . ?
C28A C1A C31A 108.8(2) . . ?
C18A C1A C31A 111.6(2) . . ?
C31B C1A H1 97.2(15) . . ?
C28A C1A H1 105.4(15) . . ?
C18A C1A H1 104.0(15) . . ?
C31A C1A H1 112.0(15) . . ?
C32A C31A C36A 119.6(4) . . ?
C32A C31A C1A 124.0(3) . . ?
C36A C31A C1A 116.3(4) . . ?
C31A C32A C33A 121.0(4) . . ?
C31A C32A H32D 119.5 . . ?
C33A C32A H32D 119.5 . . ?
C32A C33A C34A 119.4(5) . . ?
C32A C33A H33C 120.3 . . ?
C34A C33A H33C 120.3 . . ?
C33A C34A C35A 122.3(4) . . ?
C33A C34A H34C 118.9 . . ?
C35A C34A H34C 118.9 . . ?
C34A C35A C36A 116.4(4) . . ?
C34A C35A H35C 121.8 . . ?
C36A C35A H35C 121.8 . . ?
C31A C36A C35A 121.2(5) . . ?
C31A C36A H36C 117(3) . . ?
C35A C36A H36C 121(3) . . ?
C36B C31B C32B 119.2(8) . . ?
C36B C31B C1A 123.7(8) . . ?
C32B C31B C1A 117.1(7) . . ?
C33B C32B C31B 125.0(8) . . ?
C33B C32B H32E 117.5 . . ?
C31B C32B H32E 117.5 . . ?
C34B C33B C32B 115.0(8) . . ?
C34B C33B H33D 122.5 . . ?
C32B C33B H33D 122.5 . . ?
C33B C34B C35B 124.2(7) . . ?
C33B C34B H34D 117.9 . . ?
C35B C34B H34D 117.9 . . ?
C36B C35B C34B 116.6(8) . . ?
C36B C35B H35D 121.7 . . ?
C34B C35B H35D 121.7 . . ?
C31B C36B C35B 120.0(10) . . ?
C31B C36B H36C 132(8) . . ?
C35B C36B H36C 108(8) . . ?
C31B C36B H36D 120.0 . . ?
C35B C36B H36D 120.0 . . ?
H36C C36B H36D 12.0 . . ?
_diffrn_measured_fraction_theta_max
_diffrn_reflns_theta_full
_diffrn_measured_fraction_theta_full
_refine_diff_density_max
_refine_diff_density_min
0.998
26.00
0.998
0.481
-0.339
218
CIF File For [{tri(3-methylindolyl)methane}(AlMe2)3]•0.60(C7H8)
_audit_creation_method
_chemical_name_systematic
;
?
;
_chemical_name_common
_chemical_melting_point
_chemical_formula_moiety
_chemical_formula_sum
SHELXL-97
?
?
'C34 H40 Al3 N3, 0.60 •0.60(C7 H8)'
' C34 H40 Al3 N3, 0.60 •0.60(C7 H8)'
_chemical_formula_weight
626.91
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Al' 'Al' 0.0645 0.0514
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
_symmetry_space_group_name_H-M
'Triclinic'
'P -1'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
_cell_length_a
_cell_length_b
_cell_length_c
_cell_angle_alpha
_cell_angle_beta
_cell_angle_gamma
_cell_volume
_cell_formula_units_Z
_cell_measurement_temperature
_cell_measurement_reflns_used
_cell_measurement_theta_min
_cell_measurement_theta_max
10.2695(12)
12.3448(14)
15.0435(18)
77.768(3)
86.788(2)
88.308(3)
1860.6(4)
2
–133
984
2.85
33.19
_exptl_crystal_description
_exptl_crystal_colour
_exptl_crystal_size_max
_exptl_crystal_size_mid
_exptl_crystal_size_min
_exptl_crystal_density_meas
'rectangular brick'
'colorless'
.40
.35
.30
?
219
_exptl_crystal_density_diffrn
_exptl_crystal_density_method
_exptl_crystal_F_000
_exptl_absorpt_coefficient_mu
_exptl_absorpt_correction_type
_exptl_absorpt_correction_T_min
_exptl_absorpt_correction_T_max
_exptl_absorpt_process_details
1.119
'not measured'
668
0.130
multi-scan
0.861
1.000
'sadabs (Sheldrick, 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
_diffrn_radiation_wavelength
_diffrn_radiation_type
_diffrn_radiation_source
_diffrn_radiation_monochromator
_diffrn_measurement_device_type
_diffrn_measurement_method
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
?
_diffrn_reflns_number
_diffrn_reflns_av_R_equivalents
_diffrn_reflns_av_sigmaI/netI
_diffrn_reflns_limit_h_min
_diffrn_reflns_limit_h_max
_diffrn_reflns_limit_k_min
_diffrn_reflns_limit_k_max
_diffrn_reflns_limit_l_min
_diffrn_reflns_limit_l_max
_diffrn_reflns_theta_min
_diffrn_reflns_theta_max
_reflns_number_total
_reflns_number_gt
_reflns_threshold_expression
–133
0.71073
MoK\a
'fine-focus sealed tube'
'graphite'
'Bruker platform with 4k CCD'
'omega scans'
_computing_data_collection
_computing_cell_refinement
_computing_data_reduction
_computing_structure_solution
_computing_structure_refinement
_computing_molecular_graphics ?
_computing_publication_material ?
'Smart 5.630 '
'Saintplus 5.45 '
'Saintplus 5.45'
'SHELXS-97 (Sheldrick, 1990)'
'SHELXL-97 (Sheldrick, 1997)'
13288
0.0171
0.0235
-12
12
-15
14
-17
18
1.69
26.00
7270
6868
>2sigma(I)
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
220
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1062P)^2^+1.4420P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary
difmap
_atom_sites_solution_hydrogens
diffmap
_refine_ls_hydrogen_treatment
refall
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
7270
_refine_ls_number_parameters
387
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.0571
_refine_ls_R_factor_gt
0.0548
_refine_ls_wR_factor_ref
0.1733
_refine_ls_wR_factor_gt
0.1700
_refine_ls_goodness_of_fit_ref
1.045
_refine_ls_restrained_S_all
1.045
_refine_ls_shift/su_max
0.000
_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Al1 Al 0.37533(5) 0.98079(5) 0.17363(4) 0.02463(17) Uani 1 1 d . . .
Al2 Al 0.34285(6) 0.88702(5) 0.40971(4) 0.02775(17) Uani 1 1 d . . .
Al3 Al 0.29578(6) 0.70930(5) 0.26463(4) 0.02716(17) Uani 1 1 d . . .
N1 N 0.30846(15) 0.99940(13) 0.29736(11) 0.0250(3) Uani 1 1 d . . .
N2 N 0.23958(15) 0.77068(14) 0.37328(11) 0.0255(3) Uani 1 1 d . . .
N3 N 0.26470(15) 0.85079(13) 0.17543(11) 0.0241(3) Uani 1 1 d . . .
C1 C 0.09229(17) 0.91422(15) 0.28100(13) 0.0236(4) Uani 1 1 d . . .
H1A H -0.0004 0.9357 0.2804 0.028 Uiso 1 1 calc R . .
C2 C 0.5621(2) 0.94615(19) 0.16897(16) 0.0342(5) Uani 1 1 d . . .
H2A H 0.5897 0.9382 0.1086 0.051 Uiso 1 1 calc R . .
H2B H 0.5793 0.8782 0.2115 0.051 Uiso 1 1 calc R . .
H2C H 0.6092 1.0051 0.1845 0.051 Uiso 1 1 calc R . .
C3 C 0.3051(2) 1.10521(18) 0.08566(15) 0.0328(5) Uani 1 1 d . . .
H3A H 0.3350 1.0994 0.0252 0.049 Uiso 1 1 calc R . .
H3B H 0.3341 1.1735 0.0980 0.049 Uiso 1 1 calc R . .
221
H3C H 0.2115 1.1039 0.0905 0.049 Uiso 1 1 calc R . .
C4 C 0.2438(2) 0.9313(2) 0.51127(16) 0.0389(5) Uani 1 1 d . . .
H4A H 0.2899 0.9877 0.5311 0.058 Uiso 1 1 calc R . .
H4B H 0.2332 0.8682 0.5607 0.058 Uiso 1 1 calc R . .
H4C H 0.1597 0.9598 0.4920 0.058 Uiso 1 1 calc R . .
C5 C 0.5275(2) 0.8474(2) 0.42210(18) 0.0426(6) Uani 1 1 d . . .
H5A H 0.5718 0.9064 0.4396 0.064 Uiso 1 1 calc R . .
H5B H 0.5651 0.8356 0.3650 0.064 Uiso 1 1 calc R . .
H5C H 0.5363 0.7807 0.4678 0.064 Uiso 1 1 calc R . .
C6 C 0.4777(2) 0.6584(2) 0.2666(2) 0.0446(6) Uani 1 1 d . . .
H6A H 0.4855 0.5902 0.3109 0.067 Uiso 1 1 calc R . .
H6B H 0.5309 0.7134 0.2825 0.067 Uiso 1 1 calc R . .
H6C H 0.5063 0.6464 0.2076 0.067 Uiso 1 1 calc R . .
C7 C 0.1650(2) 0.60411(18) 0.25017(17) 0.0375(5) Uani 1 1 d . . .
H7A H 0.1783 0.5353 0.2926 0.056 Uiso 1 1 calc R . .
H7B H 0.1726 0.5917 0.1892 0.056 Uiso 1 1 calc R . .
H7C H 0.0795 0.6335 0.2616 0.056 Uiso 1 1 calc R . .
C10 C 0.16833(18) 1.01346(16) 0.29171(13) 0.0242(4) Uani 1 1 d . . .
C11 C 0.1271(2) 1.11752(17) 0.29454(14) 0.0286(4) Uani 1 1 d . . .
C12 C 0.2419(2) 1.17902(17) 0.30342(14) 0.0316(4) Uani 1 1 d . . .
C13 C 0.2601(3) 1.2896(2) 0.30802(18) 0.0440(6) Uani 1 1 d . . .
H13A H 0.1896 1.3390 0.3061 0.053 Uiso 1 1 calc R . .
C14 C 0.3853(3) 1.3236(2) 0.3154(2) 0.0520(7) Uani 1 1 d . . .
H14A H 0.3989 1.3969 0.3183 0.062 Uiso 1 1 calc R . .
C15 C 0.4913(3) 1.2505(2) 0.31864(19) 0.0480(6) Uani 1 1 d . . .
H15A H 0.5742 1.2756 0.3245 0.058 Uiso 1 1 calc R . .
C16 C 0.4758(2) 1.1407(2) 0.31333(16) 0.0373(5) Uani 1 1 d . . .
H16A H 0.5468 1.0920 0.3147 0.045 Uiso 1 1 calc R . .
C17 C 0.3497(2) 1.10687(17) 0.30583(13) 0.0292(4) Uani 1 1 d . . .
C18 C -0.0076(2) 1.16638(19) 0.28683(18) 0.0397(5) Uani 1 1 d . . .
H18A H -0.0676 1.1102 0.2813 0.060 Uiso 1 1 calc R . .
H18B H -0.0099 1.2256 0.2340 0.060 Uiso 1 1 calc R . .
H18C H -0.0319 1.1948 0.3402 0.060 Uiso 1 1 calc R . .
C20 C 0.10877(18) 0.81636(16) 0.35952(13) 0.0241(4) Uani 1 1 d . . .
C21 C 0.01964(19) 0.76189(16) 0.42095(14) 0.0271(4) Uani 1 1 d . . .
C22 C 0.0900(2) 0.67530(17) 0.48083(14) 0.0292(4) Uani 1 1 d . . .
C23 C 0.0496(2) 0.59421(19) 0.55666(16) 0.0384(5) Uani 1 1 d . . .
H23A H -0.0377 0.5888 0.5768 0.046 Uiso 1 1 calc R . .
C24 C 0.1426(3) 0.5224(2) 0.60076(18) 0.0476(6) Uani 1 1 d . . .
H24A H 0.1174 0.4684 0.6514 0.057 Uiso 1 1 calc R . .
C25 C 0.2741(3) 0.5298(2) 0.57046(18) 0.0487(6) Uani 1 1 d . . .
H25A H 0.3349 0.4805 0.6014 0.058 Uiso 1 1 calc R . .
C26 C 0.3154(2) 0.6088(2) 0.49544(17) 0.0390(5) Uani 1 1 d . . .
H26A H 0.4026 0.6134 0.4750 0.047 Uiso 1 1 calc R . .
C27 C 0.2213(2) 0.68154(17) 0.45159(14) 0.0291(4) Uani 1 1 d . . .
C28 C -0.1241(2) 0.7836(2) 0.42892(18) 0.0393(5) Uani 1 1 d . . .
H28A H -0.1477 0.8453 0.3817 0.059 Uiso 1 1 calc R . .
H28B H -0.1470 0.8004 0.4873 0.059 Uiso 1 1 calc R . .
H28C H -0.1698 0.7191 0.4228 0.059 Uiso 1 1 calc R . .
C30 C 0.12952(18) 0.88074(15) 0.19166(13) 0.0236(4) Uani 1 1 d . . .
C31 C 0.0543(2) 0.87000(16) 0.12337(14) 0.0284(4) Uani 1 1 d . . .
C32 C 0.1399(2) 0.83338(17) 0.05539(15) 0.0306(4) Uani 1 1 d . . .
C33 C 0.1177(3) 0.8075(2) -0.02877(17) 0.0426(6) Uani 1 1 d . . .
H33A H 0.0345 0.8131 -0.0508 0.051 Uiso 1 1 calc R . .
C34 C 0.2233(3) 0.7734(2) -0.07820(17) 0.0477(6) Uani 1 1 d . . .
H34A H 0.2102 0.7557 -0.1341 0.057 Uiso 1 1 calc R . .
222
C35 C 0.3482(3) 0.7651(2) -0.04600(17) 0.0426(6) Uani 1 1 d . . .
H35A H 0.4172 0.7427 -0.0811 0.051 Uiso 1 1 calc R . .
C36 C 0.3719(2) 0.78943(18) 0.03722(16) 0.0340(5) Uani 1 1 d . . .
H36A H 0.4554 0.7835 0.0589 0.041 Uiso 1 1 calc R . .
C37 C 0.2661(2) 0.82313(16) 0.08700(14) 0.0272(4) Uani 1 1 d . . .
C38 C -0.0900(2) 0.8880(2) 0.11759(18) 0.0414(5) Uani 1 1 d . . .
H38A H -0.1248 0.9123 0.1708 0.062 Uiso 1 1 calc R . .
H38B H -0.1299 0.8197 0.1140 0.062 Uiso 1 1 calc R . .
H38C H -0.1078 0.9433 0.0642 0.062 Uiso 1 1 calc R . .
C50 C -0.2131(10) 0.5890(11) -0.0435(7) 0.118(6) Uiso 0.30 1 d PG A 1
C51 C -0.1521(8) 0.5785(10) 0.0382(8) 0.100(5) Uiso 0.30 1 d PG A 1
C55 C -0.2189(10) 0.5339(10) 0.1201(7) 0.098(5) Uiso 0.30 1 d PG A 1
C52 C -0.3467(10) 0.4998(10) 0.1204(5) 0.089(4) Uiso 0.30 1 d PG A 1
C53 C -0.4078(8) 0.5103(8) 0.0387(6) 0.093(4) Uiso 0.30 1 d PG . 1
C54 C -0.3410(10) 0.5549(10) -0.0432(5) 0.095(4) Uiso 0.30 1 d PG . 1
C56 C -0.5472(9) 0.4796(14) 0.0313(10) 0.128(7) Uiso 0.30 1 d PG . 1
C60 C -0.0978(8) 0.5541(10) 0.0595(8) 0.104(5) Uiso 0.30 1 d PG B 3
C61 C -0.1547(10) 0.5127(11) 0.1456(7) 0.103(5) Uiso 0.30 1 d PG B 3
C62 C -0.2878(10) 0.4929(10) 0.1562(6) 0.100(5) Uiso 0.30 1 d PG B 3
C63 C -0.3640(8) 0.5145(8) 0.0807(7) 0.109(5) Uiso 0.30 1 d PG B 3
C64 C -0.3071(10) 0.5559(11) -0.0054(6) 0.126(7) Uiso 0.30 1 d PG B 3
C65 C -0.1740(11) 0.5757(12) -0.0159(7) 0.096(5) Uiso 0.30 1 d PG B 3
C66 C -0.5207(9) 0.4795(14) 0.0745(12) 0.120(6) Uiso 0.30 1 d PG B 3
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Al1 0.0203(3) 0.0256(3) 0.0269(3) -0.0029(2) -0.0008(2) -0.0019(2)
Al2 0.0236(3) 0.0307(3) 0.0276(3) -0.0017(2) -0.0052(2) -0.0039(2)
Al3 0.0234(3) 0.0224(3) 0.0337(3) -0.0019(2) -0.0015(2) 0.0027(2)
N1 0.0224(8) 0.0244(8) 0.0278(8) -0.0042(6) -0.0029(6) -0.0032(6)
N2 0.0202(8) 0.0247(8) 0.0291(8) 0.0008(7) -0.0041(6) 0.0000(6)
N3 0.0205(8) 0.0247(8) 0.0270(8) -0.0052(6) -0.0016(6) 0.0005(6)
C1 0.0184(8) 0.0228(9) 0.0284(10) -0.0029(7) -0.0016(7) 0.0016(7)
C2 0.0236(10) 0.0378(12) 0.0400(12) -0.0063(9) 0.0019(8) -0.0025(8)
C3 0.0329(11) 0.0339(11) 0.0290(10) -0.0006(8) -0.0017(8) -0.0022(9)
C4 0.0411(12) 0.0446(13) 0.0323(11) -0.0095(10) -0.0028(9) -0.0084(10)
C5 0.0269(11) 0.0531(15) 0.0441(13) 0.0012(11) -0.0110(9) -0.0048(10)
C6 0.0304(11) 0.0358(12) 0.0621(16) -0.0003(11) -0.0004(11) 0.0110(9)
C7 0.0417(12) 0.0254(10) 0.0453(13) -0.0069(9) -0.0004(10) -0.0044(9)
C10 0.0225(9) 0.0254(9) 0.0233(9) -0.0022(7) 0.0002(7) -0.0005(7)
C11 0.0338(11) 0.0241(9) 0.0258(9) -0.0022(8) 0.0040(8) -0.0003(8)
C12 0.0416(12) 0.0271(10) 0.0252(10) -0.0044(8) 0.0034(8) -0.0044(9)
C13 0.0599(16) 0.0270(11) 0.0448(13) -0.0087(10) 0.0059(11) -0.0056(10)
C14 0.0710(19) 0.0298(12) 0.0572(16) -0.0123(11) -0.0001(13) -0.0178(12)
C15 0.0551(15) 0.0413(14) 0.0485(14) -0.0073(11) -0.0057(12) -0.0232(12)
C16 0.0386(12) 0.0365(12) 0.0362(11) -0.0036(9) -0.0064(9) -0.0121(9)
C17 0.0355(11) 0.0267(10) 0.0247(9) -0.0036(8) -0.0007(8) -0.0067(8)
C18 0.0377(12) 0.0300(11) 0.0492(14) -0.0065(10) 0.0055(10) 0.0076(9)
C20 0.0202(9) 0.0232(9) 0.0288(10) -0.0053(7) -0.0029(7) -0.0002(7)
C21 0.0252(10) 0.0249(9) 0.0309(10) -0.0055(8) 0.0013(8) -0.0015(7)
223
C22 0.0311(10) 0.0261(10) 0.0296(10) -0.0040(8) 0.0001(8) -0.0032(8)
C23 0.0424(12) 0.0347(12) 0.0345(11) -0.0003(9) 0.0059(9) -0.0063(9)
C24 0.0559(15) 0.0413(13) 0.0375(13) 0.0102(10) 0.0000(11) -0.0061(11)
C25 0.0495(15) 0.0430(14) 0.0460(14) 0.0111(11) -0.0157(11) 0.0016(11)
C26 0.0317(11) 0.0376(12) 0.0425(13) 0.0051(10) -0.0090(9) 0.0001(9)
C27 0.0303(10) 0.0258(10) 0.0296(10) -0.0008(8) -0.0046(8) -0.0037(8)
C28 0.0256(11) 0.0354(12) 0.0519(14) -0.0008(10) 0.0091(9) -0.0001(9)
C30 0.0199(9) 0.0205(9) 0.0289(10) -0.0018(7) -0.0027(7) 0.0005(7)
C31 0.0265(10) 0.0253(10) 0.0334(10) -0.0048(8) -0.0074(8) 0.0006(7)
C32 0.0335(11) 0.0267(10) 0.0321(11) -0.0063(8) -0.0060(8) 0.0002(8)
C33 0.0494(14) 0.0437(13) 0.0386(13) -0.0148(10) -0.0140(10) 0.0010(11)
C34 0.0638(17) 0.0490(14) 0.0351(12) -0.0190(11) -0.0057(11) -0.0003(12)
C35 0.0529(14) 0.0367(12) 0.0395(13) -0.0134(10) 0.0059(11) -0.0002(10)
C36 0.0357(11) 0.0295(10) 0.0367(11) -0.0081(9) 0.0033(9) -0.0016(9)
C37 0.0317(10) 0.0214(9) 0.0283(10) -0.0044(7) -0.0025(8) -0.0025(7)
C38 0.0276(11) 0.0503(14) 0.0494(14) -0.0149(11) -0.0151(10) 0.0046(10)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Al1 C3 1.952(2) . ?
Al1 C2 1.954(2) . ?
Al1 N3 1.9882(17) . ?
Al1 N1 2.0044(18) . ?
Al2 C4 1.953(2) . ?
Al2 C5 1.953(2) . ?
Al2 N1 1.9876(18) . ?
Al2 N2 1.9940(18) . ?
Al3 C7 1.948(2) . ?
Al3 C6 1.954(2) . ?
Al3 N2 1.9930(18) . ?
Al3 N3 1.9938(18) . ?
N1 C17 1.438(3) . ?
N1 C10 1.449(2) . ?
N2 C27 1.439(3) . ?
N2 C20 1.450(2) . ?
N3 C37 1.441(3) . ?
N3 C30 1.447(2) . ?
C1 C20 1.513(3) . ?
C1 C10 1.514(3) . ?
C1 C30 1.514(3) . ?
C1 H1A 0.9800 . ?
C2 H2A 0.9600 . ?
224
C2 H2B 0.9600 . ?
C2 H2C 0.9600 . ?
C3 H3A 0.9600 . ?
C3 H3B 0.9600 . ?
C3 H3C 0.9600 . ?
C4 H4A 0.9600 . ?
C4 H4B 0.9600 . ?
C4 H4C 0.9600 . ?
C5 H5A 0.9600 . ?
C5 H5B 0.9600 . ?
C5 H5C 0.9600 . ?
C6 H6A 0.9600 . ?
C6 H6B 0.9600 . ?
C6 H6C 0.9600 . ?
C7 H7A 0.9600 . ?
C7 H7B 0.9600 . ?
C7 H7C 0.9600 . ?
C10 C11 1.349(3) . ?
C11 C12 1.448(3) . ?
C11 C18 1.494(3) . ?
C12 C17 1.397(3) . ?
C12 C13 1.400(3) . ?
C13 C14 1.382(4) . ?
C13 H13A 0.9300 . ?
C14 C15 1.389(4) . ?
C14 H14A 0.9300 . ?
C15 C16 1.388(3) . ?
C15 H15A 0.9300 . ?
C16 C17 1.390(3) . ?
C16 H16A 0.9300 . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C20 C21 1.350(3) . ?
C21 C22 1.448(3) . ?
C21 C28 1.495(3) . ?
C22 C27 1.394(3) . ?
C22 C23 1.401(3) . ?
C23 C24 1.382(4) . ?
C23 H23A 0.9300 . ?
C24 C25 1.401(4) . ?
C24 H24A 0.9300 . ?
C25 C26 1.382(3) . ?
C25 H25A 0.9300 . ?
C26 C27 1.394(3) . ?
C26 H26A 0.9300 . ?
C28 H28A 0.9600 . ?
C28 H28B 0.9600 . ?
C28 H28C 0.9600 . ?
C30 C31 1.350(3) . ?
C31 C32 1.447(3) . ?
C31 C38 1.496(3) . ?
C32 C37 1.398(3) . ?
C32 C33 1.402(3) . ?
C33 C34 1.386(4) . ?
C33 H33A 0.9300 . ?
225
C34 C35 1.390(4) . ?
C34 H34A 0.9300 . ?
C35 C36 1.384(3) . ?
C35 H35A 0.9300 . ?
C36 C37 1.389(3) . ?
C36 H36A 0.9300 . ?
C38 H38A 0.9600 . ?
C38 H38B 0.9600 . ?
C38 H38C 0.9600 . ?
C50 C51 1.3900 . ?
C50 C54 1.3900 . ?
C51 C55 1.3900 . ?
C55 C52 1.3900 . ?
C52 C53 1.3900 . ?
C53 C56 1.155(18) 2_465 ?
C53 C54 1.3900 . ?
C53 C56 1.5083 . ?
C54 C56 1.23(2) 2_465 ?
C56 C53 1.16(3) 2_465 ?
C56 C54 1.227(16) 2_465 ?
C56 C56 1.34(2) 2_465 ?
C60 C61 1.3900 . ?
C60 C65 1.3900 . ?
C61 C62 1.3900 . ?
C62 C63 1.3900 . ?
C63 C64 1.3900 . ?
C63 C66 1.6922 . ?
C64 C65 1.3900 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C3 Al1 C2 119.78(10) . . ?
C3 Al1 N3 107.33(8) . . ?
C2 Al1 N3 113.40(9) . . ?
C3 Al1 N1 106.85(9) . . ?
C2 Al1 N1 112.42(9) . . ?
N3 Al1 N1 93.80(7) . . ?
C4 Al2 C5 119.02(11) . . ?
C4 Al2 N1 107.89(9) . . ?
C5 Al2 N1 113.27(9) . . ?
C4 Al2 N2 106.49(9) . . ?
C5 Al2 N2 113.37(10) . . ?
N1 Al2 N2 93.70(7) . . ?
C7 Al3 C6 117.41(11) . . ?
C7 Al3 N2 107.58(9) . . ?
C6 Al3 N2 112.59(10) . . ?
C7 Al3 N3 108.16(9) . . ?
C6 Al3 N3 114.00(9) . . ?
N2 Al3 N3 94.60(7) . . ?
C17 N1 C10 103.20(16) . . ?
226
C17 N1 Al2 110.46(12) . . ?
C10 N1 Al2 107.84(12) . . ?
C17 N1 Al1 106.03(12) . . ?
C10 N1 Al1 105.45(12) . . ?
Al2 N1 Al1 122.19(9) . . ?
C27 N2 C20 103.01(15) . . ?
C27 N2 Al3 109.70(13) . . ?
C20 N2 Al3 107.53(12) . . ?
C27 N2 Al2 107.87(13) . . ?
C20 N2 Al2 106.45(12) . . ?
Al3 N2 Al2 120.82(8) . . ?
C37 N3 C30 103.17(15) . . ?
C37 N3 Al1 111.31(12) . . ?
C30 N3 Al1 109.18(12) . . ?
C37 N3 Al3 106.49(12) . . ?
C30 N3 Al3 105.51(12) . . ?
Al1 N3 Al3 119.78(8) . . ?
C20 C1 C10 112.08(16) . . ?
C20 C1 C30 110.07(15) . . ?
C10 C1 C30 111.46(15) . . ?
C20 C1 H1A 107.7 . . ?
C10 C1 H1A 107.7 . . ?
C30 C1 H1A 107.7 . . ?
Al1 C2 H2A 109.5 . . ?
Al1 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
Al1 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
Al1 C3 H3A 109.5 . . ?
Al1 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
Al1 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
Al2 C4 H4A 109.5 . . ?
Al2 C4 H4B 109.5 . . ?
H4A C4 H4B 109.5 . . ?
Al2 C4 H4C 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?
Al2 C5 H5A 109.5 . . ?
Al2 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
Al2 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
Al3 C6 H6A 109.5 . . ?
Al3 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
Al3 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
Al3 C7 H7A 109.5 . . ?
Al3 C7 H7B 109.5 . . ?
H7A C7 H7B 109.5 . . ?
227
Al3 C7 H7C 109.5 . . ?
H7A C7 H7C 109.5 . . ?
H7B C7 H7C 109.5 . . ?
C11 C10 N1 112.50(17) . . ?
C11 C10 C1 130.19(18) . . ?
N1 C10 C1 117.28(16) . . ?
C10 C11 C12 106.68(18) . . ?
C10 C11 C18 129.0(2) . . ?
C12 C11 C18 124.27(19) . . ?
C17 C12 C13 119.6(2) . . ?
C17 C12 C11 107.80(18) . . ?
C13 C12 C11 132.6(2) . . ?
C14 C13 C12 118.4(2) . . ?
C14 C13 H13A 120.8 . . ?
C12 C13 H13A 120.8 . . ?
C13 C14 C15 121.3(2) . . ?
C13 C14 H14A 119.3 . . ?
C15 C14 H14A 119.3 . . ?
C16 C15 C14 121.3(2) . . ?
C16 C15 H15A 119.3 . . ?
C14 C15 H15A 119.3 . . ?
C15 C16 C17 117.2(2) . . ?
C15 C16 H16A 121.4 . . ?
C17 C16 H16A 121.4 . . ?
C16 C17 C12 122.2(2) . . ?
C16 C17 N1 127.9(2) . . ?
C12 C17 N1 109.81(18) . . ?
C11 C18 H18A 109.5 . . ?
C11 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C11 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
C21 C20 N2 112.58(17) . . ?
C21 C20 C1 130.33(17) . . ?
N2 C20 C1 117.10(16) . . ?
C20 C21 C22 106.58(17) . . ?
C20 C21 C28 128.50(19) . . ?
C22 C21 C28 124.92(18) . . ?
C27 C22 C23 119.8(2) . . ?
C27 C22 C21 107.89(18) . . ?
C23 C22 C21 132.3(2) . . ?
C24 C23 C22 118.4(2) . . ?
C24 C23 H23A 120.8 . . ?
C22 C23 H23A 120.8 . . ?
C23 C24 C25 121.1(2) . . ?
C23 C24 H24A 119.5 . . ?
C25 C24 H24A 119.5 . . ?
C26 C25 C24 121.2(2) . . ?
C26 C25 H25A 119.4 . . ?
C24 C25 H25A 119.4 . . ?
C25 C26 C27 117.5(2) . . ?
C25 C26 H26A 121.2 . . ?
C27 C26 H26A 121.2 . . ?
C26 C27 C22 122.0(2) . . ?
C26 C27 N2 128.1(2) . . ?
228
C22 C27 N2 109.94(17) . . ?
C21 C28 H28A 109.5 . . ?
C21 C28 H28B 109.5 . . ?
H28A C28 H28B 109.5 . . ?
C21 C28 H28C 109.5 . . ?
H28A C28 H28C 109.5 . . ?
H28B C28 H28C 109.5 . . ?
C31 C30 N3 112.63(17) . . ?
C31 C30 C1 129.94(18) . . ?
N3 C30 C1 117.38(16) . . ?
C30 C31 C32 106.63(18) . . ?
C30 C31 C38 128.2(2) . . ?
C32 C31 C38 125.17(19) . . ?
C37 C32 C33 119.5(2) . . ?
C37 C32 C31 107.86(18) . . ?
C33 C32 C31 132.6(2) . . ?
C34 C33 C32 118.2(2) . . ?
C34 C33 H33A 120.9 . . ?
C32 C33 H33A 120.9 . . ?
C33 C34 C35 121.4(2) . . ?
C33 C34 H34A 119.3 . . ?
C35 C34 H34A 119.3 . . ?
C36 C35 C34 121.3(2) . . ?
C36 C35 H35A 119.4 . . ?
C34 C35 H35A 119.4 . . ?
C35 C36 C37 117.4(2) . . ?
C35 C36 H36A 121.3 . . ?
C37 C36 H36A 121.3 . . ?
C36 C37 C32 122.3(2) . . ?
C36 C37 N3 128.02(19) . . ?
C32 C37 N3 109.69(18) . . ?
C31 C38 H38A 109.5 . . ?
C31 C38 H38B 109.5 . . ?
H38A C38 H38B 109.5 . . ?
C31 C38 H38C 109.5 . . ?
H38A C38 H38C 109.5 . . ?
H38B C38 H38C 109.5 . . ?
C51 C50 C54 120.0 . . ?
C55 C51 C50 120.0 . . ?
C51 C55 C52 120.0 . . ?
C53 C52 C55 120.0 . . ?
C56 C53 C54 56.7(11) 2_465 . ?
C56 C53 C52 176.7(11) 2_465 . ?
C54 C53 C52 120.0 . . ?
C56 C53 C56 58.9(11) 2_465 . ?
C54 C53 C56 115.6 . . ?
C52 C53 C56 124.4 . . ?
C56 C54 C53 51.9(10) 2_465 . ?
C56 C54 C50 171.9(10) 2_465 . ?
C53 C54 C50 120.0 . . ?
C53 C56 C54 71.3(10) 2_465 2_465 ?
C53 C56 C56 73.8(16) 2_465 2_465 ?
C54 C56 C56 145(2) 2_465 2_465 ?
C53 C56 C53 121.1(14) 2_465 . ?
C54 C56 C53 167.3(18) 2_465 . ?
C56 C56 C53 47.3(7) 2_465 . ?
229
C61 C60 C65 120.0 . . ?
C60 C61 C62 120.0 . . ?
C63 C62 C61 120.0 . . ?
C62 C63 C64 120.0 . . ?
C62 C63 C66 128.2 . . ?
C64 C63 C66 111.2 . . ?
C63 C64 C65 120.0 . . ?
C64 C65 C60 120.0 . . ?
_diffrn_measured_fraction_theta_max
_diffrn_reflns_theta_full
_diffrn_measured_fraction_theta_full
_refine_diff_density_max
_refine_diff_density_min
_refine_diff_density_rms
0.993
26.00
0.993
1.023
-0.342
0.090
230
CIF File for [{di(3-methylindolyl)imidazolylmethane}AlEt]
_audit_creation_method
_chemical_name_systematic
;
?
;
_chemical_name_common
_chemical_melting_point
_chemical_formula_moiety
_chemical_formula_sum
SHELXL-97
?
?
'C32 H32 Al N4'
'C32 H32 Al N4'
_chemical_formula_weight
499.60
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Al' 'Al' 0.0645 0.0514
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
_symmetry_space_group_name_H-M
triclinic
P-1
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
_cell_length_a
_cell_length_b
_cell_length_c
_cell_angle_alpha
_cell_angle_beta
_cell_angle_gamma
_cell_volume
_cell_formula_units_Z
_cell_measurement_temperature
_cell_measurement_reflns_used
_cell_measurement_theta_min
_cell_measurement_theta_max
_exptl_crystal_description
_exptl_crystal_colour
_exptl_crystal_size_max
_exptl_crystal_size_mid
_exptl_crystal_size_min
11.3139(11)
15.6164(14)
17.2642(16)
86.455(2)
87.184(2)
76.554(2)
2959.1(5)
4
–133
?
1.83
26.00
Square
light green
.30
30
.30
231
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn
_exptl_crystal_density_method
_exptl_crystal_F_000
_exptl_absorpt_coefficient_mu
_exptl_absorpt_correction_type
_exptl_absorpt_correction_T_min
_exptl_absorpt_correction_T_max
_exptl_absorpt_process_details
1.121
'not measured'
1060
0.094
multi-scan
0.837
1.00
'sadabs (Sheldrick, 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
_diffrn_radiation_wavelength
_diffrn_radiation_type
_diffrn_radiation_source
_diffrn_radiation_monochromator
_diffrn_measurement_device_type
_diffrn_measurement_method
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
?
_diffrn_reflns_number
_diffrn_reflns_av_R_equivalents
_diffrn_reflns_av_sigmaI/netI
_diffrn_reflns_limit_h_min
_diffrn_reflns_limit_h_max
_diffrn_reflns_limit_k_min
_diffrn_reflns_limit_k_max
_diffrn_reflns_limit_l_min
_diffrn_reflns_limit_l_max
_diffrn_reflns_theta_min
_diffrn_reflns_theta_max
_reflns_number_total
_reflns_number_gt
_reflns_threshold_expression
–133
0.71073
MoK\a
'fine-focus sealed tube'
'graphite'
'Bruker platform with 4k CCD'
'omega scans'
_computing_data_collection
_computing_cell_refinement
_computing_data_reduction
_computing_structure_solution
_computing_structure_refinement
_computing_molecular_graphics ?
_computing_publication_material ?
'Smart 5.630 '
'Saintplus 5.45 '
'Saintplus 5.45'
'SHELXS-97 (Sheldrick, 1990)'
'SHELXL-97 (Sheldrick, 1997)'
21154
0.0159
0.0243
-13
13
-17
19
-21
21
1.83
26.00
11565
10423
>2sigma(I)
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
232
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1016P)^2^+2.5183P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary
difmap
_atom_sites_solution_hydrogens
geom
_refine_ls_hydrogen_treatment
mixed
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
11565
_refine_ls_number_parameters
667
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.0673
_refine_ls_R_factor_gt
0.0620
_refine_ls_wR_factor_ref
0.1814
_refine_ls_wR_factor_gt
0.1756
_refine_ls_goodness_of_fit_ref
1.032
_refine_ls_restrained_S_all
1.032
_refine_ls_shift/su_max
15.000
_refine_ls_shift/su_mean
0.026
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Al1 Al 0.21163(5) 0.44708(4) 0.18193(3) 0.02554(15) Uani 1 1 d . . .
Al2 Al 0.29006(5) -0.07185(4) 0.31232(3) 0.02657(15) Uani 1 1 d . . .
N1 N 0.05321(15) 0.43851(11) 0.21095(9) 0.0253(3) Uani 1 1 d . . .
N2 N 0.28911(15) 0.37980(11) 0.26684(10) 0.0268(4) Uani 1 1 d . . .
N3 N 0.19955(16) 0.55711(11) 0.23124(10) 0.0271(4) Uani 1 1 d . . .
N4 N 0.14378(16) 0.63179(11) 0.33566(10) 0.0282(4) Uani 1 1 d . . .
N11 N 0.24276(16) -0.11107(11) 0.22085(10) 0.0281(4) Uani 1 1 d . . .
N12 N 0.15628(16) -0.08887(11) 0.37417(11) 0.0302(4) Uani 1 1 d . . .
N13 N 0.21899(17) 0.05180(11) 0.28664(11) 0.0316(4) Uani 1 1 d . . .
N14 N 0.06331(18) 0.14772(11) 0.23842(11) 0.0338(4) Uani 1 1 d . . .
C1 C 0.11586(17) 0.47287(12) 0.33847(11) 0.0234(4) Uani 1 1 d . . .
H1A H 0.0835 0.4825 0.3917 0.028 Uiso 1 1 calc R . .
C2 C 0.2712(2) 0.43206(17) 0.07513(13) 0.0401(5) Uani 1 1 d . . .
H2A H 0.2881 0.3697 0.0656 0.048 Uiso 1 1 calc R . .
233
H2B H 0.2065 0.4619 0.0414 0.048 Uiso 1 1 calc R . .
C3 C 0.3833(3) 0.4653(2) 0.05203(18) 0.0596(8) Uani 1 1 d . . .
H3A H 0.4049 0.4544 -0.0015 0.089 Uiso 1 1 calc R . .
H3B H 0.4491 0.4353 0.0838 0.089 Uiso 1 1 calc R . .
H3C H 0.3673 0.5275 0.0591 0.089 Uiso 1 1 calc R . .
C4 C 0.4524(2) -0.10649(17) 0.35223(13) 0.0370(5) Uani 1 1 d . . .
H4A H 0.4678 -0.1679 0.3706 0.044 Uiso 1 1 calc R . .
H4B H 0.5110 -0.1015 0.3102 0.044 Uiso 1 1 calc R . .
C5 C 0.4722(3) -0.0509(2) 0.41857(16) 0.0505(6) Uani 1 1 d . . .
H5A H 0.5539 -0.0711 0.4357 0.076 Uiso 1 1 calc R . .
H5B H 0.4159 -0.0566 0.4610 0.076 Uiso 1 1 calc R . .
H5C H 0.4590 0.0099 0.4005 0.076 Uiso 1 1 calc R . .
C6 C 0.04578(19) -0.01290(13) 0.25964(13) 0.0320(5) Uani 1 1 d . . .
H6A H -0.0373 0.0080 0.2416 0.038 Uiso 1 1 calc R . .
C10 C 0.02035(17) 0.45169(12) 0.28899(11) 0.0233(4) Uani 1 1 d . . .
C11 C -0.09422(18) 0.44142(12) 0.30786(12) 0.0256(4) Uani 1 1 d . . .
C12 C -0.13967(18) 0.42019(13) 0.23701(12) 0.0272(4) Uani 1 1 d . . .
C13 C -0.2502(2) 0.40224(15) 0.21751(14) 0.0354(5) Uani 1 1 d . . .
H13A H -0.3115 0.4013 0.2552 0.043 Uiso 1 1 calc R . .
C14 C -0.2664(2) 0.38597(16) 0.14141(15) 0.0400(5) Uani 1 1 d . . .
H14A H -0.3396 0.3746 0.1279 0.048 Uiso 1 1 calc R . .
C15 C -0.1737(2) 0.38632(15) 0.08431(14) 0.0385(5) Uani 1 1 d . . .
H15A H -0.1866 0.3751 0.0335 0.046 Uiso 1 1 calc R . .
C16 C -0.0636(2) 0.40309(14) 0.10212(12) 0.0321(5) Uani 1 1 d . . .
H16A H -0.0026 0.4032 0.0641 0.039 Uiso 1 1 calc R . .
C17 C -0.04670(18) 0.41985(12) 0.17887(12) 0.0263(4) Uani 1 1 d . . .
C18 C -0.1620(2) 0.45272(15) 0.38435(13) 0.0340(5) Uani 1 1 d . . .
H18A H -0.1110 0.4671 0.4220 0.051 Uiso 1 1 calc R . .
H18B H -0.1850 0.3989 0.4011 0.051 Uiso 1 1 calc R . .
H18C H -0.2337 0.4994 0.3791 0.051 Uiso 1 1 calc R . .
C20 C 0.22843(18) 0.39781(12) 0.33834(11) 0.0247(4) Uani 1 1 d . . .
C21 C 0.2818(2) 0.34242(13) 0.39749(12) 0.0296(4) Uani 1 1 d . . .
C22 C 0.3852(2) 0.28524(14) 0.36202(13) 0.0331(5) Uani 1 1 d . . .
C23 C 0.4771(2) 0.21543(15) 0.39093(17) 0.0451(6) Uani 1 1 d . . .
H23A H 0.4772 0.1976 0.4433 0.054 Uiso 1 1 calc R . .
C24 C 0.5669(2) 0.17389(17) 0.34036(19) 0.0541(7) Uani 1 1 d . . .
H24A H 0.6281 0.1277 0.3591 0.065 Uiso 1 1 calc R . .
C25 C 0.5680(2) 0.19975(17) 0.26144(19) 0.0503(7) Uani 1 1 d . . .
H25A H 0.6304 0.1708 0.2288 0.060 Uiso 1 1 calc R . .
C26 C 0.4781(2) 0.26774(15) 0.23083(16) 0.0391(5) Uani 1 1 d . . .
H26A H 0.4784 0.2843 0.1782 0.047 Uiso 1 1 calc R . .
C27 C 0.38716(19) 0.31034(13) 0.28192(13) 0.0301(4) Uani 1 1 d . . .
C28 C 0.2445(2) 0.34102(16) 0.48174(13) 0.0411(5) Uani 1 1 d . . .
H28A H 0.1716 0.3857 0.4901 0.062 Uiso 1 1 calc R . .
H28B H 0.3082 0.3521 0.5116 0.062 Uiso 1 1 calc R . .
H28C H 0.2298 0.2843 0.4976 0.062 Uiso 1 1 calc R . .
C30 C 0.15107(17) 0.55501(12) 0.30336(11) 0.0247(4) Uani 1 1 d . . .
C31 C 0.1902(2) 0.68592(14) 0.28174(13) 0.0346(5) Uani 1 1 d . . .
H31A H 0.1967 0.7433 0.2883 0.041 Uiso 1 1 calc R . .
C32 C 0.2244(2) 0.63932(14) 0.21763(13) 0.0319(4) Uani 1 1 d . . .
H32A H 0.2588 0.6593 0.1720 0.038 Uiso 1 1 calc R . .
C33 C 0.0958(3) 0.65507(16) 0.41333(14) 0.0422(6) Uani 1 1 d . . .
H33A H 0.0696 0.6061 0.4391 0.063 Uiso 1 1 calc R . .
H33B H 0.0281 0.7051 0.4097 0.063 Uiso 1 1 calc R . .
H33C H 0.1582 0.6694 0.4424 0.063 Uiso 1 1 calc R . .
C40 C -0.1348(2) 0.67072(16) 0.16875(14) 0.0426(6) Uani 1 1 d . . .
234
C41 C -0.1149(3) 0.7187(2) 0.22940(19) 0.0644(9) Uani 1 1 d . . .
H41A H -0.0494 0.7455 0.2273 0.077 Uiso 1 1 calc R . .
C42 C -0.1976(5) 0.7263(3) 0.29572(19) 0.0888(15) Uani 1 1 d . . .
H42A H -0.1861 0.7579 0.3376 0.107 Uiso 1 1 calc R . .
C43 C -0.2946(4) 0.6862(3) 0.2967(2) 0.0813(13) Uani 1 1 d . . .
H43A H -0.3489 0.6911 0.3393 0.098 Uiso 1 1 calc R . .
C44 C -0.3107(3) 0.6407(2) 0.2368(2) 0.0735(10) Uani 1 1 d . . .
H44A H -0.3765 0.6143 0.2381 0.088 Uiso 1 1 calc R . .
C45 C -0.2329(3) 0.63210(18) 0.17400(18) 0.0541(7) Uani 1 1 d . . .
H45A H -0.2461 0.5993 0.1334 0.065 Uiso 1 1 calc R . .
C46 C -0.0509(3) 0.6595(2) 0.09797(18) 0.0663(9) Uani 1 1 d . . .
H46A H 0.0128 0.6896 0.1036 0.099 Uiso 1 1 calc R . .
H46B H -0.0959 0.6837 0.0529 0.099 Uiso 1 1 calc R . .
H46C H -0.0161 0.5979 0.0922 0.099 Uiso 1 1 calc R . .
C50 C -0.3166(3) -0.0648(2) 0.00875(16) 0.0543(7) Uani 1 1 d . . .
C51 C -0.3185(2) -0.12471(19) 0.07205(16) 0.0471(6) Uani 1 1 d . . .
H51A H -0.2948 -0.1849 0.0650 0.056 Uiso 1 1 calc R . .
C52 C -0.3549(3) -0.0954(2) 0.14440(17) 0.0522(7) Uani 1 1 d . . .
H52A H -0.3540 -0.1358 0.1864 0.063 Uiso 1 1 calc R . .
C53 C -0.3927(3) -0.0068(2) 0.15529(19) 0.0627(8) Uani 1 1 d . . .
H53A H -0.4179 0.0130 0.2045 0.075 Uiso 1 1 calc R . .
C54 C -0.3932(4) 0.0523(2) 0.0933(2) 0.0696(9) Uani 1 1 d . . .
H54A H -0.4190 0.1124 0.1005 0.084 Uiso 1 1 calc R . .
C55 C -0.3560(3) 0.0237(2) 0.02053(18) 0.0611(8) Uani 1 1 d . . .
H55A H -0.3575 0.0646 -0.0212 0.073 Uiso 1 1 calc R . .
C56 C -0.27302(9) -0.09458(7) -0.07007(6) 0.0926(13) Uani 1 1 d . . .
H56A H -0.2784 -0.0442 -0.1056 0.139 Uiso 1 1 calc R . .
H56B H -0.3226 -0.1315 -0.0872 0.139 Uiso 1 1 calc R . .
H56C H -0.1900 -0.1273 -0.0682 0.139 Uiso 1 1 calc R . .
C74 C 0.50129(9) 0.46258(7) 0.40914(6) 0.080(2) Uiso 0.50 1 d PR . 1
C73 C 0.45529(9) 0.53910(7) 0.36438(6) 0.161(6) Uiso 0.50 1 d PR A 1
C72 C 0.42189(9) 0.61971(7) 0.39889(6) 0.47(3) Uiso 0.50 1 d PR A 1
C71 C 0.43450(9) 0.62381(7) 0.47817(6) 0.339(17) Uiso 0.50 1 d PR . 1
C70 C 0.48050(9) 0.54730(7) 0.52294(6) 0.090(3) Uiso 0.50 1 d PR . 1
C75 C 0.51389(9) 0.46668(7) 0.48843(6) 2.0(3) Uiso 0.50 1 d PR . 1
C60 C 0.51155(9) 0.49451(7) 0.53689(6) 0.0572(14) Uiso 0.50 1 d PR . 3
C61 C 0.53844(9) 0.42706(7) 0.48541(6) 0.330(19) Uiso 0.50 1 d PR . 3
C62 C 0.51277(9) 0.44522(7) 0.40739(6) 0.43(3) Uiso 0.50 1 d PR . 3
C63 C 0.46022(9) 0.53082(7) 0.38084(6) 0.0503(14) Uiso 0.50 1 d PR . 3
C64 C 0.43333(9) 0.59827(7) 0.43232(6) 0.085(2) Uiso 0.50 1 d PR . 3
C65 C 0.45900(9) 0.58012(7) 0.51034(6) 0.0414(11) Uiso 0.50 1 d PR . 3
C110 C 0.12097(9) -0.07658(7) 0.20346(6) 0.0297(4) Uani 1 1 d R . .
C111 C 0.09135(9) -0.10531(7) 0.13514(6) 0.0331(5) Uani 1 1 d R . .
C112 C 0.20075(9) -0.16287(7) 0.10698(6) 0.0318(5) Uani 1 1 d R . .
C113 C 0.23101(9) -0.21303(7) 0.04112(6) 0.0395(5) Uani 1 1 d R . .
H11A H 0.1730 -0.2126 0.0047 0.047 Uiso 1 1 calc R . .
C114 C 0.3480(3) -0.26297(17) 0.03113(14) 0.0440(6) Uani 1 1 d . . .
H11B H 0.3685 -0.2964 -0.0124 0.053 Uiso 1 1 calc R . .
C115 C 0.4364(2) -0.26411(17) 0.08553(14) 0.0419(5) Uani 1 1 d . . .
H11C H 0.5146 -0.2983 0.0775 0.050 Uiso 1 1 calc R . .
C116 C 0.4097(2) -0.21547(15) 0.15084(13) 0.0343(5) Uani 1 1 d . . .
H11D H 0.4685 -0.2166 0.1869 0.041 Uiso 1 1 calc R . .
C117 C 0.2921(2) -0.16468(13) 0.16101(12) 0.0293(4) Uani 1 1 d . . .
C118 C -0.0285(2) -0.08257(18) 0.09627(16) 0.0465(6) Uani 1 1 d . . .
H11E H -0.0867 -0.0423 0.1269 0.070 Uiso 1 1 calc R . .
H11F H -0.0569 -0.1353 0.0914 0.070 Uiso 1 1 calc R . .
235
H11G H -0.0187 -0.0555 0.0456 0.070 Uiso 1 1 calc R . .
C120 C 0.04364(19) -0.05610(13) 0.34077(13) 0.0311(4) Uani 1 1 d . . .
C121 C -0.0507(2) -0.07042(14) 0.38828(15) 0.0353(5) Uani 1 1 d . . .
C122 C 0.0037(2) -0.11655(14) 0.45667(14) 0.0347(5) Uani 1 1 d . . .
C123 C -0.0422(2) -0.15435(17) 0.52448(15) 0.0445(6) Uani 1 1 d . . .
H12A H -0.1255 -0.1483 0.5329 0.053 Uiso 1 1 calc R . .
C124 C 0.0382(3) -0.20046(18) 0.57822(15) 0.0490(6) Uani 1 1 d . . .
H12B H 0.0086 -0.2270 0.6224 0.059 Uiso 1 1 calc R . .
C125 C 0.1634(3) -0.20804(17) 0.56748(14) 0.0446(6) Uani 1 1 d . . .
H12C H 0.2154 -0.2384 0.6052 0.054 Uiso 1 1 calc R . .
C126 C 0.2116(2) -0.17120(15) 0.50179(13) 0.0360(5) Uani 1 1 d . . .
H12D H 0.2949 -0.1762 0.4951 0.043 Uiso 1 1 calc R . .
C127 C 0.1317(2) -0.12646(13) 0.44598(12) 0.0305(4) Uani 1 1 d . . .
C128 C -0.1845(2) -0.04243(17) 0.37471(19) 0.0505(7) Uani 1 1 d . . .
H12E H -0.1971 -0.0126 0.3245 0.076 Uiso 1 1 calc R . .
H12F H -0.2235 -0.0033 0.4139 0.076 Uiso 1 1 calc R . .
H12G H -0.2185 -0.0934 0.3771 0.076 Uiso 1 1 calc R . .
C130 C 0.1062(2) 0.06361(13) 0.26180(13) 0.0313(4) Uani 1 1 d . . .
C131 C 0.1524(2) 0.19269(14) 0.25017(14) 0.0387(5) Uani 1 1 d . . .
H13B H 0.1472 0.2526 0.2399 0.046 Uiso 1 1 calc R . .
C132 C 0.2481(2) 0.13307(14) 0.27933(13) 0.0356(5) Uani 1 1 d . . .
H13C H 0.3214 0.1448 0.2923 0.043 Uiso 1 1 calc R . .
C133 C -0.0566(2) 0.18552(15) 0.20751(16) 0.0460(6) Uani 1 1 d . . .
H13D H -0.1005 0.1400 0.2054 0.069 Uiso 1 1 calc R . .
H13E H -0.0475 0.2111 0.1562 0.069 Uiso 1 1 calc R . .
H13F H -0.1006 0.2302 0.2406 0.069 Uiso 1 1 calc R . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Al1 0.0310(3) 0.0226(3) 0.0223(3) 0.0005(2) 0.0025(2) -0.0059(2)
Al2 0.0295(3) 0.0252(3) 0.0275(3) -0.0016(2) -0.0037(2) -0.0106(2)
N1 0.0308(8) 0.0234(8) 0.0218(8) -0.0011(6) -0.0015(6) -0.0065(7)
N2 0.0278(8) 0.0226(8) 0.0290(9) 0.0003(6) -0.0004(7) -0.0045(7)
N3 0.0323(9) 0.0220(8) 0.0273(8) 0.0024(6) 0.0003(7) -0.0084(7)
N4 0.0336(9) 0.0220(8) 0.0302(9) -0.0017(7) -0.0012(7) -0.0088(7)
N11 0.0319(9) 0.0238(8) 0.0306(9) -0.0003(7) -0.0053(7) -0.0100(7)
N12 0.0302(9) 0.0269(9) 0.0347(9) 0.0017(7) -0.0025(7) -0.0095(7)
N13 0.0392(10) 0.0244(9) 0.0345(9) -0.0024(7) -0.0025(8) -0.0135(7)
N14 0.0462(11) 0.0195(8) 0.0348(10) -0.0015(7) 0.0017(8) -0.0064(7)
C1 0.0290(9) 0.0217(9) 0.0204(9) 0.0004(7) -0.0014(7) -0.0078(7)
C2 0.0501(14) 0.0400(13) 0.0294(11) -0.0018(9) 0.0075(10) -0.0108(11)
C3 0.0479(15) 0.070(2) 0.0545(17) 0.0078(14) 0.0119(13) -0.0071(14)
C4 0.0299(11) 0.0471(13) 0.0348(12) -0.0040(10) -0.0013(9) -0.0098(9)
C5 0.0537(15) 0.0643(17) 0.0419(14) -0.0023(12) -0.0125(12) -0.0283(13)
C6 0.0309(10) 0.0217(10) 0.0439(12) 0.0027(9) -0.0089(9) -0.0069(8)
C10 0.0291(10) 0.0188(9) 0.0221(9) 0.0007(7) -0.0022(7) -0.0056(7)
C11 0.0281(10) 0.0203(9) 0.0280(10) 0.0003(7) -0.0015(8) -0.0050(7)
C12 0.0299(10) 0.0205(9) 0.0299(10) 0.0000(7) -0.0047(8) -0.0030(7)
C13 0.0307(11) 0.0316(11) 0.0442(13) -0.0028(9) -0.0053(9) -0.0066(9)
C14 0.0366(12) 0.0374(12) 0.0482(14) -0.0035(10) -0.0147(10) -0.0098(10)
236
C15 0.0490(13) 0.0332(11) 0.0344(12) -0.0024(9) -0.0163(10) -0.0085(10)
C16 0.0416(12) 0.0274(10) 0.0270(10) -0.0004(8) -0.0060(9) -0.0065(9)
C17 0.0318(10) 0.0182(9) 0.0283(10) 0.0004(7) -0.0060(8) -0.0040(7)
C18 0.0331(11) 0.0379(12) 0.0320(11) -0.0025(9) 0.0040(9) -0.0112(9)
C20 0.0291(10) 0.0216(9) 0.0252(9) 0.0009(7) -0.0026(7) -0.0096(8)
C21 0.0363(11) 0.0227(9) 0.0319(11) 0.0017(8) -0.0093(8) -0.0100(8)
C22 0.0358(11) 0.0233(10) 0.0421(12) 0.0013(9) -0.0142(9) -0.0088(8)
C23 0.0477(14) 0.0291(11) 0.0575(16) 0.0008(11) -0.0256(12) -0.0030(10)
C24 0.0443(14) 0.0327(13) 0.082(2) -0.0059(13) -0.0279(14) 0.0048(11)
C25 0.0329(12) 0.0368(13) 0.079(2) -0.0160(13) -0.0045(12) 0.0006(10)
C26 0.0330(11) 0.0308(11) 0.0530(14) -0.0073(10) 0.0008(10) -0.0054(9)
C27 0.0281(10) 0.0203(9) 0.0433(12) -0.0024(8) -0.0046(9) -0.0076(8)
C28 0.0557(15) 0.0387(12) 0.0296(11) 0.0076(9) -0.0112(10) -0.0124(11)
C30 0.0274(9) 0.0205(9) 0.0265(10) -0.0003(7) -0.0032(7) -0.0058(7)
C31 0.0450(12) 0.0216(10) 0.0395(12) 0.0020(8) -0.0008(10) -0.0136(9)
C32 0.0374(11) 0.0250(10) 0.0345(11) 0.0057(8) -0.0001(9) -0.0115(8)
C33 0.0614(15) 0.0331(12) 0.0356(12) -0.0115(10) 0.0077(11) -0.0172(11)
C40 0.0488(14) 0.0346(12) 0.0355(12) 0.0040(10) -0.0053(10) 0.0078(10)
C41 0.069(2) 0.0522(17) 0.064(2) -0.0052(14) -0.0266(16) 0.0060(14)
C42 0.132(4) 0.067(2) 0.0412(17) -0.0156(16) -0.030(2) 0.039(2)
C43 0.087(3) 0.072(2) 0.057(2) 0.0160(18) 0.0143(19) 0.031(2)
C44 0.070(2) 0.0567(19) 0.076(2) 0.0227(18) 0.0144(18) 0.0115(16)
C45 0.0583(17) 0.0379(14) 0.0586(17) 0.0088(12) -0.0033(13) 0.0015(12)
C46 0.070(2) 0.066(2) 0.0477(16) 0.0103(14) 0.0097(14) 0.0096(16)
C50 0.0453(15) 0.079(2) 0.0418(14) 0.0053(13) -0.0027(11) -0.0221(14)
C51 0.0408(13) 0.0480(15) 0.0517(15) 0.0054(12) -0.0042(11) -0.0104(11)
C52 0.0523(15) 0.0586(17) 0.0469(15) 0.0150(13) -0.0001(12) -0.0201(13)
C53 0.079(2) 0.0622(19) 0.0497(17) -0.0053(14) 0.0074(15) -0.0231(16)
C54 0.095(3) 0.0478(17) 0.069(2) 0.0040(15) -0.0017(18) -0.0241(17)
C55 0.075(2) 0.0618(19) 0.0524(17) 0.0231(14) -0.0110(15) -0.0322(16)
C56 0.091(3) 0.142(4) 0.0464(19) -0.011(2) 0.0100(18) -0.032(3)
C110 0.0341(11) 0.0214(9) 0.0359(11) 0.0036(8) -0.0098(9) -0.0106(8)
C111 0.0421(12) 0.0248(10) 0.0361(11) 0.0051(8) -0.0123(9) -0.0145(9)
C112 0.0444(12) 0.0275(10) 0.0287(10) 0.0040(8) -0.0067(9) -0.0190(9)
C113 0.0571(15) 0.0391(12) 0.0294(11) -0.0001(9) -0.0079(10) -0.0244(11)
C114 0.0596(16) 0.0465(14) 0.0329(12) -0.0111(10) 0.0055(11) -0.0259(12)
C115 0.0444(13) 0.0436(13) 0.0414(13) -0.0103(10) 0.0081(10) -0.0176(11)
C116 0.0375(11) 0.0350(11) 0.0347(11) -0.0047(9) -0.0006(9) -0.0164(9)
C117 0.0397(11) 0.0243(10) 0.0281(10) 0.0005(8) -0.0024(8) -0.0163(8)
C118 0.0488(14) 0.0457(14) 0.0484(14) 0.0044(11) -0.0223(12) -0.0155(11)
C120 0.0303(10) 0.0215(9) 0.0417(12) -0.0019(8) -0.0021(9) -0.0060(8)
C121 0.0310(11) 0.0222(10) 0.0525(14) -0.0089(9) 0.0047(9) -0.0053(8)
C122 0.0386(12) 0.0242(10) 0.0426(12) -0.0105(9) 0.0093(9) -0.0097(9)
C123 0.0496(14) 0.0414(13) 0.0455(14) -0.0159(11) 0.0194(11) -0.0175(11)
C124 0.0709(18) 0.0497(15) 0.0316(12) -0.0084(11) 0.0153(12) -0.0265(13)
C125 0.0665(17) 0.0440(14) 0.0281(11) -0.0024(10) -0.0022(11) -0.0222(12)
C126 0.0466(13) 0.0335(11) 0.0309(11) -0.0045(9) -0.0009(9) -0.0149(10)
C127 0.0382(11) 0.0234(10) 0.0319(11) -0.0062(8) 0.0045(9) -0.0108(8)
C128 0.0307(12) 0.0380(13) 0.080(2) -0.0068(13) 0.0055(12) -0.0032(10)
C130 0.0396(11) 0.0217(10) 0.0330(11) -0.0006(8) -0.0017(9) -0.0080(8)
C131 0.0564(14) 0.0222(10) 0.0402(12) -0.0049(9) 0.0066(10) -0.0156(10)
C132 0.0490(13) 0.0281(11) 0.0347(11) -0.0063(9) 0.0054(10) -0.0188(10)
C133 0.0545(15) 0.0250(11) 0.0539(15) 0.0040(10) -0.0090(12) 0.0001(10)
_geom_special_details
;
237
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Al1 N1 1.8699(18) . ?
Al1 N2 1.8785(18) . ?
Al1 N3 1.9380(18) . ?
Al1 C2 1.941(2) . ?
Al2 N12 1.8696(19) . ?
Al2 N11 1.8735(18) . ?
Al2 C4 1.939(2) . ?
Al2 N13 1.9439(19) . ?
N1 C17 1.380(3) . ?
N1 C10 1.395(2) . ?
N2 C27 1.382(3) . ?
N2 C20 1.394(3) . ?
N3 C30 1.337(3) . ?
N3 C32 1.381(3) . ?
N4 C30 1.337(3) . ?
N4 C31 1.385(3) . ?
N4 C33 1.457(3) . ?
N11 C117 1.383(3) . ?
N11 C110 1.398(2) . ?
N12 C127 1.382(3) . ?
N12 C120 1.397(3) . ?
N13 C130 1.335(3) . ?
N13 C132 1.381(3) . ?
N14 C130 1.334(3) . ?
N14 C131 1.385(3) . ?
N14 C133 1.461(3) . ?
C1 C30 1.513(3) . ?
C1 C10 1.516(3) . ?
C1 C20 1.517(3) . ?
C2 C3 1.506(4) . ?
C4 C5 1.534(3) . ?
C6 C130 1.511(3) . ?
C6 C120 1.518(3) . ?
C6 C110 1.516(2) . ?
C10 C11 1.364(3) . ?
C11 C12 1.436(3) . ?
C11 C18 1.493(3) . ?
C12 C13 1.404(3) . ?
C12 C17 1.417(3) . ?
C13 C14 1.382(3) . ?
C14 C15 1.404(4) . ?
C15 C16 1.384(3) . ?
238
C16 C17 1.397(3) . ?
C20 C21 1.365(3) . ?
C21 C22 1.433(3) . ?
C21 C28 1.495(3) . ?
C22 C23 1.405(3) . ?
C22 C27 1.414(3) . ?
C23 C24 1.375(4) . ?
C24 C25 1.397(4) . ?
C25 C26 1.387(4) . ?
C26 C27 1.394(3) . ?
C31 C32 1.353(3) . ?
C40 C41 1.381(4) . ?
C40 C45 1.378(4) . ?
C40 C46 1.503(4) . ?
C41 C42 1.436(6) . ?
C42 C43 1.384(6) . ?
C43 C44 1.334(6) . ?
C44 C45 1.355(4) . ?
C50 C55 1.375(5) . ?
C50 C51 1.396(4) . ?
C50 C56 1.489(3) . ?
C51 C52 1.368(4) . ?
C52 C53 1.373(5) . ?
C53 C54 1.369(5) . ?
C54 C55 1.372(5) . ?
C74 C70 1.1948(19) 2_666 ?
C74 C73 1.3900 . ?
C74 C75 1.3900 . ?
C73 C72 1.3900 . ?
C72 C71 1.3900 . ?
C71 C70 1.3900 . ?
C71 C75 1.490(2) 2_666 ?
C70 C75 0.296(2) 2_666 ?
C70 C74 1.1948(19) 2_666 ?
C70 C75 1.3900 . ?
C70 C70 1.677(2) 2_666 ?
C75 C70 0.296(2) 2_666 ?
C75 C75 1.108(2) 2_666 ?
C75 C71 1.490(2) 2_666 ?
C60 C61 1.268(2) 2_666 ?
C60 C60 1.3057(19) 2_666 ?
C60 C62 1.361(2) 2_666 ?
C60 C61 1.3900 . ?
C60 C65 1.3900 . ?
C60 C65 1.430(2) 2_666 ?
C60 C63 1.4806(19) 2_666 ?
C60 C64 1.513(2) 2_666 ?
C61 C65 0.128(2) 2_666 ?
C61 C60 1.268(2) 2_666 ?
C61 C62 1.3900 . ?
C61 C64 1.4806(19) 2_666 ?
C62 C60 1.361(2) 2_666 ?
C62 C63 1.3900 . ?
C62 C65 1.4807(19) 2_666 ?
C63 C64 1.3900 . ?
C63 C60 1.4806(19) 2_666 ?
239
C64 C65 1.3900 . ?
C64 C61 1.481(2) 2_666 ?
C64 C60 1.513(2) 2_666 ?
C65 C61 0.128(2) 2_666 ?
C65 C60 1.430(2) 2_666 ?
C65 C62 1.481(2) 2_666 ?
C110 C111 1.3708 . ?
C111 C112 1.4331 . ?
C111 C118 1.501(3) . ?
C112 C113 1.4039 . ?
C112 C117 1.420(2) . ?
C113 C114 1.380(3) . ?
C114 C115 1.402(4) . ?
C115 C116 1.380(3) . ?
C116 C117 1.391(3) . ?
C120 C121 1.366(3) . ?
C121 C122 1.433(3) . ?
C121 C128 1.500(3) . ?
C122 C123 1.410(3) . ?
C122 C127 1.424(3) . ?
C123 C124 1.380(4) . ?
C124 C125 1.398(4) . ?
C125 C126 1.385(3) . ?
C126 C127 1.394(3) . ?
C131 C132 1.349(4) . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Al1 N2 97.15(8) . . ?
N1 Al1 N3 94.79(7) . . ?
N2 Al1 N3 92.62(8) . . ?
N1 Al1 C2 120.40(10) . . ?
N2 Al1 C2 123.47(10) . . ?
N3 Al1 C2 121.33(9) . . ?
N12 Al2 N11 96.39(8) . . ?
N12 Al2 C4 120.26(9) . . ?
N11 Al2 C4 124.71(9) . . ?
N12 Al2 N13 94.33(8) . . ?
N11 Al2 N13 94.34(8) . . ?
C4 Al2 N13 119.77(9) . . ?
C17 N1 C10 105.39(16) . . ?
C17 N1 Al1 139.45(14) . . ?
C10 N1 Al1 115.13(13) . . ?
C27 N2 C20 105.63(17) . . ?
C27 N2 Al1 139.64(15) . . ?
C20 N2 Al1 114.50(13) . . ?
C30 N3 C32 106.73(17) . . ?
C30 N3 Al1 111.73(13) . . ?
C32 N3 Al1 141.53(15) . . ?
C30 N4 C31 107.59(17) . . ?
240
C30 N4 C33 126.62(18) . . ?
C31 N4 C33 125.79(18) . . ?
C117 N11 C110 105.86(15) . . ?
C117 N11 Al2 139.67(15) . . ?
C110 N11 Al2 114.46(11) . . ?
C127 N12 C120 105.90(17) . . ?
C127 N12 Al2 139.30(15) . . ?
C120 N12 Al2 114.80(14) . . ?
C130 N13 C132 106.69(18) . . ?
C130 N13 Al2 111.56(13) . . ?
C132 N13 Al2 141.49(16) . . ?
C130 N14 C131 107.46(19) . . ?
C130 N14 C133 126.1(2) . . ?
C131 N14 C133 126.40(19) . . ?
C30 C1 C10 108.55(15) . . ?
C30 C1 C20 108.22(16) . . ?
C10 C1 C20 109.86(15) . . ?
C3 C2 Al1 116.37(19) . . ?
C5 C4 Al2 113.41(17) . . ?
C130 C6 C120 108.69(18) . . ?
C130 C6 C110 107.00(16) . . ?
C120 C6 C110 110.92(15) . . ?
C11 C10 N1 112.85(17) . . ?
C11 C10 C1 130.91(18) . . ?
N1 C10 C1 116.23(16) . . ?
C10 C11 C12 105.26(17) . . ?
C10 C11 C18 128.42(19) . . ?
C12 C11 C18 126.28(18) . . ?
C13 C12 C17 119.54(19) . . ?
C13 C12 C11 133.6(2) . . ?
C17 C12 C11 106.89(17) . . ?
C14 C13 C12 119.0(2) . . ?
C13 C14 C15 120.9(2) . . ?
C16 C15 C14 121.3(2) . . ?
C15 C16 C17 118.2(2) . . ?
N1 C17 C16 129.3(2) . . ?
N1 C17 C12 109.60(17) . . ?
C16 C17 C12 121.15(19) . . ?
C21 C20 N2 112.70(18) . . ?
C21 C20 C1 130.66(18) . . ?
N2 C20 C1 116.64(16) . . ?
C20 C21 C22 105.10(19) . . ?
C20 C21 C28 128.7(2) . . ?
C22 C21 C28 126.24(19) . . ?
C23 C22 C27 119.2(2) . . ?
C23 C22 C21 133.4(2) . . ?
C27 C22 C21 107.40(18) . . ?
C24 C23 C22 118.8(3) . . ?
C23 C24 C25 121.3(2) . . ?
C26 C25 C24 121.4(2) . . ?
C25 C26 C27 117.5(2) . . ?
N2 C27 C26 129.1(2) . . ?
N2 C27 C22 109.16(19) . . ?
C26 C27 C22 121.7(2) . . ?
N4 C30 N3 110.25(17) . . ?
N4 C30 C1 128.76(18) . . ?
241
N3 C30 C1 120.97(17) . . ?
C32 C31 N4 106.85(18) . . ?
C31 C32 N3 108.57(19) . . ?
C41 C40 C45 119.0(3) . . ?
C41 C40 C46 121.2(3) . . ?
C45 C40 C46 119.8(3) . . ?
C40 C41 C42 118.5(4) . . ?
C43 C42 C41 119.3(3) . . ?
C44 C43 C42 120.3(4) . . ?
C43 C44 C45 121.3(4) . . ?
C44 C45 C40 121.7(3) . . ?
C55 C50 C51 118.4(3) . . ?
C55 C50 C56 119.9(2) . . ?
C51 C50 C56 121.7(3) . . ?
C52 C51 C50 120.5(3) . . ?
C51 C52 C53 120.3(3) . . ?
C54 C53 C52 119.5(3) . . ?
C53 C54 C55 120.6(3) . . ?
C54 C55 C50 120.6(3) . . ?
C70 C74 C73 129.91(10) 2_666 . ?
C70 C74 C75 9.93(10) 2_666 . ?
C73 C74 C75 120.0 . . ?
C74 C73 C72 120.0 . . ?
C71 C72 C73 120.0 . . ?
C72 C71 C70 120.0 . . ?
C72 C71 C75 108.88(7) . 2_666 ?
C70 C71 C75 11.13(7) . 2_666 ?
C75 C70 C74 126.0(5) 2_666 2_666 ?
C75 C70 C75 16.1(4) 2_666 . ?
C74 C70 C75 110.08(10) 2_666 . ?
C75 C70 C71 104.0(4) 2_666 . ?
C74 C70 C71 129.91(10) 2_666 . ?
C75 C70 C71 120.0 . . ?
C75 C70 C70 13.3(3) 2_666 2_666 ?
C74 C70 C70 112.87(14) 2_666 2_666 ?
C75 C70 C70 2.81(7) . 2_666 ?
C71 C70 C70 117.21(7) . 2_666 ?
C70 C75 C75 159.7(5) 2_666 2_666 ?
C70 C75 C70 163.9(4) 2_666 . ?
C75 C75 C70 4.25(10) 2_666 . ?
C70 C75 C74 44.0(4) 2_666 . ?
C75 C75 C74 115.77(10) 2_666 . ?
C70 C75 C74 120.0 . . ?
C70 C75 C71 64.9(4) 2_666 2_666 ?
C75 C75 C71 135.34(16) 2_666 2_666 ?
C70 C75 C71 131.12(7) . 2_666 ?
C74 C75 C71 108.87(7) . 2_666 ?
C61 C60 C60 65.35(10) 2_666 2_666 ?
C61 C60 C62 63.71(9) 2_666 2_666 ?
C60 C60 C62 129.04(16) 2_666 2_666 ?
C61 C60 C61 121.38(9) 2_666 . ?
C60 C60 C61 56.03(9) 2_666 . ?
C62 C60 C61 174.79(8) 2_666 . ?
C61 C60 C65 1.78(9) 2_666 . ?
C60 C60 C65 63.98(9) 2_666 . ?
C62 C60 C65 65.11(8) 2_666 . ?
242
C61 C60 C65 120.0 . . ?
C61 C60 C65 126.21(15) 2_666 2_666 ?
C60 C60 C65 60.88(8) 2_666 2_666 ?
C62 C60 C65 169.83(16) 2_666 2_666 ?
C61 C60 C65 4.96(8) . 2_666 ?
C65 C60 C65 124.86(8) . 2_666 ?
C61 C60 C63 122.08(14) 2_666 2_666 ?
C60 C60 C63 172.25(16) 2_666 2_666 ?
C62 C60 C63 58.39(8) 2_666 2_666 ?
C61 C60 C63 116.49(8) . 2_666 ?
C65 C60 C63 123.50(8) . 2_666 ?
C65 C60 C63 111.61(13) 2_666 2_666 ?
C61 C60 C64 176.73(17) 2_666 2_666 ?
C60 C60 C64 117.16(14) 2_666 2_666 ?
C62 C60 C64 113.70(13) 2_666 2_666 ?
C61 C60 C64 61.17(7) . 2_666 ?
C65 C60 C64 178.51(8) . 2_666 ?
C65 C60 C64 56.29(7) 2_666 2_666 ?
C63 C60 C64 55.33(7) 2_666 2_666 ?
C65 C61 C60 160.4(10) 2_666 2_666 ?
C65 C61 C60 105.6(9) 2_666 . ?
C60 C61 C60 58.62(9) 2_666 . ?
C65 C61 C62 133.1(9) 2_666 . ?
C60 C61 C62 61.39(9) 2_666 . ?
C60 C61 C62 120.0 . . ?
C65 C61 C64 43.3(8) 2_666 2_666 ?
C60 C61 C64 122.08(14) 2_666 2_666 ?
C60 C61 C64 63.51(8) . 2_666 ?
C62 C61 C64 176.37(7) . 2_666 ?
C60 C62 C63 65.11(8) 2_666 . ?
C60 C62 C61 54.90(8) 2_666 . ?
C63 C62 C61 120.0 . . ?
C60 C62 C65 58.39(8) 2_666 2_666 ?
C63 C62 C65 123.50(8) . 2_666 ?
C61 C62 C65 3.63(7) . 2_666 ?
C64 C63 C62 120.0 . . ?
C64 C63 C60 63.51(8) . 2_666 ?
C62 C63 C60 56.50(8) . 2_666 ?
C65 C64 C63 120.0 . . ?
C65 C64 C61 3.63(7) . 2_666 ?
C63 C64 C61 116.49(8) . 2_666 ?
C65 C64 C60 58.84(7) . 2_666 ?
C63 C64 C60 61.17(7) . 2_666 ?
C61 C64 C60 55.33(7) 2_666 2_666 ?
C61 C65 C64 133.1(9) 2_666 . ?
C61 C65 C60 17.9(9) 2_666 . ?
C64 C65 C60 120.0 . . ?
C61 C65 C60 69.4(9) 2_666 2_666 ?
C64 C65 C60 64.87(8) . 2_666 ?
C60 C65 C60 55.14(8) . 2_666 ?
C61 C65 C62 43.3(8) 2_666 2_666 ?
C64 C65 C62 176.37(7) . 2_666 ?
C60 C65 C62 56.50(8) . 2_666 ?
C60 C65 C62 111.61(13) 2_666 2_666 ?
C111 C110 N11 112.38(8) . . ?
C111 C110 C6 130.88(9) . . ?
243
N11 C110 C6 116.70(12) . . ?
C110 C111 C112 105.3 . . ?
C110 C111 C118 128.58(12) . . ?
C112 C111 C118 126.13(12) . . ?
C113 C112 C117 118.81(10) . . ?
C113 C112 C111 133.8 . . ?
C117 C112 C111 107.37(10) . . ?
C114 C113 C112 119.14(11) . . ?
C113 C114 C115 121.0(2) . . ?
C116 C115 C114 121.3(2) . . ?
C115 C116 C117 117.9(2) . . ?
N11 C117 C116 129.10(19) . . ?
N11 C117 C112 109.09(17) . . ?
C116 C117 C112 121.80(18) . . ?
C121 C120 N12 112.4(2) . . ?
C121 C120 C6 131.2(2) . . ?
N12 C120 C6 116.42(18) . . ?
C120 C121 C122 105.66(19) . . ?
C120 C121 C128 128.4(2) . . ?
C122 C121 C128 125.9(2) . . ?
C123 C122 C127 119.0(2) . . ?
C123 C122 C121 133.9(2) . . ?
C127 C122 C121 107.00(19) . . ?
C124 C123 C122 119.0(2) . . ?
C123 C124 C125 121.2(2) . . ?
C126 C125 C124 121.3(3) . . ?
C125 C126 C127 118.2(2) . . ?
N12 C127 C126 129.6(2) . . ?
N12 C127 C122 109.07(19) . . ?
C126 C127 C122 121.3(2) . . ?
N14 C130 N13 110.37(19) . . ?
N14 C130 C6 128.5(2) . . ?
N13 C130 C6 121.07(18) . . ?
C132 C131 N14 106.95(19) . . ?
C131 C132 N13 108.5(2) . . ?
_diffrn_measured_fraction_theta_max
_diffrn_reflns_theta_full
_diffrn_measured_fraction_theta_full
_refine_diff_density_max
_refine_diff_density_min
_refine_diff_density_rms
0.996
26.00
0.996
1.133
-0.920
0.069
244
CIF File For [(tris(pyrrolyl-α-methyl)amine)Al(HNMe2)]
_audit_creation_method
_chemical_name_systematic
;
?
;
_chemical_name_common
_chemical_melting_point
_chemical_formula_moiety
_chemical_formula_sum
SHELXL-97
?
?
'C23 H29 Al N5'
'C23 H29 Al N5'
_chemical_formula_weight
402.49
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Al' 'Al' 0.0645 0.0514
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
_symmetry_space_group_name_H-M
monoclinic
P2(1)/n
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'
_cell_length_a
_cell_length_b
_cell_length_c
_cell_angle_alpha
_cell_angle_beta
_cell_angle_gamma
_cell_volume
_cell_formula_units_Z
_cell_measurement_temperature
_cell_measurement_reflns_used
_cell_measurement_theta_min
_cell_measurement_theta_max
_exptl_crystal_description
_exptl_crystal_colour
_exptl_crystal_size_max
_exptl_crystal_size_mid
12.3285(6)
10.4147(5)
17.4485(8)
90.00
97.7140(10)
90.00
2220.07(18)
4
-133
?
1.91
26.00
Rectangle
Colorless
.45
.40
245
_exptl_crystal_size_min
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn
_exptl_crystal_density_method
_exptl_crystal_F_000
_exptl_absorpt_coefficient_mu
_exptl_absorpt_correction_type
_exptl_absorpt_correction_T_min
_exptl_absorpt_correction_T_max
_exptl_absorpt_process_details
.40
1.204
'not measured'
860
0.110
multi-scan
0.892
1.000
'sadabs (Sheldrick, 1997)
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
_diffrn_radiation_wavelength
_diffrn_radiation_type
_diffrn_radiation_source
_diffrn_radiation_monochromator
_diffrn_measurement_device_type
_diffrn_measurement_method
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
?
_diffrn_reflns_number
_diffrn_reflns_av_R_equivalents
_diffrn_reflns_av_sigmaI/netI
_diffrn_reflns_limit_h_min
_diffrn_reflns_limit_h_max
_diffrn_reflns_limit_k_min
_diffrn_reflns_limit_k_max
_diffrn_reflns_limit_l_min
_diffrn_reflns_limit_l_max
_diffrn_reflns_theta_min
_diffrn_reflns_theta_max
_reflns_number_total
_reflns_number_gt
_reflns_threshold_expression
–133
0.71073
MoK\a
'fine-focus sealed tube'
'graphite'
'Bruker platform with 4k CCD'
'omega scans'
_computing_data_collection
_computing_cell_refinement
_computing_data_reduction
_computing_structure_solution
_computing_structure_refinement
_computing_molecular_graphics ?
_computing_publication_material ?
'Smart 5.630 '
'Saintplus 5.45 '
'Saintplus 5.45'
'SHELXS-97 (Sheldrick, 1990)'
'SHELXL-97 (Sheldrick, 1997)'
14974
0.0168
0.0172
-11
15
-12
12
-21
21
1.91
26.00
4355
4093
>2sigma(I)
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
246
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0674P)^2^+0.5590P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary
difmap
_atom_sites_solution_hydrogens
geom
_refine_ls_hydrogen_treatment
mixed
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
4355
_refine_ls_number_parameters
391
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.0375
_refine_ls_R_factor_gt
0.0353
_refine_ls_wR_factor_ref
0.1083
_refine_ls_wR_factor_gt
0.1056
_refine_ls_goodness_of_fit_ref
1.096
_refine_ls_restrained_S_all
1.096
_refine_ls_shift/su_max
0.014
_refine_ls_shift/su_mean
0.001
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Al1 Al 0.91964(3) 0.07290(3) 0.236341(19) 0.01939(12) Uani 1 1 d . . .
N4 N 0.98569(8) -0.09025(10) 0.23241(6) 0.0221(2) Uani 1 1 d . . .
N5 N 0.82485(9) 0.03129(11) 0.31972(6) 0.0251(2) Uani 1 1 d . . .
N1 N 1.02936(8) 0.12132(10) 0.15795(6) 0.0228(2) Uani 1 1 d . . .
C10 C 1.08280(10) 0.25921(12) 0.26619(7) 0.0242(3) Uani 1 1 d . . .
N3 N 0.81264(9) 0.11547(10) 0.15272(6) 0.0234(2) Uani 1 1 d . . .
N2 N 0.98753(9) 0.21467(10) 0.29059(6) 0.0229(2) Uani 1 1 d . . .
C1 C 1.12584(10) 0.18189(12) 0.20479(8) 0.0259(3) Uani 1 1 d . . .
C3 C 1.05867(11) 0.00080(12) 0.12029(8) 0.0264(3) Uani 1 1 d . . .
C13 C 0.96367(11) 0.29948(12) 0.34680(7) 0.0256(3) Uani 1 1 d . . .
C30 C 1.05690(10) -0.10473(12) 0.17789(7) 0.0231(3) Uani 1 1 d . . .
C33 C 0.98874(11) -0.20595(12) 0.27157(8) 0.0257(3) Uani 1 1 d . . .
C31 C 1.10380(11) -0.22443(13) 0.18335(8) 0.0279(3) Uani 1 1 d . . .
247
C2 C 0.96974(11) 0.21253(13) 0.10164(8) 0.0281(3) Uani 1 1 d . . .
C12 C 1.04121(11) 0.39400(13) 0.35750(8) 0.0289(3) Uani 1 1 d . . .
C20 C 0.85200(11) 0.17399(12) 0.09034(7) 0.0266(3) Uani 1 1 d . . .
C11 C 1.11807(11) 0.36847(13) 0.30572(8) 0.0281(3) Uani 1 1 d . . .
C23 C 0.70146(11) 0.09937(13) 0.13090(8) 0.0276(3) Uani 1 1 d . . .
C32 C 1.05951(11) -0.28898(13) 0.24345(8) 0.0295(3) Uani 1 1 d . . .
C21 C 0.76784(13) 0.19264(14) 0.03146(8) 0.0339(3) Uani 1 1 d . . .
C22 C 0.67190(12) 0.14590(14) 0.05763(8) 0.0341(3) Uani 1 1 d . . .
C40 C 0.23396(11) 0.40146(13) 0.05801(8) 0.0289(3) Uani 1 1 d . . .
C45 C 0.27932(13) 0.28211(14) 0.04582(9) 0.0354(3) Uani 1 1 d . . .
C46 C 0.27252(14) 0.47912(16) 0.12908(9) 0.0376(3) Uani 1 1 d . . .
C41 C 0.15094(12) 0.44795(16) 0.00298(9) 0.0365(3) Uani 1 1 d . . .
C43 C 0.16068(15) 0.2611(2) -0.07498(10) 0.0497(5) Uani 1 1 d . . .
C44 C 0.24255(16) 0.21164(17) -0.02073(11) 0.0468(4) Uani 1 1 d . . .
C42 C 0.11503(14) 0.37888(19) -0.06310(9) 0.0456(4) Uani 1 1 d . . .
C4 C 0.74172(13) -0.07266(15) 0.30128(10) 0.0346(3) Uani 1 1 d . . .
C5 C 0.89043(13) 0.00594(14) 0.39688(8) 0.0314(3) Uani 1 1 d . . .
H2A H 0.9779(14) 0.2963(17) 0.1256(10) 0.035(4) Uiso 1 1 d . . .
H13 H 0.9002(14) 0.2873(15) 0.3708(9) 0.030(4) Uiso 1 1 d . . .
H2B H 1.0006(14) 0.2126(16) 0.0533(10) 0.034(4) Uiso 1 1 d . . .
H23 H 0.6557(13) 0.0586(15) 0.1659(9) 0.030(4) Uiso 1 1 d . . .
H3A H 1.0018(13) -0.0147(15) 0.0753(9) 0.029(4) Uiso 1 1 d . . .
H12 H 1.0401(14) 0.4608(17) 0.3934(10) 0.036(4) Uiso 1 1 d . . .
H1B H 1.1745(13) 0.1134(16) 0.2279(9) 0.032(4) Uiso 1 1 d . . .
H5D H 0.7875(13) 0.1006(17) 0.3242(9) 0.028(4) Uiso 1 1 d . . .
H1A H 1.1687(13) 0.2337(15) 0.1731(9) 0.026(4) Uiso 1 1 d . . .
H11 H 1.1839(14) 0.4160(15) 0.2977(9) 0.030(4) Uiso 1 1 d . . .
H3B H 1.1318(13) 0.0108(15) 0.1010(9) 0.028(4) Uiso 1 1 d . . .
H32 H 1.0749(14) -0.3713(19) 0.2618(10) 0.042(5) Uiso 1 1 d . . .
H31 H 1.1545(14) -0.2553(17) 0.1529(10) 0.034(4) Uiso 1 1 d . . .
H33 H 0.9462(14) -0.2188(16) 0.3134(10) 0.034(4) Uiso 1 1 d . . .
H22 H 0.6028(17) 0.1432(19) 0.0287(11) 0.051(5) Uiso 1 1 d . . .
H21 H 0.7746(17) 0.228(2) -0.0185(12) 0.055(5) Uiso 1 1 d . . .
H45 H 0.3347(15) 0.2497(17) 0.0823(10) 0.037(4) Uiso 1 1 d . . .
H41 H 0.1160(16) 0.534(2) 0.0094(11) 0.052(5) Uiso 1 1 d . . .
H46A H 0.3213(16) 0.4274(19) 0.1680(11) 0.049(5) Uiso 1 1 d . . .
H42 H 0.0572(17) 0.409(2) -0.1019(12) 0.055(6) Uiso 1 1 d . . .
H5C H 0.9416(19) 0.076(2) 0.4136(13) 0.065(6) Uiso 1 1 d . . .
H46B H 0.3131(19) 0.556(2) 0.1172(12) 0.062(6) Uiso 1 1 d . . .
H44 H 0.2749(17) 0.135(2) -0.0253(12) 0.052(5) Uiso 1 1 d . . .
H4C H 0.677(2) -0.042(3) 0.2734(16) 0.088(8) Uiso 1 1 d . . .
H46C H 0.2085(19) 0.511(2) 0.1537(13) 0.066(6) Uiso 1 1 d . . .
H5A H 0.9319(17) -0.074(2) 0.3950(12) 0.058(6) Uiso 1 1 d . . .
H5B H 0.8440(18) 0.007(2) 0.4326(13) 0.064(6) Uiso 1 1 d . . .
H43 H 0.1334(18) 0.214(2) -0.1220(13) 0.062(6) Uiso 1 1 d . . .
H4A H 0.766(2) -0.135(3) 0.2706(17) 0.098(9) Uiso 1 1 d . . .
H4B H 0.723(2) -0.104(3) 0.3432(17) 0.094(9) Uiso 1 1 d . . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
248
Al1 0.0204(2) 0.0187(2) 0.0201(2) 0.00108(12) 0.00623(14) 0.00027(13)
N4 0.0227(5) 0.0205(5) 0.0238(5) 0.0013(4) 0.0061(4) -0.0006(4)
N5 0.0264(5) 0.0232(5) 0.0275(6) 0.0000(4) 0.0103(4) -0.0004(5)
N1 0.0251(5) 0.0209(5) 0.0239(5) 0.0026(4) 0.0088(4) 0.0015(4)
C10 0.0220(6) 0.0212(6) 0.0298(6) 0.0048(5) 0.0055(5) 0.0005(5)
N3 0.0241(5) 0.0230(5) 0.0237(5) 0.0003(4) 0.0052(4) 0.0023(4)
N2 0.0233(5) 0.0221(5) 0.0243(5) 0.0004(4) 0.0068(4) -0.0016(4)
C1 0.0229(6) 0.0229(6) 0.0336(7) 0.0036(5) 0.0100(5) -0.0010(5)
C3 0.0302(7) 0.0249(6) 0.0264(6) 0.0000(5) 0.0123(5) 0.0027(5)
C13 0.0271(6) 0.0259(6) 0.0244(6) -0.0012(5) 0.0055(5) 0.0003(5)
C30 0.0215(6) 0.0230(6) 0.0256(6) -0.0016(5) 0.0061(5) -0.0003(5)
C33 0.0284(6) 0.0215(6) 0.0277(6) 0.0035(5) 0.0053(5) -0.0021(5)
C31 0.0256(6) 0.0243(6) 0.0347(7) -0.0033(5) 0.0073(5) 0.0028(5)
C2 0.0342(7) 0.0263(7) 0.0256(6) 0.0075(5) 0.0109(5) 0.0038(5)
C12 0.0316(7) 0.0241(6) 0.0299(7) -0.0029(5) 0.0001(5) 0.0005(5)
C20 0.0340(7) 0.0236(6) 0.0232(6) 0.0021(5) 0.0072(5) 0.0057(5)
C11 0.0245(6) 0.0233(6) 0.0362(7) 0.0027(5) 0.0026(5) -0.0021(5)
C23 0.0252(6) 0.0250(6) 0.0321(7) -0.0046(5) 0.0028(5) 0.0015(5)
C32 0.0323(7) 0.0201(6) 0.0358(7) 0.0024(5) 0.0032(6) 0.0013(5)
C21 0.0445(8) 0.0327(7) 0.0237(6) 0.0008(5) 0.0021(6) 0.0081(6)
C22 0.0331(7) 0.0337(7) 0.0329(7) -0.0053(6) -0.0051(6) 0.0060(6)
C40 0.0326(7) 0.0294(7) 0.0262(6) -0.0002(5) 0.0092(5) -0.0053(5)
C45 0.0415(8) 0.0329(7) 0.0349(7) 0.0002(6) 0.0162(7) -0.0015(6)
C46 0.0434(8) 0.0347(8) 0.0341(8) -0.0062(6) 0.0024(7) 0.0010(7)
C41 0.0322(7) 0.0405(8) 0.0370(8) 0.0039(6) 0.0055(6) -0.0086(6)
C43 0.0505(10) 0.0669(12) 0.0342(8) -0.0146(8) 0.0145(7) -0.0301(9)
C44 0.0592(11) 0.0357(8) 0.0528(10) -0.0132(7) 0.0339(9) -0.0123(8)
C42 0.0381(8) 0.0640(11) 0.0343(8) -0.0005(8) 0.0030(7) -0.0187(8)
C4 0.0310(8) 0.0348(8) 0.0394(8) 0.0035(6) 0.0102(6) -0.0099(6)
C5 0.0407(8) 0.0313(7) 0.0241(6) 0.0017(5) 0.0111(6) -0.0035(6)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Al1 N3 1.8838(11) . ?
Al1 N2 1.8878(11) . ?
Al1 N4 1.8894(11) . ?
Al1 N5 2.0314(11) . ?
Al1 N1 2.1099(10) . ?
N4 C33 1.3833(16) . ?
N4 C30 1.3866(16) . ?
N5 C4 1.4958(18) . ?
N5 C5 1.4978(18) . ?
249
N1 C3 1.4839(16) . ?
N1 C2 1.4880(16) . ?
N1 C1 1.4898(17) . ?
C10 C11 1.3708(19) . ?
C10 N2 1.3821(16) . ?
C10 C1 1.4934(18) . ?
N3 C23 1.3826(17) . ?
N3 C20 1.3905(16) . ?
N2 C13 1.3807(16) . ?
C3 C30 1.4915(17) . ?
C13 C12 1.3674(19) . ?
C30 C31 1.3721(18) . ?
C33 C32 1.3655(19) . ?
C31 C32 1.4154(19) . ?
C2 C20 1.4934(19) . ?
C12 C11 1.419(2) . ?
C20 C21 1.372(2) . ?
C23 C22 1.370(2) . ?
C21 C22 1.410(2) . ?
C40 C45 1.391(2) . ?
C40 C41 1.393(2) . ?
C40 C46 1.5031(19) . ?
C45 C44 1.397(2) . ?
C41 C42 1.381(2) . ?
C43 C42 1.377(3) . ?
C43 C44 1.387(3) . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N3 Al1 N2 114.93(5) . . ?
N3 Al1 N4 116.36(5) . . ?
N2 Al1 N4 123.87(5) . . ?
N3 Al1 N5 101.22(5) . . ?
N2 Al1 N5 93.83(5) . . ?
N4 Al1 N5 97.25(5) . . ?
N3 Al1 N1 83.39(4) . . ?
N2 Al1 N1 81.86(4) . . ?
N4 Al1 N1 82.79(4) . . ?
N5 Al1 N1 174.74(5) . . ?
C33 N4 C30 105.45(10) . . ?
C33 N4 Al1 138.48(9) . . ?
C30 N4 Al1 116.00(8) . . ?
C4 N5 C5 109.72(11) . . ?
C4 N5 Al1 116.34(9) . . ?
C5 N5 Al1 112.85(8) . . ?
C3 N1 C2 112.06(10) . . ?
C3 N1 C1 112.16(10) . . ?
C2 N1 C1 112.28(10) . . ?
C3 N1 Al1 107.48(7) . . ?
C2 N1 Al1 106.13(8) . . ?
250
C1 N1 Al1 106.24(7) . . ?
C11 C10 N2 110.41(11) . . ?
C11 C10 C1 133.58(12) . . ?
N2 C10 C1 116.01(11) . . ?
C23 N3 C20 105.95(11) . . ?
C23 N3 Al1 138.59(9) . . ?
C20 N3 Al1 115.32(9) . . ?
C10 N2 C13 105.97(10) . . ?
C10 N2 Al1 116.49(8) . . ?
C13 N2 Al1 137.23(9) . . ?
N1 C1 C10 106.71(10) . . ?
N1 C3 C30 107.37(10) . . ?
C12 C13 N2 110.23(12) . . ?
C31 C30 N4 110.54(11) . . ?
C31 C30 C3 132.24(12) . . ?
N4 C30 C3 116.75(10) . . ?
C32 C33 N4 110.51(11) . . ?
C30 C31 C32 106.39(11) . . ?
N1 C2 C20 107.51(10) . . ?
C13 C12 C11 107.00(12) . . ?
C21 C20 N3 109.87(12) . . ?
C21 C20 C2 133.20(12) . . ?
N3 C20 C2 116.72(11) . . ?
C10 C11 C12 106.38(11) . . ?
C22 C23 N3 110.11(13) . . ?
C33 C32 C31 107.10(12) . . ?
C20 C21 C22 106.94(12) . . ?
C23 C22 C21 107.13(13) . . ?
C45 C40 C41 118.58(14) . . ?
C45 C40 C46 121.19(14) . . ?
C41 C40 C46 120.22(14) . . ?
C40 C45 C44 120.29(16) . . ?
C42 C41 C40 121.21(16) . . ?
C42 C43 C44 120.18(15) . . ?
C43 C44 C45 119.84(16) . . ?
C43 C42 C41 119.88(17) . . ?
_diffrn_measured_fraction_theta_max
_diffrn_reflns_theta_full
_diffrn_measured_fraction_theta_full
_refine_diff_density_max
_refine_diff_density_min
_refine_diff_density_rms
1.000
26.00
1.000
0.283
-0.256
0.048
251