Structure and bonding of transition metal complexes
by Donald Leslie Ward
A thesis submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree of
DOCTOR OF PHILOSOPHY in Chemistry
Montana State University
© Copyright by Donald Leslie Ward (1972)
Abstract:
The crystal and molecular structures of two transition metal complexes were solved by the X-ray
diffraction method; a comparison of the. first structure with an independent, duplicate determination of
the structure has yielded information about the precision of the X-ray method and a. study of the
second structure has yielded information about the relationship between the geometry of the molecule
in the crystal and the geometry when free of the intermolecular forces in the crystal.
Ethylenebisbiguanidenickel(II) chloride monohydrate crystallizes in space group P21/c with a =
6.905(5)A, b = 11.680(4)A, c = 18.038(22)A, β = 101,41(10)°, and Z =4. The nickel(II) ion is in
square-planar configuration and the complex ion is essentially planar except for the ethylene bridge.
Extensive hydrogen bpnding, involving the water of hydration and the two chloride ions, joins the
complex ions into infinite sheets parallel to the (100) plane with additional hydrogen bonds acting
between the sheets. The final R is 3,1% for 1714 observed intensities.
The comparison of the atomic parameters and standard deviations of the two independent
determinations of the structure has indicated general good agreement between the. two determinations.
However, the comparison also indicates that there are significant differences between certain classes of
parameters and that the estimated standard deviations of the two determinations have been
underestimated, on the average, by a factor of about 1.7,
Dicarbonylnitrosyltriphenylphosphlnecobalt(0) crystallizes in space group Pl with a = 11.055(2)A, b =
11.024(4)A, c = 10.260(2)A, α 121.07(2)°, β= 101.01(2)°, γ=105.14(2)°, and Z = 2. The cobalt and
phosphorus atoms are in approximately tetrahedral configurations and the nitrosyl and carbonyl groups
are disordered. There is no indication of hydrogen bonding. The final R is 3.2% for 2006 observed
intensities.
Non-bonded repulsion energies were calculated for the molecule with respect to rotation about the
Co-P bond and about the three P-C (phenyl) bonds for the molecule in the crystal and for the free
molecule. It was found that the configuration in the crystal minimizes the energy in the crystal but that
the free molecule rotates approximately 20° about the Co-P bond to minimize the. energy. STRUCTURE AND BONDING QF
TRANSITION METAL COMPLEXES .
by
DONALD LESLIE WARD
A thesis submitted to the Graduate Faculty in partial
fulfillment of the requirements fpr. the degree
of
DOCTOR OF PHILOSOPHY '
in
Chemistry
Approved:
Head, Major Department,
Chairman, Examining Committee
Graduate tfDean
MONTANA STATE UNIVERSITY
Bozeman, Montana
June, 1972
iii
ACKNOWLEDGMENT
I wish to thank Dr. Charles N. Caughlan for his advice
and guidance and other members of the faculty of Montana
State University for their help,
I wish to acknowledge the National Aeronautics and
Space Administration and the Petroleum Research Fund of
the American Chemical Society for fellowships while
working on the research.
Also I wish to thank the
Computing Center of Montana State University for grants
of computing time.
Finally, I wish to thank my wife, Joan, for her
patience, understanding and support while this research
was being completed.
TABLE OF CONTENTS
'Page
LIST OF TABLES
. . . . . . . . „ „ ..
LIST OF FIGURES
. . , .................. .. '. ., . ... ... v iii
ABSTRACT
. .... vi
. . . ... . . . . . . . ... . . . . . . . .
INTRODUCTION
. . ix
. . . . . . . . . . . . . . . . . . . .
PART I
/'
f .
Ethylenebisbiguanidenickel(II) chloride- monohydrate'
INTRODUCTION
. ■.........................3
I. The Crystal and Molecular Structure
Preparation of the crystals
.
6
. .
6
. . .........
................ ..
Density d e t e r m i n a t i o n ...................' . . . . .
6
Determination of space group and cell parameters .
7
Collection of the data . . . . . ' ................. 7
Determination of the structure 6 . , ...............10
The structure
.............
. . . . . . . . . . .
11
Hydrogen bonding ............................. ' . . . 18
Bonding within the complex
ion .'.
.
II. The Comparison of the Two Determinations
Experimental d i f f e r e n c e s ...............
... . , '.
26
... . .. . 28,
. . . . .
28
Refinement differences . . . . . . . . . . . . . .
28
Comparison of parameter differences.
. . . . . . .
29
The CHI-square t e s t ..............
. •. . . . . .
30
The half-normal probability plot analysis'
SUMMARY AND CONCLUSIONS
. . . .
. . ..
.■ .
...
. 32
. .' . ..
. 40
V
PART II
Dicarbony lhitrosyltripheny Iph.osphinecobalt (O)
INTRODUCTION
........................
I. The Crystal and Molecular Structure
Preparation of the crystals
Density determination
. . . . . . . . . .
43
. '.......... „ . ' 45
45
. . . . . . . . . . .
...............
45
. . . . . .
Determination of space group and cell parameters .
46
Collection of the d a t a ............... ..
46
Determination of the structure ...................
4$
The s t r u c t u r e ........... ................... ..
58
Bonding to the cobalt(O) a t o m ................... 62
II. The Study of the Angular C o n f i g u r a t i o n ........... 69
Introduction . . . . . . .
The molecule in the crystal
The free molecule
...............
^
P . . . .
SUMMARY AND CONCLUSIONS
APPENDIX I .
69
. . . . . . . . . . .
. . . . . . . . . .
59
.
71
.
76
Normal Probability Plot Analysis . . . . .
79
APPENDIX II. Determining the External Geometry and
Dimensions of a Single Crystal .................... gg
LITERATURE CITED
. . . . . . . .
.............
. . . .
87
vi
LIST OF TABLES
PART I
Page
Ethylenebisbiguanidenickel(II) chloride monohydrate
TABLE I
Crystal Data
TABLE 2
Observed and Calculated Structure Factors .
TABLE 3
Positional Parameters of Non -hydrogen Atoms ♦ ' 14
TABLE 4
Thermal Parameters of Non-hydrogen Atoms
TABLE 5
Hydrogen Atom Parameters
TABLE 6 .
Least-squares Planes
TABLE 7
Bond Distances
. . . . . .
•
O
O
O
0
0
O
.
TABLE S
Bond Angles . . . . . . . .
0
0
e
0
e
0
0
. .i. 20
TABLE 9
Hydrogen Bonding
.
.
.
•
.
.
.
*
TABLE 10
CHI-square Test . . . . . .
31
TABLE 11
6P^ for Nickel and .Chlorine Bin'S-
34
. . . . . . .
•
O
O
•
...
e
.
. . . . .
•
.
•
.
12
. .
0
S
15
. . ■ 16
. •■ 17
.
.
19
22
PART II
Dicarbonylnitrosyltriphenylphosphinecobait(O)
TABLE 12
Crystal Data . . . . . . . . . . . . . . . . .
47
TABLE 13
Observed and Calculated Structure Factors . .
51
TABLE 14
Positional Parameters of Non-hydrogen Atoms .
55
TABLE 15 __ Thermal Parameters of Non-hydrogen Atoms'
TABLE 16
Hydrogen Atom Parameters
TABLE 17
Least-squares Planes
TABLE IS
Bond Distances
. . . . .
.
56
........
.57
.. .....................
61
. . .... .......
63
vii
TABLE 19
Bond A n g l e s ............. .......... .......... 64
TABLE 20
Comparison of Nitrosyl and Carbonyl
Bond Distances
TABLE 21
. . . 0
. . . . . . . . . . 6 6
Non-bonded Repulsion Energies . . .
... . . . 74
viii
LIST OF FIGURES
PART I
Page
Ethylenebisbiguanidenickel(II )chloride monohydrate
FIGURE I
Bond Distances and A n g l e s .................... .21
FIGURE 2
Crystal Structure Projected
onto (100) Plane
24
FIGURE 3
Crystal Structure Projected
onto (010) Plane
25
FIGURE 4
Half-normal Probability Plot for
Parameters . . . .
FIGURE 5
o
e
e
e
o
e
all
e
e
e
t
o
o
Half-normal Probability Plot for Nickel and
Chlorine Pi j ts ............................
FIGURE 6
35
Half-normal Probability Plot for Nickel and
36
Chlorine P n ' s .............
FIGURE 7
33
Half-normal Probability Plot for Nickel and
■Chlorine Pij’s (i^j)
. . . * . * * . * * .
37
PART II
Dicarbonylnitrosyltriphenylphosphinecobalt(O)
FIGURE 8
Molecular Structure
. . * ......... *
. «
65
FIGURE 9
Stereographia Packing Diagram
FIGURE 10
Non-bonded Repulsion Energies as a Function
of Rotation about the Co^P Bond
59
» » * * *
72
APPENDIX II
FIGURE Il
Graphical Illustration of View Through the
Alignment Microscope of the Diffractometer
84
ABSTRACT
The crystal and molecular structures of two transition
metal complexes were solved by the X-ray diffraction method;
a comparison of the. first structure.with-an independent, ■
duplicate determination of the structure has yielded •
information about the precision of the X-ray method and a.
study of the second structure has yielded information about
the relationship between the geometry of the molecule in the
crystal and the geometry when free of the inbermpiecuiar■■
forces in the crystal.
Ethylenebisbiguanidenickel( II) chloride monohydrate
crystallizes in space group PZ^/c with a = 6.905(5)A,
b = 11.6S0(4)A, c = 18.038(22)A, P= 101,41(10)9, and Z = 4 .
The nickel(II) ion is in square-planar configuration and
the complex ipn is essentially planar except, for the
ethylene bridge.
Extensive hydrogen bonding, involving
the water of hydration and the two chloride ions, joins the
complex ions into infinite sheets parallel to. the (100 ) ■
plane with additional hydrogen bonds acting between the
sheets.
The final R is 3.1% for 1714 observed.intensities.
The comparison of the atomic parameters and standard
deviations of the two independent determinations of the '
structure has indicated general good agreemeht between t h e .
two determinations.
However, the comparison also indicates
that there are significant differences between certain
classes of parameters and that the estimated'standard
deviations of the two determinations have been under­
estimated, on the average, by a factor of about 1 .7 .
Dicarbonylnitrosyltriphenylphosphlnecobalt(O)
crystallizes in space group Pl with a = 11.055(-2)A,
b = 11.024(4)A, c = 10.260(2)A,
a- 1 2 1 .0 7 (2 )0 ,
P = 101.01(2)°, Y = 105.14(2)°, and Z = 2.
The cobalt and
phosphorus atoms are in approximately tetrahedral
configurations and the nitrosyl and carbonyl groups are
disordered.
There is no indication;of hydrogen bonding. ■
The final R is 3.2% for 200.6 observed intensities.
Non-bonded repulsion energies were calculated for the
molecule with respect to rotation about t h e .Go-P bond and
about the three P-C (phenyl) bonds for the molecule in the
crystal and for the free molecule.
If was found that the
configuration in the crystal minimizes the energy in the.
crystal but that the free molecule rotates, approximately
20° about the Co-P bond, to minimize the. energy.
INTRODUCTION
This dissertation is divided into two parts,'egch.
presenting a different crystal structure which makes
significant contributions to the literature.
The first,
that of ethylenebisbiguanidenickel(II) chloride monohydrate
(3 1 ), represents a duplicate, independent, accurate,
diffractometer, X-ray determination of the structure.Significant information concerning the precision of the
X-ray method has been learned from a comparison of t h e '
two determinations of the structure of this compound.
The second, that of dicarbonylnitrosyltriphenylphosphinecobalt(O)
(3 3 ), was investigated to assist in
understanding its role in the catalysis of the dimerization
of norbornadiene (bicyclo [-2 •2 «l] hepta- 2 ,5-diene) (21 ).
A study of the structure has yielded information concerning
the relationship between the geometry of the molecule in
the crystal and the geometry of the molecule when free of.
the intermolecular forces in the crystal.
PART I
Ethylenebisbiguanidenickel(II) chloride monohydrate
INTRODUCTION
The original purpose of this study -was the
determination of the structure of ethylenebisbiguanidenickel(II)chloride monohydrate and the study of the nature
of the tetradentate ligand along with its effect on the
nickel coordination.
When the structure determination,
was completed, prepublication notice was received from
Professor Richard Marsh of the California Institute of
Technology indicating an independent determination of ,the
structure there (l8 ).
The consideration of the precision
of the two determinations, the different methods of data
collection and solution of the structure suggested that
these duplicate structure determinations present an ideal
case to study the accuracy and precision of X-ray crystal
structure determinations.
Such a study is presented along
with the structural details of the crystal.
The precision of an experimentally-determined
parameter is indicated by the estimated standard deviation.
The estimated standard deviations for the atomic parameters,
determined in X-ray crystal structure studies have been phe
subject of questions concerning their accuracy.
Several
statistical methods are available for the comparison of
two sets of parameters with respect to their standard
4
deviations.
A simple method is to compare the differences,
between corresponding parameters to the. standard deviations;
this can be done for individual p a r a meters,for groups of
parameters, or for all parameters at once.
The information
obtained from this method would indicate agreement or lack
of agreement between the two sets of parameters with respect
to the standard deviations but does not indicate the
correctness of the estimate of the standard deviations.
Another method is the CHI-square test which has been
applied to the comparison of parameter sets by -HanpLltdn (15).
In this method, parameter differences are weighted by.the
standard deviations and the sum of the squares of tfyese
weighted differences
(for j parameters)
squared with j degrees of freedom.
is tested as CHI-
One may reject the
postulate that the weighted differences are from a normaldistribution with zero mean at'the
level if the tabulated .
value of CHI-squared (j ,a ) is less than the.sum of the
squares of the weighted differences..
One would expect the-
postulate to be true only if there are no systematic errors
in the weighted differences; standard deviations that are
too small may result from systematic errors and would causethe postulate to be rejected.
The CHI-square test can
indicate the presence of differences from the -normal .
5
distribution but can not determine the 'cause of the '
differences.
A new method for the comparison of parameter sets has' / ■
been presented by Abrahams and Keve (2),
This method is
the normal probability plot analysis and has the features of
being able to indicate the correctness of the estimated
standard deviations and to give an average factor by;which ■
to multiply the estimated standard deviations to obtain a
set consistent with the normal distribution.
Weighted
differences are calculated and ordered in order of increasing
magnitude and plotted against the normal distribution for
the. same number of elements.
If the differences themselves
follow a normal distribution, the plot will be linear and
the slope indicates the average factor by which the estimated
standard deviations have been underestimated.
The crystal structure of ethylenebisbiguanidenickel(£1) t
chloride monohydrate is reported in Section I,' a condensed ■
description of the normal probability plot analysis method
is given in Appendix I, and a comparison of the parameter ■
sets of the two duplicate determinations is given i n ■
Section II..
SECTION I
THE CRYSTAL AND MOLECULAR STRUCTURE QF
Et h y l e n e b i s b i g u a n i d e n i c k e l ( H ) c h l o r i d e m o n o h y d r a t e
Preparation of the crystals
Crystals of ethylenebisbiguanidenickel (II)cfrloricie
monohydrate were prepared by Dr. David J. MacDonald .(24)
from nickel(II) chloride hexahydrate, ethyleriedia,mine dl- ■
hydrochloride and cyanoguanidine using a modification pf'
the method reported by Ray (27) fop the preparation of
ethylenebisbiguanidecopper(II)sulfate.
Using R a y ’s method
one obtains the starting materials in a finely divided
condition and mixes them thoroughly; the mixture is melted
with constant stiring, cooled, treated with an aqueous
solution of (NH^gSO^, neutralized with ammonia, filtered,
and washed with cold water.
Dark red-orange crystals ■
are obtained.
■j
Density determination
The presence of one molecule of water- per formula unit
was determined from the weight loss of a finely ground
sample heated to IlO0G for 16 h o u r s ; a loss of 4*$ 6 % was
observed compared to.a theoretical loss of 4.79%.
The
density, measured by flotation in a carbpntetrachloride- '
7
bromoform mixture is 1.740 g. CirT^e
For four molecules in
the unit cell and one molecule of water per formula unit,
the calculated density is 1 .7 5 0 g.cm""^.
.
'
Determination of space group and cell parameters
Preliminary photographic examination of a single
crystal of ethylenebisbiguanidenickel( II) chloride mono-r
hydrate showed the conditions for reflection to be
hOl: I = 2n, and O k O : k = 2n, uniquely determining the
space group P2^/c.
Precise unit cell parameters were
determined by least-squares refinement of the 29 values of
14 general reflections measured on a General Electric XRD-5
diffractometer using a G. E. single crystal orienter and
M o Kq, ( ^=0.71069A) radiation.
in Table I.
The crystal data is listed
It was discovered that a P 2 -jyn cell could be
chosen which would give a P angle nearer to 90 ° than is the
angle for the P2^/c cell.
This cell was not used so that
the results of this structure determination could be easily
compared to those of other determinations '
Collection of the data
The unique intensity data were collected by 9-29 scans
using zirconium-filtered MoK
(X=0.71069A) radiation and a
General Electric XRD-5 diffractometer equipped with a
TABLE
L
Crystal data
Ethylenebisblguanidenlckel(I I )chloride monohydrate
C6N10Hl6NiC 1 2*H2 0
F *w * 375.91
F(OOO) = 776
Monoclinic, space group P2^/c
a =
6.905(5)A
b = 11.6S0(4)
c
1 8 .0 3 8 (2 3 )
3 = 101.41(10)
V = 1426.OA 3
4
Din = 1.740 g.cm ” 3
Dx = 1.750 g.cm " 3
9
scintillation counter, pulse-height discriminator., and a
G. E. single crystal orienter. ' Sixty^second scans
(2 ° in 29) were used with stationary backgrounds measured
for 30 seconds each at the start and fipish of each scan,
The crystal was mounted with the a axis parallel tq the
spindle axis.
A chart recording of diffracted intensity
v s . 29 was monitored during data collection to insure that
the reflections were centered in the scan, range;
•The
intensities of the standard reflections monitored during
data collection showed no systematic variations; there was
no evidence of radiation damage to the crystal.
Of the
2228 unique reflections which were examined out to 48 °
in 29, 1714 had an intensity greater than twice the.
standard deviation of the intensity; the remaining . 314
reflections were coded as "unobserved” and were. not. included
in the refinement.
The dimensions of the crystal were measured using a ,
calibrated "Whipple disc" in the alignment microscope of
the diffractometer (see Appendix II)
well-shaped, bound by the planes
(32),
{1 0 1 },
The crystal was
{001 } , {Oil}, and
{Oil}, and Its dimensions in the directions of a, b , and c*
were approximately .82mm,
.28 mm, and .13 mm, respectively.
The linear absorption coefficient for MoKa radiation Is
10
I S . 21 cm- 1 ; absorption corrections, using the method of
de Meulenaer and Tompa (25) calculated transmission
coefficients
(!/Iq ) ranging from O.S95 to O. 7 6 3 . .
Determination of the structure
The positions of the nickel and one chlorine atom were
determined from an E -map calculated using 230 reflections
whose signs had been determined by the. symbolic addition
procedure.
Several repetitions of Fourier syntheses
yielded the positions of the remaining non-hydrogen atom$.■
Full-matrix least-squares refinement, refining all atoms
anisotropically and using unit weights, reduced R to 5.S%
and R^pd to 8.1% where R and Rwtc^ are defined as
and the function minimized during refinement was
S w( IF0{ - ~
|FC) )2
Absorption corrections were applied reducing R to 4„9% and
^wtd to 6.1%.
The positions of the hydrogen, atoms were,
determined from a difference Fourier.
Block-diagonal
least-squares refinement, refining hydrogen atoms
isotropically and the non-hydrogen atoms anisotropically,
-
11
using the weighting scheme described by Stout and Jensen "
(29), and applying anomalous dispersion corrections (2 0 )
for nickel (AfT = 0 .4 , A f ” = 1 .2 ) and for chlorine
(Af» = 0.1, Afr' = 0.2) , reduced R to 3.12% and Rw td to
4.S7%.
The observed and calculated structure factors are '
listed in Table 2 for the 1714 ”observed" reflections;.
. .
The positional parameters of the non-hydrogen atoms arelisted in Table 3, the thermal parameters for the non­
hydrogen atoms are listed in Table 4, and the'hydrogen atom
parameters are listed in Table $.
The structure
All atoms lie in general positions.
The nickel atoms
are in square planar configuration and lie nearly; along the
lines x, 0 ,0 and x ,i ,i with distances of 3.621(1)
and .
3 .5 49 (1 )A between the nickel atoms on each of these lines,
The tetradentate ethylenebisbiguanide ligand is
essentially planar around the nickel.
Ieast^sqpares
planes were calculated using several sets of atoms within
the complex ion and using unit weights for each atom; the
equations for these planes are given in Table 6 . .. .The
nickel and the four coordinating nitrogens lie very close
to the pla n e ; the deviation for the nickel i s ..0013 A and.,
the deviations for the nitrogens are -.OOOlA for N(I) and "-
12
TABLE 2
Observed and calculated structure factors.
ZSRSiSK -S=SS-RZSRSSRi -SS-S-IS=S'- -SSSSSS- -SZ===- = - -S--S = S - - S = =
ZZiSSSS -S=SS-S=SSSSSi -ES-S-ZS=S- -EZSSSS- ;£S=Z=Z=- -E--Z -E-S-ZSS
-T=SSZS . - Y E Z - T t Z = SS ;--7“T:-SZS ! = T i - T = ]-"T':S?Z % - Y E % - V r S Z
-EZZySiSSRRS-SRSSZ -ESZS?=SSS--ZRKSSS -EZ=ZSZ-ZKZZ ZE-ZSRZ- -E=ZZ=SZ:
-ESZZTZSSSRS-SSSKS »E=SirSSSS-Z-SSZSS »£S=SSS*SSS2 -E-ZSSS- ^ESiSSTS:
.-,''T-T-T-T-TV-TZSS .-•==-•;* T-T-T-TT Z=S ^jo-T-T-ITTZ Jjo-TTTT .j =~t * t S=SS=SS-SS-SRZSSSi- -EZKRSiiZSRRS-SSRRKi= "ER-SSS-SiSSZSSKiSKR-R
E1
gRSSSSS-iS'SSZSSSi- JiEiERKiiZEKSS-SSERiRS JERZSKi-ZSSREZiRRESRR-K
S’
T-T-T-TT-TZS==SSSSZ .JO-T"T*I — T=-TSS=SSZ jJOT~T"T*TT-T-T-T'TSSSi
-S--I-RiSK=-KiSSS=-=-Z -K=K-ZSESZSZEEEEK-SiZK “E*ZRKS-=SgSR--SZSi
E:
-K--Z-RZZR=-EiERZZZZ-Z ;EiR-ZSK=Z=SRSKEK*S'iS Ji-Z=RS-ZigZS--SSS=
El
o j TT-T-TT-TT-TS==SS=ZS
.j T=T-T-tT*T-T*TSS==SZ ;JOT“T"TI— T--TTSS=
TTT-=RT=S-SKSr =ESRTg-STS-ZiSSiK-=SESRRigKSZZ "E-Ri'SZgZS-Si?=-=--==
SIT-SRTS=-ZKZK J e -RTS-ITT-ZSRSiK-SRSSgRiRRZ=- Je -SS'SSRZS-RSTS-SS-ZK'
* TT-T-TT-TTTTT ;J°T=T"T-I=T-T-T-TZg=SSS= ZSZS .jojT= T-T-I-T-T-TZZ=='
TE-RTRKSSR - E-S-ZiTZSgRS=KT-SZ-iESSS -KiKTKZR=RT = -KSSSS=E = S ZKiiKEiE
TRZgTKKSSR JE-R-SES-STRSiKg-SZ-RKKiS JgEKIK=S=RV=-K=SSgSSS= JESiKRiK
-TTZZSSSSZ . J-T~T"T-T”T*r-TTTSZ==S=S .jjT ”T" IT-T-T-TSS=SSZ
R - -?Sg-iKgRK-STgiSSi ZR *ERZKR-R-'0RRZIER-JS-=KREK=TRKg 'EKSiT=SKRi Sg
Z-Kg=EgiKSRK-KTKZSSiSg JEKZKE-K--TEgSTZTKTS-=KRSKZTgRS JERSSTS=RKRiI
I' -T-T-T-SZ=SS=iSZZiSS .j o j T=TT'I-TT-T-T= TZZ = =SSSZZtSS .J» JT~~»'; * j*«
K-EKTSRiii=Si-KE=- SKRKKRSTKRKR 0KKSgS=RiiSiZKS -E=ZSTi-TSSRRSTRg-ST
E-iKTSKiiTZSZ-RKS- JEKKEKgTiSKR JER=RiZgRSR=Rg- jE-ZKTE-TiSKKSVRS-gT
.I-T-TTT-TS= .jO--T--I-TT .JO'--TSZSZiZSg .Jo-yo?mo.
T E - K E-K-KZZ-SRTKKiKSZS -K-ZS==Sg=SSSRgSSKSgiSS-EKZi -K- = SKTKK-SSZR
ZKZ-K-RTZ-ZIS-SREKEZR=-Z =E--S==Zi-=ZRERSSSSgZ=Z-KgS= iE*=SRTgR'"=Kg
-T-T'I-T-— T ============ Jjo-T-T-'-T-T-T-TSZ==S==IISI .J“-T~T"T'IT-T
ZgR-RERgZRZSggSE-Z=SR ”E -Rg-EZSgiiSTI=SKSSSiSS-RRZg'SRZSS 'KiRZSSZSERK-ERgKZZi-SZ=K-ZSZK Jg'Eg-SZiEiZSTT-SSSZSgRI-Rg=R-=SSSR JEEKZB=Z=S
-TT-TSZ=S=:=ZZZZiiSSg Jjo-TT-T-I-TT-T-T-TS==SS==SSZSiiSSg
RE— Z— ESSSSESSg =K-=R-:E::-"=Z32ZKS SKSS--KSS=--:- =E-=-= 0EETi=ES
S E - =— EK=SiESZg J e -SK'SKSS— S-SBiKI JEZ!-— R=IZ--S- Jg-=ZS JEERRZSB
-T-T--T-T-ZZ==S= J j j T-T'.'-TTT-T-TZZ= .j j T ~”T o t »«- t TT J j j T0 I .j o ~~' i «
ZR S=SSEiSR -KKZZRSZTKSi-KgZSSRZSVKIK-SZ-SiS -KESggZgggE = TKRZ=KIZ--IZKSISSEISR jEiiSVSSZES=-SgSgSgZ=TRKK--I-SIZ JEZ=RKZSgZK=IRR==ESS--SSSiiS=IISS j j j VT0T 'I-T-T-T-T-TS=S==SiSSZ=II ; j o j V-TT'I-'T*T'TZS==BiS
- E-KZRSS'ISEKKiZ=-Si=TSIE=SKRZS=IS 0EKSgTSSRER-TTZIZTSKiEKTZKKSKK-g
J e -EZRSE-TKKStiZ=-Zg=ISTS=SEEZZi = R JERiETVSgSR'TTRSVIKEESITVERIRt-K
Jjo-V0--IT-T-T-T-Ts==S=Zz=SZZZZSSg .-'0 j V 0T-T-I-T-T-T-T-ZS==S=S=SZ=Z
K-Ri-Eg==S= -E=-ZS-SSSEZZSg=Z= -EEZZS=ESEiSg SK-KSIgZ=-" =KZViKSRZ S
S-KS-EgS==S JE=-SR-SgRgSZZg=Z= J e SKTKSKKRSTS Je ZREIS==-- J e STKRSR= J
ITrTTZ==S=Z JjoTTTITTVTTZ==S=Z T jVVTTTTTT==: !jVITITTT = = J j TTTTTT= T
0ETS=EZKS=E= -KSTE-RSSKISSSSZSS °ES0RSTSB k =-S=RSEESK 0K0SE=RSZEZK-S
JESSgSSSS=E= Je e ZK-SS=SKZS=Z=Z= Je S'ZZTS=Z=' SBiZSSSg JE-KESERZKiE-S
.---- ZS==I8 JjTTTITTVTT=SS=S=S .-'0TTTTTvTT=SSSSSISg °-TT ITTTTSSBI=
13
TABLE 2
Continued
"f'SE-scss-j
"ssisisrs
- e r s '*:- 2- *£ s s -: s *: s * e : ^ e -- S -S s s i s : « e : s s s s s = s - s “ e s s s s s s :
{-"•“ ST-TSS
.--VS-T-VSSSS
.^V-T-TTVTTS . - V T - T T T S T T
TTTSTT
=22::= -e -s :- k :s - s s s s s : - s s s s - s -Essssssssssss-sssss- -e s s r - s -: s s s
=SSSSS ^E-ST-S=S-SRSSS:-SSSS-K -ESTSSSSTSSSKC-SSSSS- ^E=SS-S-=SSS
-TSSS= ;J — V-T-T'-TT-S-T-TSSSS
.--V-T " - T - T - T -TSSSlS
.J=-^-T-TT- S
SESSSS= SRTSSSSSSVSSTKSR -EK- =S=KfRSKSSSS- R- SSSSS ' E = V W K S l S K = R S S
SSKSSSRRKVKSREKKTSSVK== ^EK-SS=KSRSSSSSK2R-SFKS2 %EKVVSZ:1RR:==S
^riS=R
.J°V-T " -TT-T-S- T-T2SSS1=
.J-V-S-T- - T S = S
K — SSSS— SSRS- SER--S-RKTRSS-KlK RE-KRRlKSKS »ESS5K1S = --S "ESSSSS
KS-KSSS--SS=K- fER--R-SKTRSS-KlS f£-KSRSSSSS “E S I SSRKS--S ^ESKSSS
0 T-T--T--S-TTR
.J=-V- TT-T--VSTTS .J=-V- T- TTS
.-1T- TTSSSS=S .--V- T-
=TRSSR -EKSSKSSRRKSRSSSSSSKSVKS-S-SKS: -E- S-KSSK-SSKS==SSS=S r S -E
STKSSR ^EKSR-SSSSRSZSSRR=SKSVKK-S- SKKS ^ e -SSKSKR- =SS=S=- ZlKKSS ^E
RRSSSS
.--V-TT'T-T-T-TT-TSSRRRRSSllSIR
=S-SK-S=R =ERRKK- I-R=RSS RE*
. - - V -- T T - T -T-T--SSRRl=
0ESSK=tSKSSVRKKSS -KSK=RSSSSKfKVRV-S
=S-RS-SSR ^ERRKK-I-R=-R= %E- ^E R SSKKZKRKT=KK== %ESRSERSK=KTK=RV-:
--V-TTT2R
.J=-V-TI-TTTTS .-V .J°-T - T- -TSS=R=== . J°-VT"T*." T = - T - T-
=KSRSSS-KfS-TRKSl=-SS -ETSRKfKS-S=KRK=TKSRRSRK--R -EI==RT=SRT-=KS
=SRSfSS-KVR-TSKSl=-SR ;EVSSSfRS2SSS=SSySSKR-=K-'S “ESISSSRKZT-RST
-T-T- T- T SSRRSS=I=S=R= . - V - T-T *T“T - T-T-T SSRRRSilR
.J=-V-= -T-T - T -T
- R KSSSRVKSI- S- SI “ERKSK- IRS=SKfSKSKSKSSSSS- SR- = K = K -=R= -ES=RSlSS=
SSKRR=RRKKS- S -KV ^ERKZKSTfS=-S*SSZSKSSSESS- - S-= K S S -=R1 ^ES=SR=SS=
TSRRRRR==Sl=R=SK .J=-R- T - T -T-T-T-T- TTSSRRRR==I=S==R=SK
.J=-R- T- T -
T- S=Kf=K- KSRKS
'ERK=R=RZR=KZ-SKK=R- S- ==KRER= SE- S--KR=K=K=KK- == R
'T- S==RRK-RZRRZ
'ERRS==KZKRSS-KKK=KSS- ==KKK== -E-S--RRSS=K=KK-=R 1
-T-T-TSSRR==== .-'-V- T - T -T-T-T-T- T- TSRRRR=I=
-T-TT-T-TTT=SR
RSVSK=RRVKSSSfVKS=S=S-=S -ESE=Z-Sg- S=KSKR--=SSfRRTSR==ITSS-K - 'ES
,'RRVSE=ZSfESSKSTKS=R=S-SS ^ESRSff-ST- ==SSSS— R S S S S S V RSSlST=K-S-T-T-TT- TSSR==R=S:ZSSRRS
'ES
.J.-v---?- :-?.- -T-T- T=SRRSR==S=Z=RSS .JO
KSZTZKEES=E-S “EZRKTSRRSSESRKI=TS=RSS-R=SKSSS=-K-E S=- -EERKfRERZ?
.SRVfZESKS=K-R ^ESTSfSEVS=SSSKfRVSIKRS-ESKKSIS
V- TSSSR==I==K .J--V-Y-T-T-THS
-S-SSR- -EKRSfSSfZV
___________________________________
-ERZR=ZfKRR-SZRE-RKKKK--RRR -KffffK=KTRKRSK=R-KZK=RKS=- = SR-SR
=SS f EgKR=ZSEZR-SE=K- RRKKS--SSi ^EftlS=SgRSS- KRR-ZZK=RSS=-= =E- RR
=== J j-V-T- T- T-V-TT T =========== .j j --" = - TT-VT-T- TSSRRRR==== .J— T
IKZT==K= -ESSSffSS=SRKgSKKSK-KVS=KEKRS-R- = -KKKttVRfffKf- E--EK S = R E -K
.'ZZf==K= ^EKffTffEK=ES=ESttKZSKVRSKtffffT- =- = ^ESKtgT SE ZKff-K--tKS=ffr-f
I=RR==SS •J--VV- -T- -T- T- S-T S=RR-==S==RRR=
. J - V -T -T -TT-T-T-T-TSS=R
!EEKEEK =EKK 0EK-ZSKSffTSSKVtRt - K R K -K tKfKRfSSVRKTKKIf-R -K SR-K=KS=
i s g E K K ^EKZ ^ES-KKKofff ZSRfEKR ^ E = K -gfSTKSf S=SZK SE S V f = - R R = S R = S t l
joVTTT
.j VT Jjo-T- T-V -TSSRl==S .J — V-T-T - T-T- T- T-TSR=SR=S=S=RR==S
ItRKff -ES=Z=TZRffffSSEKffff -ER=ZKT=ZffSKffSS- -K - K K S -S S K K -TK=SffS- - E R "
IS=Rff ^ESRS=VK=SRffSESSS ^E==EKVZZSffKSSf-R - E K g -RSRK-RR=RR=- ^ E 2 "
VVVV JjoVVVVfVVT=RR=== j jTVVIfTVSRR====== Ij o VTTTTTfTR==Z== TjVVV
14
TABLE 3
Positional parameters of non-hydrogen atoms in
ethylenebisbiguanidenickel(II)chloride monohydrate
(parameters x l o \
Atom
Ni
Cl(I)
Cl(Z)
0
N(I)
N(Z)
N(3)
N(4)
N(5)
N(6 )
N(V)
N(G)
N(9)
N(IO)
C(I)
C(Z)
C(3)
C (4)
C (5)
C(6 )
e.s.d.ls in parentheses)
x/a
2573(.8)
Z472(2.0)
3329(2.3)
1234(6)
2892(5)
3 6 0 0 (6 )
3634(6)
3490(6)
2960(5)
2258(5)
1 7 4 8 (6 )
1 6 4 1 (6 )
1539(6)
2175(5)
3 3 8 0 (6 )
3324(6)
2574(8)
Z686(7)
1 9 0 7 (6 )
1 8 2 5 (6 )
zA
39K.5)
-3613(1.0)
-Z87(l.l)
-4484(3)
786(3)
1930(3)
2704(3)
3874(3)
1906(3)
38(3)
-1133(3)
-1920(3)
-3073(3)
-1125(3)
1748(4)
2793(4)
2116(4)
990(4)
-952(4)
-2009(4)
z/c
88(.3)
-2753(o7)
-3462(.7)
-1Z58(2)
1 1 0 3 (2 )
ZI8 3 (2)
IOZO(Z)
5(2)
-190(Z)
-942(2)
-2007 (2 )
-862(2)
1 5 1 (2 )
335(2)
1429(2)
2 4 2 (2 )
-1 0 0 8 (2 )
-1 4 2 0 (2 )
-1 2 6 4 (2 )
-97(2)
15
TABLE 4
Thermal parameters of non-hydrogen atoms in
ethylenebisbiguanidenickel(II )chloride monohydrate
(parameters x l o \
Atom
eU
^22
e.s.d.'s in parentheses)
hi
Ni
138(1.3) 36(0.4)
6 1 (1 .1 )
Cl(I) 254(3.8)
Cl( 2 ) 418(4.9)
57(1.1)
0
126(5)
388(13)
Nd)
40(3)
214(11)
N (2) , 283(13)
65(4)
2 3 6 (1 2 )
Nd)
38(3)
42(3)
N(4)
337(14)
172(11)
39(3)
N(5)
N( 6 ) 174(10)
4K3)
327(14)
55(3)
N(7)
N(B)
233(12)
36(3)
294(13)
4K3)
N(9)
N(IO) 208(11)
41(3)
1 3 1 (1 2 )
C(I)
50(4) .
C( 2 ) 148(12)
4K4)
308(16)
(1(3)
48(4)
e(4) 224(14)
57(4).
c(5) 1 5 2 (1 2 )
56(4)
C( 6 ) 1 1 2 (1 1 )
42(4)
P12
16(0.2)
1(1.4)
-9(3.2)
29(0.5)
23(0.5) -45(3.8)
-80(12)
33(2)
17(1)
-3(9)
16(1)
-37(11)
19(1)
-30(9)
-32(11)
18(1)
-3(8)
18(1)
9(8)
1 6 (1 )
21(2)
KU)
2 1 (1 )
-3(9)
29(2)
-17(11)
2 1 (1 )
-2(9)
22(2)
17(10)
2 1 (2 )
-1 0 (1 0 )
15(2)
-24(13)
0 (1 2 )
18(2)
17(2)
1 8 (1 1 )
2 7 (2 )
1 4 (1 0 )
h.3
hi
20(0.8) -1(0.4)
3 2 (2 .2 ) -23(1.2)
28(2.4) 11(1.2)
65(7)
-29(4)
3K6)
2(3)
27(7)
-8(4)
19(6)
-9(3)
39(7)
-6(3)
2 3 (6 )
-2(3)
21(6)
-6(3)
4K7)
-15(4)
29(6)
-10(3)
26(7)
7(4)
4 0 (6 )
0(3)
24(7)
. -2(4)
35(7)
4(4)
33(8)
0(4.)
43(8)
4(4)
20(7)
-8(4)
16(7)
2(4)
The expression for the anisotropic thermal parameters
is of the form:
e x p C - P ^ h 2 ~ ^2
2
^
~ ^12 hk
16
TABLE 5
Hydrogen atom parameters in
ethylenebisbiguanidenickel(II)chloride monohydrate
(positional parameters xlO^, e,s.d. 1s in parentheses)
Atom
x/a
v/b
s/c
H(I)
H(2)
H(3)
H(4)
H(5)
H( 6 )
H(7)
H( 8 )
H(9)
H(IO)
H(Il)
H(12)
H (13)
H(H)
H(15)
H (16)
H(17)
H(l3)
275(6)
386(7)
436(6)
' 390(6)
350(5)
315(6)
110(3)
377(6)
417(5)
173(6)
220(7)
177(6)
134(6)
139(7)
190(8)
213(7)
190(9)
-2(3)
31(3)
130(4)
239(4)
323(3)
437(3)
402(4)
245(5)
264(4)
90(3)
93(3)
-$3(4)
-134(4)
-253(3)
-356(4)
-340(4)
-132(4)
-454(5)
-486(5)
1 4 5 (2 )
251(3)
234(2)
1 2 5 (2 )
3 1 (2 )
-46(2)
-120(3)
-1 1 3 (2 )
-1 5 1 (2 )
-194(2)
-227(3)
- 2 1 3 (2 )
-103(2)
-1 7 (2 )
58(3)
76(3)
-150(3)
-138(3)
Biso
3.7(1.0)
6 0 6 (1 .4 )
4.4(1.I)
3.9(1.0)
1 .6 (0 .7)
4 .4 (1 .I)
8 .6 (1 .6 )
4 .6 (1 .I)
2:3(0.9)
3.7(1.0)
5.3(1.2)
4 .8 (1 .I)
4 .0 (1 .0 )
5.4(1.2)
7.2(1. 4 )
5.7(1.3)
10.9 (2 .0 )
9.4(1.7)
17
TABLE 6
Least-squares planes referred to orthogonal axes in
ethylenebisbiguanidenickel(II)chloride monohydrate
X = x+
Z oCos p; Y = y; Z = Z oS i n g .
L .S . p l ane:
IX + mY + nZ - d = 0.0
sum of squares of deviations of atoms from plane:
Atoms in plane
I
m
n
S
d
S
.88800
.15444 -.43321 ' 1.509
.07755
.89528
.15778 -.4 1 6 6 2
1.494
.01102
Ni, N(l), NO)-,
N($),C(1),C(2)
.89177
.17699 -.41643
1.461
.00486
Ni, N( 6 ), N(7),
N(8),N(9),N(IO),
C(5),C(6)
.88120
.15823 -.44547
1.483
.00165
Ni, N( 6 ) , N(8 ).
N(IO),C($),C(6 )
.88400
.16043 -.43912
1.492
.00073
Ni, N(l), N(5),
N( 6 ) ,N(IO)
.88380
.15368 -.44190
1 .4 8 8
.00000
Ni, N ( I ) . N ( 2 ) ,
N(3),N(4),N(5),
N(6),N(7),N(8),
N(9),N(IO),
C(I),0(2),0(3),
C(4),C(5),C(6)
Ni, N d ) , N(2) ,
N(3),N(4),N(5),
C(1),C(2)
N(6) and
0005A for N ( 5 ) and N(IO).
The maximum deviation
from the plane of the complex ion (excluding hydrogens)
is
+.16A for the ethylene carbons; the diviations for- t h e ,
remaining atoms are less than .0$A.
The maximum deviations
from the individual six-membered ripgs are .04 and .02A., '
The bond distances within the ethylenebisbiguanide.r- \
nickel(II)
-
complex ion and the water of hydration are
listed in Table 7 and the bond angles are listed in Table 8;
the bond distances and angles are also shown in Figure I.
Hydrogen bonding
The criteria of Hamilton and Ibers (I?) was used to
ascertain whether a hydrogen bond exists between two
electronegative atoms: Knowing that a hydrogen atom lies
approximately along the line connecting the two electro-'
negative atoms, a hydrogen bond exists if the distance from
the hydrogen to the more weakly bound atom is considerably
less than the sum of the van der Waal's radii.
The following van der Waal's' radii were obtained from
Bondi (6): Cl, 1.75A; 0, 1.52A; N, I . 55A; aliphatic.C , 1.70A;
aliphatic H, 1.20A; and aromatic H , I eOA-,
All-hydrogen bopd
interactions involving the'water of hydration and the, t w p ■
chloride ions are listed in Table 9.
°°®calc an(^
H = «=BcaIc are the sums of the appropriate van der Waal's'
19
TABLE 7
Bond distances in
ethylenebisbiguanidenickel(II) chloride monohydrate
Bond
distance
Bond
Ni --- N (I)
N i --- N (5)
N i N (6 )
Ni --- N(IO)
N(I) — -C(I)
N(Z)--C(I)
i.sssd)A
N(I)-H(I)
N(Z)-H(Z)
l.S7Z(3)
l.S7A(3)
1.360(3)
I.ZSl(S)
1.353(5)
N O ) - C(I)
1.363(5)
N(3)— C(Z)
1.376(5)
N(A)--C(Z)
1.3A7(5)
N($)--C(Z). 1.293(5)
N(5)— C(3)
l.A63(S)
N( 6 )— C(A)
l.A72(5)
N( 6 )— C(S)
1.295(5)
N(Y)--C(S)
N (S)-C(S)
N ( S ) - C( 6 )
N (9) ——C (6 )
N(IO)-C(6 )
C d ) - C(A)
1.3AK6)
1.375(5)
1.365(5)
1.3A3(S)
1.233(5)
1.519(6)
N(Z)--Hd)
N(3)— H(A)
N (A)-H(S)
N ( A ) - H( 6 )
■ C (3)— H(7)
.C( 3 )— H(S)
C ( A ) - H(9)
C(A)-H(IO)
N(Y)--H(Il)
N(7)- H ( I Z )
N ( S ) - H(13)
N(9)- H ( I A )
N(9)— H(IS)
N(IO)-H(16)
0 — —— ——H (17)
0 — —— ——H (IS)
distance
0.36
0.93
0 .7 6
0.30
0.73
0.3 a
I.OS
I.OZ
I.OS
1.02
0.90
0.35
0.32
0.31
0 .3 5
0.30
0 .7 0
O .9 6
(A)
(5)
(A)
(A)
(3)
(S)
(5)
(A)
(A)
(A)
(A)
(A)
(A)
(A)
(5)
(5)
(6 )
(6 )
20
TABLE S
Bond angles in
N(I)N(I)N(I)N(5)N(5)N(6 )Ni-Ni-—
Ni-——
Ni-——
N(I)N(I)N(2) C(I)-
N(3)N(3)“
N(A)N(6 )N( 6 )N(7)C (5) N(d)N(d)N(9)Ni-——
Ni-——
C(2)C(A)N(5)C(3) H(17)
Ni-—— -N(S)
Ni ——— ■N(6 )
Ni-—— -N(IO)
N i ——— N(6 )
Ni-—— N(IO)
Ni-—— -N(IO)
N(I)- c(i)
N( 5) - -C(2)
N( 6 )- C(5)
N(IO) - 0 (6 )
C(I)- -N (2)
C(I)- -N(3)
C(I) - N (3)
N(3) -C (2)
C(2)- -N(A)
C (2) - -N(5)
C (2) -N(5)
e d i ­ -N (7)
cts) -N(B)
c ( $) - -N(B)
N(d)- -C (6)
C(6) N(9)
C (6) - -N(IO)
C (6 )7 -N(IO)
N(5)- -C (3)
N( 6 )- -C (A)
N(5)- -C (3)
N( 6 )- -C (5)
C (3) - -C (A)
C(A)- -N(6 )
-H(IB)
angle
9 2 .0 (2 )
178.4(2)
89.7(2)
86.4(1)
1 7 8 .4 (2 )
9 2 .0 (2 )
129.5(3)
12B.K3)
12B.0(3)
129.6(3)
12A.2(A)
121.A(A)
11A.3(4)
126.B(A)
113.1(A)
121.8(A)
125.1(A)
12A.O(A)
122.0(A)
11A.0(A)
127.0(A)
H A . 5 (A)
121.3(A)
124.1(4)
114.B(3)
114.6(3)
116.7(3)
117.0(3)
109.3(4)
109.4(4)
119. (6 )
Atoms.
•H
Atoms
I
ethylenebisbiguanidenickel(II)chloride monohyirate
e
Ni-———N(I),-H(I)
123. (3)
C(I)-N(I)-H(I)
1 0 8 . (3)
C(lj— N(2)— H(2)
1 1 8 . ■(3)
C(1)„N(2)-,H(3)
114. (3)
H(2)~-N(2)— H(3). 107. (A)
C ( I ) - N(3)— H(A) ■. 1 1 6 . (3)
C(2)— N(3)— H(A)
117. (3)
0(2)-,N(A)--H(S)
C(2)-rN(4)--H(6) . 120. (3)
H(5)— N ( A ) - H(6 )
118. (A)N(5)-C(3)-H(7) . H I , (3)
N( 5 )— C(3 )— H(B)
10$, (2)
H(7)— C(3)— H(B) . 114. (4)
C ( A ) - C(3)— H(7)
107. (3)
C ( A ) - C(3)— H(B)
108. (2)
C(3)— C ( A ) - H(9)
107. (2 )
C (3)— C(A)--H(IO) 111. (2)
H(9) T-C(A)--H(IO) H O . (3) ■
N(6 )— C ( A ) - H(9)
109. (2 )
N(6 ),-C(A)-H(IO) 111. (2)
C(5)— N(7)— H(H)
117. (3)
C(5)— N(7>— H(12) .114, (3)
H(Il)-N(7)— H(12) 122. (A)
C(S)-N(B)-,H(13) 1 2 0 . (3
C (6 )— N($)-.-H (13) 113.. (3)
C (6 }——N (9) ——H (I A) H S . (3)
C (6 )— N(9)--H(IS) ■ 123. (3)
H(IA)-N(9)-H(IS). 107. (S)
Ni--- N(IO) i-H(l6 ) 1 22 . (3)
C (6 )— N(IO)-H(16) 1 08 . (3)
21
'0.93(5}
1.358(5)
0.86(4}
1.288(51 ^ y 8151
1.281(5)
1.368(5)
1.858(3)
1.860(3)
1.872(3)
1.874(3)
0.80(41
1.376(5)
1.375(51
0)0.96(6)
T 2 » (5 I
1.347(5)
1.468(5)
0.78(31
1.519(61
1.472(5)
1.02(41
r
113.96(37)
NO)— N i - N(6)
N ( S ) - N i------NOOI
N(5)— C(3I — H17I
NISI — CI31— H(8I
C(4)— C(3)— H(7)
CI4I— C(3)— H (8)
178.3505)
178.4005)
00.6 (28)
107.6 123)
107.2 1281
108.1 (23)
1(8.9(60)
^ ^ ® i.
H(7)— C(3)— H(8) 03.9 (36!
N(6)— 0(4)— HI9) 108.9 09)
N(6)— 0(41— H(IO) 110.5(22)
0(3)'— 0(41 H (91 107.2 091
0(3)— 0(4)' -H(IO) 111.2 (22)
HI9I -0141— H(IO) 109.6(29)
FIGURE I
Bond distances and bond angles of the
ethylenebisbiguanidenickel(II)
complex ion
and the water of hydration.
TABLE 9
Hydrogen bonding
angle
A--H--B
calc
A e *B
obs
A ... B
N(2*)~H(2») •• -0 1 (2 )
143.(3)
3.30
3.401(4)
N(3,T)— H(4,T).•• -Cl(2)
153.(4)
3.30
3.178(4)
.0 1 (2 )
158.(3)
3.30
N(7)-- H(Il) • • •0 1 (2 )
141.(4)
N(9")--H(15v) • •0 1 (2 )
calc
H «* B
obs
H-»»B
diff
H--B
-.1 0 1
2.95
2.61(5)
.34
.122
2.75
2.45(4)
.30
3.243(4)
.057
2.95
2.51(3)
•44
3.30
3.19K4)
.109
2.95.
2.45(4)
.50
163.(5)
3.30
3.198(4)
.102
2.95
2.38(5)
.57
0(1» ?)-H(l 8 ,M) -01(2)
163.(5)
3.27
3.230(4)
2.95
2.30(6)
.65
N(In ) - H ( I n ) • • -01(1)
168.(4)
3.30
3.319(4) -.019
2.75
2.48(4)
.28
N(2 1)— H ( 3 ’) •• -0 1 (1 )
167.(4)
3.30
3.342(4)
2.95
2.60(4)
.36
N(7)---H (1 2 ) .. -0 1 (1 )
162.(4)
3.30
3.274(4)
.026
2.95
2.45(4)
.50
N(IOn )-H(l 6 n )• -01(1)
164.(4)
3.30
3.426(4) — c126
2.75
2.65(5)
.10
O(I)--H(IV) - o •0 1 (1 )
139.(6)
3.27
3.155(4)
.115
2.95
2.59(6)
.36
•0 (1 )
139.(4)
3.0?
3.144(5)
-.074
2 .7 2
2.46(5)
.26
N(8)-- H (1 3 ) •• •0 (1 )
157.(4)
3.07
3.079(5) -.009
2.52
2.31(4)
.21
N(9)---H(14) * * •0 (1 )
163.(4)
3.07
3.002(5)
2.72
2.22L4)
...50
-B
N(4")— H(5")
N (4 ) - - H (6 ) -
I
O
f-
diff
A--B
3
O
bond
.068
23
r a d i i ; A » •eB0^g and H ‘-«B0^S are the experimentallydetermined values.
As the six-member rings appear to have
'’aromatic" character, the entries in Table 9 involving',
hydrogens bonded directly to the rings are f o r ."aromatic H-".
Through extensive hydrogen bonding involving the
water of hydration and the two chloride ions, the molecules ■
are formed into infinite sheets parallel to the (100).
planes.
These sheets are perpendicular to the.plane of the
c-glide and the molecules within one sheet are related to
each other solely by the glide relationship.
Figure 2
shows the molecules and the hydrogen bonding in one of these
sheets as projected onto the (100) plane.
Figure 3 shows
the entire structure and the hydrogen bonding as projected
onto the (010) plane.
The coordination of hydrogen atoms around the oxygen
is a distorted trigonal bipyramid.
The atoms 0, H (14)
H(17) and H(l8) lie nearly in a plane with the angles:
H (14)— 0— H (I?)
133.(5)°
H(U)-O-H(Id)
108.(4)
H(17)— 0 — H(l8)
119.(6)
. sum = 360.°
The atom H(6) is in an axial position with the angles:
H (6 )—— 0—— H (14)
8 4 .(2 )
H(6)---O - H ( I T )
89.(5)
H (6)-- O - H ( I d )
1 0 0 .(4 )
24
J
O-
-H 0---N O— C O "*0 (*)-"CL O e--Ni
FIGURE 2
Crystal structure of
ethylenebisbiguanidenickel(II)chloride monohydrate
projected onto the (1 0 0 ) plane.
I
25
FIGURE 3
Crystal structure of
ethylenebisbiguanidenickel(II)chloride monohydrate
projected onto the (010) plane.
26
The gtom H (13) is considerably distorted from the axial
position with the angles:
H (13)— 0 — H (6)
128.(1)
H (1 3 )— O - - H ( U )
53,(2)
H(13)— 0 — H(l?)
.99,(5)
H (1 3 )— O - H ( I S )
119.(4)
'
This coordination around oxygen is very similar to that
.
found by Ibers, Hamilton, and MacKenzfe (19) in their study
of sodium perxenate octahydrate in which the two hydrogen
■
atoms in a water molecule also lie in equatorial positions
in a trigonal bipyramid.
One chloride ion is five-coordinate an,d the other is
six-coordinate,
packing.
This appears to be dependent on the
•s'
Both chloride ions have four hydrogen bonds
within each sheet parallel to the (100) pla n e ; Cl(I) has
one additional bond to a hydrogen atom in an adjacent sheet
while Cl(2) has two additional bonds, one each to a.hydrogen
in both adjacent sheets.
- -
Bonding within the complex ion
The bonding within the complex ion has been studied in
detail by Holian and Marsh (18).
There are characteristics
which appear in the six-member rings which indicate a
conjugated or "aromatic" system:
(I) the planarity of the
27
rings; (2) the bond angles of approximately 120°;
(3) tfte
coordination of only three atoms around each carbon an,4
nitrogen in the rin g s ; and (4) the shortened C-N and
slightly elongated C=N bond distances.
The planarity and
angles of the terminal -NHg groups with respect tp the
six-member rings and the shortened C-N bond distance
together indicate that these, groups may also be involved
in the conjugation.
SECTION II
THE COMPARISON OF THE TWO DETERMINATIONS OF
THE CRYSTAL AND MOLECULAR STRUCTURE OF
ETHYLENEBlSBIGUANIDENICKEL(I I )CHLORIDE MONOHYDRATE
Experimental differences
The crystals used in the two studies came from .
different sources; those used by Holian and Marsh (IS)
(hereafter referred to as tiHMt') were prepared by Professor
B.D. Sharma and those used in the present study were
prepared by Dr. D.J. MacDonald.
The data collection
differed in that HM used Ni-filtered CuKa (X=l.5418A)
radiation and an automated G.E. diffractometer while the
present study used Zr-filtered MoKct (X=0.7107A) radiation
and a manual G.E. XRD-5 diffractometer.
The 9-20 scan
technique was used in both studies but HM used a scan rate
of half the 2°/minute in 29 scan rate used in the present
study.
The crystal used by HM was nearly a cube with
edges about 0 .1 mm while that used in the present study was .
rectangular with edges about 0 .8 mm, 0 .3 mm and 0 .1 mm.
'Refinement differences
The difference in radiations used led to the following
differences in the refinements: HM applied only the real
29
term for nickel in correcting for anomalous dispersion .
while the present study applied both the real and imaginary
terms for both nickel and chlorine; HM refined a secondary
extinction parameter while no evidence of extinction was
observed in the present study; and HM did not apply
absorption corrections while they were applied in the
present study.
Additional differences in the refinements
were that HM ended the refinement when the largest parameter
shift was about 0.23 times the standard deviation while the
present study ended at about 0.1$ times the standard
deviation, and that the final R of the H M .study was Lr.
for 2679 observed intensities while the final R of the
present study was 3.1% for 1714 observed intensities,
A significant difference, especially with respect to
the parameter estimated standard deviations, is that HM
refined the parameters with the full-matrix least-squares
program of Duchamp (11) while the present study used the
block diagonal least-squares program of Ahmed (3).
Comparison of parameter differences
The average difference in the x, y, or z parameters
for the non-hydrogen atoms is slightly less than the average
of the standard deviations; no individual difference, is as
great as three times the individual standard deviation.
30
The thermal parameters .for the non-hydrogen atoms show close
agreement.
The average difference in the g - Q ,
, and 3 ^
is about twice the average of the standard deviations; the
magnitudes in the present study average about 5% greater.
Not a single '3^2 > P 13 > or 323 differ in sign and the average
difference is about 0.7 times the average of the standard
deviations; the magnitudes are essentially equal in the
two structures.
The average difference in the x, y , or z parameters for
the hydrogen atoms is less than 1.3 times the average of the
standard deviations; four individual differences just exceed
three times the individual standard deviations.
Hydrogen
H (I?) in the water of hydration shows the greatest deviation
between the two structures.
The hydrogen temperature
factors follow essentially the same pattern with the average
in the present study being greater by nearly 20$.
The CHI-square test
The CHI-square test was applied to test the agreement
between the HM atomic parameters and the atomic parameters
of the present study; the results are listed in Table 10.
There appears to be little or no significant differences
between the positional parameters of the non-hydrogen atoms;
.
31
TABLE 10
CHI-square test on parameter types
(significant values at the 5$ and 1% levels
are from Owen (
))
Parameters
(non-hydrogen atoms)
1%
X
32
y
28
PU
z ■
26
191
P22
P33
376
30?
9
65
11
012
013
023
all
all
Pii
Oij
all
positional ■
thermal
(ifj)
parameters
(hydrogen atoms)
X
y
Z
Biso
all positional
all parameters
86
959
674
65
1045
44 .
40 '
28
28
112
140
(30)
(30)
(30)
(30)
(30)
(30)
(30)
(30)
(30).
(76)
(146)
(76)
(76)
(212)
(28)
(28)
(28)
(28)
(71)
(92)
*
(36)
(36)
(36)
(36)
(36)
(36)
(36)
(36)
(36)
(67)
(156)
(67)
(67)
(227)
(33)
(33)
(33)
(33)
(60)
(102)
32
however, significant differences are indicated for the
s
and the hydrogen positional parameters.
Half-normal probability plots
A half-normal probability plot was prepared by Abrahams
(I) to compare the atomic parameters and standard deviations
of the two studies; this plot is shown in Figure 4«
240 of
the 252 total parameters lie close to a straight line of
zero intercept and of slope about 1.7; the remaining 12
parameters are, with only two exceptions, nickel or chlorine
P ij 1s .
The 6
were then calculated for the nickel and
chlorine thermal parameters; these are listed in Table 11
along with the expected values for a normal distribution
containing j elements.
Figure 5 shows a half-normal
probability plot for the 18 thermal parameters of the nickel
and chlorines; it is approximately linear, of zero intercept
and of slope about 6 .5 .
Figure 6 shows a half-normal
probability plot for the 9 diagonal (
P
thermal parameters
of the nickel and chlorines; it, except for one point, is
approximately linear, of intercept about 6.2 and of slope
about 3-6.
Figure 7 shows a half-normal probability plot
for the 9 off-diagonal (Pjj, i^j) thermal parameters of the
nickel and chlorines; it indicates two separate distributions
of the parameters; o n e , consisting of the P^ 2 / 3 an^ @ 2 3 ’s
33
'=18I2
C '=16M
1:1r =22
.Cl(I)B,,
A
.cime.,
•cime.
1.00
o.
0.50
1.00
Z.00
1.50
».50
1.00
1.5
*4
FIGURE 4
Half-normal probability plot for
all parameters.
34
TABLE 11
6 p . for nickel and chlorine Sij-Ts
(expected values from Hamilton and Abrahams
Parameter
GPI
.1=18
(16))
expected values
iz9
Ni
333
13.416
2 .1 2 5
1.835
Ni
322
1 2 .0 0 0
1.712
1.370
Cl(2) 333
9.225
1.471
1.029
Cl(2) 322
9.104
1.295
.875
Cl(I) 322
9.104
1.151
.696
Cl(I) 311
2.151
1 .0 2 2
.538
0 1 (2 ) 311
7.747
.919
.393
Cl(I)
333
7.422
.220
.257
Ni
313
4 .2 4 0
.729
1.835
Cl(I)
313
3.724
.6 4 4
1.370
C l (2) 313
3.077
.563
1.029
Ni
311
1.897
■.486
Cl(I)
323
.769
.411
.875
Ni
312
.601
.339
.6 9 6
Cl(I)
312
.530
.269
,538
Cl( 2 ) 312
.466
.200
.393
Cl(2)
323
.000
.133
.257
Ni
323
.000
.066
.127
.127
35
13.0---------------------------------------------------------
12.0 -------------------------------------------BB------11.0 -------------------------------------------------------
10.0---------------------------------------------------- EL - 0
9.0 -------------------------EB--E-------------
EL
8.0 ------------------------ ------------------------------B
0
0
7.0 -------------------------- ----------------------------
6.0 ------------------------------------------------------------6Pi
5.0 --------------------------------------------------------
0
4 .0 ---------------- g - 9 ---------------------------- ------
0
3 . 0 -------------- EL
0----------------------------------------
2.0 ----------- !J5--------------------------------------
1. 0
0
00 E
o.o 4 6-00 0- - - - - - - - - - - - - - - - - - - - - - - - - - - - - 0.0
0.5
1.0
1.5
xi
FIGURE 5
Half-normal probability plot for
nickel and chlorine PjjTs
2.0
36
xi
FIGURE 6
Half-normal probability plot for
nickel and chlorine
's
37
0
4.0- ■
0
3.0-
2 .0 -
6P:
1 .0 0
0
0
0
0.O=I1= S = S =
0.0
0.5
1.0
1.5
FIGURE 7
Half-normal probability plot for
nickel and chlorine Pij-fS
(i^j)
2.0
is approximately linear of zero intercept and of slope about
0.8; the other, consisting of the 3- ^ 1s , is considerably
removed from the .first distribution.
The first plot, Figure 4, for all the parameters,
indicates that the differences between the majority of the
parameters follow a normal distribution and that the
standard deviations of both studies have been underestimated
by an average factor of about 1.7.
This plot also indicates
that the nickel and chlorine thermal parameters contain a
systematic error either in the parameters themselves or in
their standard deviations.
The second pl o t , Figure 5, for the nickel and chlorine
thermal parameters, ,assuming that the linearity and zero
intercept are real, indicates that there are systematic
•
errors in either the parameters or in the standard
deviations or in both such that the weighted differences
are 6.5 times larger than expected for a normal distribution.
The third plot, Figure 6, for the diagonal thermal
parameters of the nickel and chlorines, indicates by virtue
of the non-zero intercept.that there is a systematic error
■
in this class of parameters.
The fourth plot, Figure 7, for the off-diagonal thermal
parameters of the nickel and chlorines, indicates that the
39
P]_2 rs anc^ the P 2 3 *s belong to a normal distribution and
that the £1 3 ’s belong to a different, non-normal
distribution probably as the result of systematic errors
in these parameters or in their standard deviations.
SUMMARY AND CONCLUSIONS
The comparison of the atomic parameters determined in
two independent studies of a crystal structure has yielded
information concerning the precision of the X-ray method
of structure determination.
The methods of comparison
differed greatly in the information obtained from them.
The simple comparison of corresponding parameters
indicates that the positional parameters of both
determinations agree well (to within about three times the
standard deviations reported in the present study) and does
point out that the hydrogen B^s q tS and the non-hydrogen
P i i 1S differ significantly in'a systematic manner (the
values reported in the present study average larger by
5% and 20 %, respectively).
The CHI-square tests on various groups of parameters
at the 0 .0 5 and 0 .0 1 levels indicate general good agreement
between all classes of parameters except the non-hydrogen
P - ^ tS which show moderate differences and the non-hydrogen P i i ’s which show marked differences as a class.
It is
interesting that the CHI-square test indicates good
agreement between the hydrogen B^s o ’s.
The half-normal probability plots indicate that all the
parameter differences other than the nickel and chlorine
41
@3.1 ,s and 32.3 ’5
a normal distribution with their
standard .deviations underestimated by an .average factor
of about 1 .7 and that the nickel and chlorine P n ’s and @2.3 ’
belong to a non-normal distribution (that is, there are
significant systematic errors which affect these parameters)
The particularly interesting and important conclusion '
of this comparison is the quantitative determination of the
factor by which the standard deviations have been under­
estimated.
The question remains as to why the nickel and
chlorine 3 ^^'s and
alone were affected by whatever
systematic error exists between the two studies or within
one or the other of the studies.
PART II
Dicarbony lnitrosyltripheny lphosphinecobalt (O)'
INTRODUCTION
Dicarbonylnitrosyltriphenylphosphinecobalt(O) has been
.used as a catalyst for the dimerization of norbornadiene
(bicyclo[2-2«l]hepta-2,5-diene)
(21) »
Its catalytic action
is not completely understood and the structure was determined
to assist in furthering this understanding.
This structure provides an opportunity to study the
bonding of carbonyl, nitrosyl and tripheny!phosphine groups
to the cobalt(O) atom and also the opportunity to study the
effects of non-bonded interactions on the angular
configuration of the molecule with respect to rotation
about single bonds.
The rotation about the Co-P bond is particularly .
interesting and was studied in detail.
Considering only
the Co and P and the six carbon atoms bound to them, one
would expect that the steric interactions would favor the
staggered configuration.
The X-ray crystal structure
shows that the configuration in the crystal is actually
only 6° from being eclipsed.
Several explanations exist which may account for this
discrepancy.
and P .
One is that tt-bonding exists between the Co
Another is that the steric interactions involve
more than just the eight atoms.
Still another explanation
is that this angle is an effect of crystal packing and that
the free molecule would find another configuration more
favorable from a steric viewpoint.
An examination of molecular models indicates that the
second explanation is true and that nearly every atom in
the molecule is involved in the steric interactions.
It
does not exclude, however, the other explanations for the
discrepancy.
One means of examining the steric interactions within
the molecule is to calculate the non-bonded repulsion
energies as a function of the angles of rotation about the
single bonds.
If it is found that the molecule in the
crystal prefers, with respect to non-bonded repulsion
energies, a different angle about the Co-P bond than is
observed, the existence of v-bonding may be indicated
between Co and P .
The configuration for the free molecule
which minimizes the non-bonded repulsion energy can be
compared with the configuration found in the crystal; this
comparison should indicate whether and how much crystal
packing deforms the molecule.
The crystal structure is reported in Section I and the
study of the angular configuration is given in Section II.
SECTION I
THE CRYSTAL AND MOLECULAR STRUCTURE OF
DICARBONYLNITROSYLTRIPHENYLPHOSPHINECOBALT(O)
Preparation of the crystals
Crystals of dicarbonylnitrosyltriphenyiphosphine-'
cobalt(0) were prepared by Gerald E. Voecks as follows:
Co(CO)-^NO was purchased from Strem Chemicals, Dover, Mass.', ■
and purified by trap to trap distillation on a vacuum lin e ;
under Ng at I atm and in toluene solvent, tripheny!phosphine
and Co(CO)^NO were mixed in the molar rgtio 3:2 and heated ■
until no further evolution of CO was observed; the toluepe
was evaporated and the remaining solid disolved in a 5:1
volume ratio of hexane and dichloromethane; the solution was
put onto an alumina column and eluted with hexane.; the solidfrom the first fraction was re-crystallized from hexane
yielding the red crystalline product melting in the rapge
136.0-136.5°C.
Density determination
The density, determined by flotation in a mixture of
benzene and chloroform, is 1.39(5) g.cm"^.
Several small
crystals were used while adjusting the composition.of the
mixture as the crystals rapidly disolve in it.
46
Determination of space group and cell parameters
Preliminary photographic examination of a single
crystal of dicarbonylnitrosyltriphenylphosphinecobalt(O)
indicated that it is in the triclinic system.
Precise
parameters of the Delauney unit cell were determined by
least-squares refinement of the 29 values of 30 general
reflections measured on a General Electric XRD-5
diffractometer using a G. E. single crystal orienter and
MoKa ( X=0.71069A) radiation.
The crystal data is listed
in Table 12.
Collection of the data
The unique intensity data were collected by 9-29 scans
using zirconium-filtered MoKa (X=O.'71069A) radiation and a
General Electric XRD-5 diffractometer equipped with a
scintillation counter, pulse-height discriminator, and a
G. E. single crystal orienter.
Sixty-second scans
(2° in 29) were used with stationary backgrounds measured
for 30 seconds each at the start and finish of each scan.
The crystal was mounted with the [II 3 ] vector parallel to
the spindle axis.
A chart recording of diffracted
intensity ys_. 29 was monitored during data collection to
insure that the reflections were centered in the scan range.
Of the 2907 unique reflections which were examined within
47
TABLE 12
Crystal data
Dicarbonylnitrosyltriphenylphosphinecobalt(0 )
C 20 H 15 C o N 03 P '
f -W ‘ 4 0 7 .2 5
F(OOO) =, 416
Triclinic, space group Pl
a = 11.055(2)A
a = 1 2 1 .0 7 (2 )
b = 1 1 .0 2 4 (4 )
3 = 1 0 1 .0 1 (2 )
c = 10.260(2)
Y — 105.14(2)
N
Il
N
V = 950.31A 3
Dm = 1.39(5)g.cm " 3
Dx = 1 ,4 2 g.cm ""3
48
the range 29 ^ £0°, 2006 had an intensity greater than
twice the standard deviation of the intensity;' the remaining
901 reflections were coded as "unobserved^ and were not
included in the refinement„
The dimensions of the crystal were.measured using a
calibrated "Whipple disc" in the alignment microscope of the
diffractometer (see Appendix II)
(32) „
The crystal was
well-shaped, bound by the planes [OIO), [lOOl, {110}, {Oil},
and (101}, and its dimensions in the directions of a*, b * ,
and c were approximately .19mm,
tively.
.39mm and .56mm, respec­
The linear absorption coefficient for MoKa
radiation is 11.01 cm-^-; absorption corrections, using the '
method of de Meulenaer and Tompa (25), calculated trans­
mission coefficients
(I/l0 ) ranging from .915 to .851.
Determination of the structure
The Patterson map was consistent with two molecules
in the centric Pl cell.and from it the positions of the
cobalt and phosphorus atoms were determined.
A Fourier
map revealed the positions of the remaining non-hydrogen
atoms.
The structure was refined by full-matrix least-
squares, using the weighting scheme described by Stout and
Jensen (29), refining the nitrogen and carbons in the
nitrosyl and carbonyl groups as composite "NO atoms"
49
consisting of 1/3 N and 2/3 C in their scattering factor
curves and refining all atoms anis'otropically.
Examination of the resultant bond lengths and thermal
parameters of the nitrogen and carbons (refined as composite
"NO atoms") in the nitrosyl and carbonyl groups could not
distinguish nitrogen from the carbon atoms; the refinement
was continued assuming disorder in the nitrogen and carbons
in the nitrosyl and carbonyl groups.
The positions of the phenyl hydrogens were calculated
assuming a C-H bond length of 1.054.
The refinement of
the structure was completed by full-matrix least-squares,
refining the non-hydrogen atoms anisotropically and the
hydrogen atoms isotropically, applying anomalous dispersion
corrections to cobalt and phosphorus, and using the
weighting scheme referenced above.
The final R was 3-2%
and the final R ^ d was 3.5% where R and RwtcJ are defined as
P _
z
If 0 -F c I
2 IF 0 |
„
= / z:URi If 0 -F c I)2 15
J Z ( V S l F 0 I)2 J
and the function minimized during refinement was
S « ( IF0 I- “ |Fcl>Z
The final R including "unobserved" data was 8.8% and the
final R for "unobserved" data only was 53.1%.
50
The observed and calculated structure factors are
listed in Table 13 for the 2907 unique reflections; the
"unobserved" data are indicated by double asterisks (**) e
The positional parameters of the non-hydrogen atoms are
listed in Table 14, the thermal parameters for the non­
hydrogen atoms are listed in Table 15, and the hydrogen
atoms parameters are listed in Table 16,
A final difference Fourier map was calculated and was
essentially flat with the density ranging from + 0 ,2 7 to
-0.21.
The observed peaks do not fall at atomic positions
within the cell.
The structure was also refined with a carbon and a
nitrogen at each "NO. atom" position, refining occupation
factors and independent positional and thermal parameters.
This refinement yielded nitrogen and carbon positions
within 0.03A of the corresponding "NO atom" positions,
thermal parameters similar to those from the earlier
refinement, and a final R of 3 «2% and
of 3 = 5%»
The
parameters of the other atoms refined to within one standard
deviation of their earlier values.
were 0 .3 1 (4 ) for W(I)
0.22(4) for N(2).
The occupation factors
(corresponds to atom NC(I)) and
The occupation factors for the remaining
atoms are then 0 .4 6 for N(3), 0.69 for C(I ) , 0 .7 8 for C(2)
51
TABLE 13
Observed and calculated structure factors.
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52
TABLE 13 Continued
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53
TABLE 13 Continued
Innm
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TABLE 13 Continued
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55
TABLE 14
Positional parameters of non-hydrogen atoms in
dicarbonylnitrosyltriphenylphosphinecobalt(0)
(parameters xlQ^-, e.s.d.’s in parentheses)
Atom
Co
P
0(1)
0(2)
0(3)
NC(I)
NC (2)
NC(3)
C(H)
C (12)
C (13)
C(H)
C (15)
C (16)
C (21)
C (22)
C(23)
C (24)
C (25)
C (26)
C (31)
C (32) .
C (33) .
C(34)
0(35)
C(36)
z/c
2150(.5)
3173(.9)
684(3)
291(3)
4317(3)
1283(3)
1030(4)
3460(3)
2850(3)
2823(4)
2605(4)
2403(4)
2429(4)
1737(.6)
4462(.6)
1 0 7 2 (1.0)
-1137(3)
2809(4)
4154(4)
22(4)
2381(4)
2695(1.0
3954(3)
. 3211(4)
1553(4)
2980(5)
3389(5)
2380(6)
3468(4)
7634(4)
4172(4)
3846(5)
6377(4)
1247(4)
1798(5)
743(6)
-8 7 0 (6 )
-1447(5)
-380(4)
2657(4)
962(5)
558(5)
2700(4)
-1022(4)
1338(4)
1326(4)
-2029(5)
904(5)
18 4 6 (6)
3 2 0 6 (6)
3631(5)
5021(3)
5871(4)
-3624(5)
-4217(6)
5.00(4)
-554(5)
-3251(6)
-1658(5)
-762(6)
6 5 (6)
1111(5)
1925(4)
3646(4)
3134(5)
7256(4)
. 2569(4)
3164(5)
7821(5)
313K5)
7014(5)
5630(4)
2522(5)
5154(5)
5705(5)
1942(4)
4992(4)
3867(5)
56
TABLE 15
Thermal parameters of non-hydrogen atoms in
dicarbonylnitrosyltriphenylphosphinecobalt(0)
(parameters xldA, e.s.d.’s in parentheses)
Atom
Co
P
0(1)
0(2)
0(3)
NC(I)
NC (2)
NC(3)
C(Il)
C (12)
c (13)
C(IA)
C(15)
c (16)
C (21)
C(22)
C(23)
c (24)
C(25)
C(26)
c (31)
c (32)
0(33)
0(34)
0(35)
0(36)
hi
^22
hi
P1 2
147(0.8) 218(1.1) 180(1.0) 95(0.7)
102(1.1) 132(1.5) 119(1.5) 58(1.1)
264(6)
186(4)
316(7)
115(4)
501(10) 159(5)
174(4)
344(7)
345(8)
226(7)
181(5)
34(5)
160(6)
120(4)
193(7)
76(4)
137(5)
220(7)
277(9)
92(5)
204(8)
125(5)
201(7)
57(5)
13K6)
131(6)
93(4)
52(4)
138(5)
148(7)
165(2)
69(5)
181(8)
165(6)
259(10)
96(6)
15d(6)
237(10) 226(10)
27(6)
147(2)
27(6)
218(7)
192(9)
187(6)
88(6)
156(7)
145(7)
121(6)
135(6)
121(5)
63(5)
144(6)
148(8)
68(6)
152(7)
125(2)
173(7) . 152(8)
43(7)
277(10)
102(8)
128(9)
132(9)
201(8)
118(8)
182(9)
212(9)
148(6).
76(6)
161(7)
149(7)
110(6)
122(6)
108(4)
61(4)
107(5)
166(7)
145(7)
52(5)
206(8)
115(6)
55(6)
202(9)
102(6)
207(8)
59(6)
17K9)
146(6)
108(6)
149(7)
243(9)
189(7)
116(5)
152(7)
77(5)
Ai
108(0.7)
56(1.1)
133(4)
151(5)
71(4)
75(4)
123(5)
92(5)
47(4)
72(5)
70(6)
73(6)
70(5)
102(6)
ts i
119(0.9)
80(1,3)
213(5)
286(7)
11(6)
109(5)
145(7)
68(6)
88(5)
100(6)
165(8) .
123(9)
114(7)
99(6)
91(5)
90(6)
92(7)
92(8)
61(4)
60(5)
41(6)
80(8)
86(7)
69(6)
56(4)
43(5)
76(6)
35(6)
62(6)
63(5)
118(8)
93(6)
65(5)
95(6)
121(7)
67(7)
116(7)
106(6)
The expression for the anisotropic thermal parameters
is of the form:
e x p (-P11Ii2 -I322 Ic2 -P33 ^2-2 P12hk -2 P13W
-2P23k 4
51
TABLE 16
Hydrogen atom parameters in
dicarbonylnitrosyltriphenylphosphinecobalt(0 )
O
(positional parameters xlO , e»s.d„?s in parentheses)
Atom
H(12)
H (13)
H(H)
H(15)
H(16)
H( 22)
H(23)
H(24)
H(2$)
H(26)
H(32)
H(33)
H(34)
H(35)
H(36)
x/a
302(3)
261(3)
226(4)
239(4)
267(3)
69(3)
-9 (4)
158(3)
397(4)
457(3)
549(3)
776(3)
871(4)
732(3)
501(3)
zZk
367(4)
441(4)
268(4)
2 8 (5 )
-46(4)
-156(4)
-427(5)
-526(4)
. -356(4)
-98(4)
259(4)
359(4)
354(4)
244(4)
146(4)
z/c
293(4)
117(4)
-156(5)
-254(5)
-85(4)
6 6 (4 )
-1 0 8 (5 )
-139(4)
5(4)
162(4)
227(4)
351(4)
563(4)
659(4)
532(4)
Biso
4 .6 (0 .8 )
5.5(0.9)
7 .2 (1 .1 )
7.9(1.2)
5.0(0.9)
4.5(0.8)
7.7(1.2)
5.5(1.0)
6 .4 (1 .0 )
3 .8 (0 .8 )
4 .6 (0 .8 )
4 .0 (0 .8 )
4.9(0.9)
5.8(0.9)
4.5(0. 8 )
and 0.54 for C (3).
These values f o r .the occupation'
factors give additional justification.for the assumption
of statistical disorder in the nitrogen and carbons in the
nitrosyl and carbonyl groups and for the refinement of
these atoms as composite nNC" atoms.
The structure
The coordination about the cobalt and phosphorus is
slightly distorted from tetrahedral.
The average angle
NC-Co-P is 10$.1°, the average angle NC-Co-NC is 113.5°,
the average angle C-P-C is 103.2°, and the average angle
Co-P-C is 115.2°.
The molecule is rotated about the Co-P bond such that
the carbonyl-nitrosyl groups nearly eclipse the phenyl
groups; the angle the molecule is rotated away from being
fully eclipsed is 6° (the angle NC(I)-Co-P-C(21)).
The
phenyl groups are rotated about the P - C (xl) bonds to give a
"propeller" arrangement.
A drawing of the molecule which
also illustrates the thermal ellipsoids is shown in Figure 8.
One hydrogen atom of each phenyl ring is placed above
atom C (xl) of another ring to give the following short
non-bonded contacts:
C(Il)--H(32)
2.60(4)A
C (21)--H(16)
2.62(4)
C(3U--H(26)
2.59(4)
59
FIGURE 3
Molecular structure of
dicarbonylnitrosyltriphenylphosphinecobalt(0)
illustrating the thermal ellipsoids.
60
Taking the aromatic hydrogen van der W a a l rS radius from
Bondi (6) to be I.OA and the phenyl ring thickness of 3•2 A ,
a minimum non-bonded contact of 2.6A would be expected.
The observed distances are not significantly less than
2.6A and thereby give no indication of strong intra-
'
molecular hydrogen bond interactions.
Intermolecular non-bonded contacts between oxygen and
phenyl carbon atoms range as short as 3 -17A.
Taking fpom
Bondi (6). the van der W a a l rS radius of 1.77A for aromatic
carbon and 1.50A for carbonyl oxygen, a minimum non-bonded
contact of 3.27A would be expected..
However, the angles
0*»«H— -C are far from linear with the least a Qute- angle
being about 134°.
This far departure from linearity
coupled with the lack of oxygen^— carbon distances that are
significantly less than 3 .2 7 A indicates that there are no
strong intermolecular hydrogen bond interactions..
Least-squares planes were calculated, giving each atom
equal weight, for each of the three phenyl rings with and
without the phosphorus atom.
are given in Table 17.
-
The equations of these planes
The maximum deviations from the.
planes of the individual rings with and without the
phosphorus atom a r e , respectively:
61
TABLE I?
Least-squares planes referred to orthogonal axes in '
dicarbonylnitrosyltriphenylphosphinecobalt(0 )
I - x + y* cos Y + z»cosp; I = y«sin y + z (cosq - cose jC o s v )
//
,
sin Y
"
Z = V/(a«b«siny).
L.S. plane:
IX + mY + nZ - d = 0.0
sum of squares of deviations of atoms from pla n e :
Atoms in plane
I
m
P,C(I l ) ,0(12),
C (13) ,C(H) ,
C(15),C(16)
.91065
C ( H ) ,0(12) ,
0(13) ,C(H) ,
C (15),C(16)
v
S
n
d
S
.33336
.24411
2.796
.00020
.91110
.33019
.24670
2.790
.00004
P,C(21),C(22),
C(23),C(24),
0(25),0(26)
.15579
.63020 -.76063
-1.546
.00011
0(21),0(22),
0(23),0(24),
0(25),0(26)
.15547
.63166 -.75949
-1.552
.opooa
P,0(31),0(32),
C(33),C(34),
0(35),0(36)
-.42442
.64076
.63976
-.031
.00133
0(31),0(32),
0(33),0(34),
0(35),0(36)
-.41539
.64233
.64405
.037
.00037
62
.OlOA and. .004A for the ring containing C(Il)
.007A
.005A
0(21)
.022A
.013A
c (31)
Bond distances within the molecule are listed in
Table lg and bond angles are listed in Table 1 9 .
A
stereographic packing diagram (22 ) for the crystal is
shown in Figure 9 .
It is interesting to note that the ’’propeller”
arrangement of the phenyl rings gives a helical sense to the
molecule.
The second molecule in the unit cell, related
to the first by the center of symmetry, has the opposite
helical sense.
It appears, from the study of models,
that the interconversion between the two helical senses
is accomplished by simultaneous rotation about the Co-P
bond and about the three P - C (xl) bonds; the rotation about
the Co-P bond being approximately H O 0 .
Bonding to the cobalt(0) atom
The comparison of the M-C bond lengths with those in
Co(CO)^(NO) and other ’’pseudo-nickel carbonyls" is listed
in Table 20 and indicates' a significant shortening of the
M-NC bonds.
Ibers (12)
This phenomena was also found by Enemark and
(13) and by Frenz, Enemark, and Ibers (1 4 ) to
occur with Mn(CO)^(NO) with increasing substitution of the
63
TABLE Id
Bond distances in
dicarbonylnitrosyltriphenylphosphinecobalt(O)
Bond
C0
—
P
Co————O (I )
Co————O (2)
Co————O (3)
Co————N C (I )
Co———-NC(2)
C o————N C (3)
O(I)-NC(I)
0(2)— NC (2)
0(3)— NC(3)
P------ C (Il)
P------ C(21)
P------ c(31)
C( 1 1 ) -C( 1 2 )
C(12)-C(13)
C(1 3 )-C(1 4 )
C(U)-C(15)
C( 1 5 ) -C( 1 6 )
C( 1 6 ) -C( 1 1 )
C( 2 1 ) -C( 2 2 )
C(22)-C(23)
c (2 3 )-C (2 4 )
c (2 4 ) - c (2 5 )
distance
2 .2 2 4 (1 )A
2.863(4)
2.894(4)
2 .8 5 8 (3 )
1.717(5)
1.749(5)
1.729(4)
1 .1 5 2 (6 )
1.145(6)
1.130(5)
1 .8 2 4 (4 )
1.821(4)
1.816(4)
1 .3 8 2 (7 )
1.376(8)
1.362(7)
1.368(9)
1.384(8)
1.374(5)
1.383(6)
1.377(8)
1.361(10)
1.363(9)
Bond
c (2 5 )- C (2 6 )
C (26) -C (21)
C (3 1 )- C (3 2 )
C(32)-C(33)
0(33)-C(34)
C (34) -C (35)
0(35)-0(36)
c (3 6 )- C (3 1 )
C (1 2 )- H (1 2 )
C (13) -H (13)
C(U)-H(H)
C (15)-H(15)
C (16)- H (16)
C (22)- H (22)
C(23)-H(23)
C (24) -H( 24)
C (25)-H(25)
C (26)- H (26)
C(32)-H(32)
C (33)-H(33)
0(34) -H(34)
C(35)-H(35)
0(36)-H(36)
distance
1.374(8)
1.380(7)
1.375(6)
1.367(7)
1.371(7)
1.357(8)
1.365(7)
1 .4 0 3 (6 )
0.94 (3)
0 .9 8 (5)
0.93 (5)
0 .9 6 (4 )
0.97 (4)
0.96 (4)
0.98 (5)
0.90 (5)
0.99 (5)
0,94 (4)
0 .9 2 (4 )
0 .8 9 (4)
0 .8 8 (4 )
0 .9 6 (4 )
0.97 (4)
64
TABLE 19
Bond angles in
dicarbonylnitrosyltriphenylphosphinecobalt (O)-'
Atoms
P —————Co————NC(I)
P —————Co————N C (2)
P —————Co————N C (3)
NC(I)-Co---- NC(Z)
N C ( I ) - C o - — NC(3)
NC(Z)-Co---- NC(3)
Co ---- NC(I)-O(I)
Co---- NC(Z)-O(Z)
Co---- N C (3)-0(3)
Co————P —————C (ll)
Co————P —————C(Zl)
Co————P —————C (31)
C(Il)-P------C(Zl)
C(Il)-P----- C (31)
C(Zi)-P----- c (3 1 )
p ----- C(Il)-C(IZ)
P —————C (11)—C (1 6 )
C(Il)-C(IZ)-c(13)
C(IZ)-C(1 3 )- C (1 4 )
C (13)- C (14)- C (15)
C (1 4 )-C(1 5 )- C(1 6 )
c (1 5 )- C (1 6 )-C(Il)
C(16)-C(Il)-C(IZ)
P ------C(Zl)-C(ZZ)
p ------C(Zl)-C(Z6)
C(Z1)-C(ZZ)-C(Z3)
C(ZZ)-C(23)- C (24)
C (23)- C (24)- C (25)
C (2 4 )- C (2 5 )- C (2 6 )
C (25)- C (26)-C(Zl)
C (2 6 )- C (2 1 )- C (2 2 )
P ------C(31)-C(32)
P ------C(31)-C(36)
C (31)- C (32)- C (33)
C (32)- C (33)- C (34)
angle
104« 2(1)
106.3(2)
104.7(1)
111.4(2)
116.3(2)
I l Z .9(2)
179.0(4)
176.7(4)
176.6(4)
116.5(1)
113«9(l)
115.1(1)
10Z.9(2)
103.5(2)
1 0 3 .3 (2 )
119.4(3)
IZZ ®4(3)
1Z0.6(4)
1Z0.Z( 5 )
120.Z(5)
119.5(5)
1Z1.Z(4)
116.2(4)
117.6(3)
1Z3. 6 (3 )
1 Z 0 .5( 5 )
119.6(5)
120.6(6)
1 1 9 .6 (6 )
120.9(5)
1 1 6 .4 (4 )
123.9(3)
116.6(3)
121.6(4)
119.6(5)
Atoms
.C(33)-C(34)-C(35)
C (34)-C (35)- C (36)
C (3 5)- C (3 6 )- C (31)
C (3 6 )-C (3 1 ) -C (3 2 )'
C(Il)-C(IZ)-H(IZ)
C(IJ)-C(IZ)-H(IZ)
C(IZ)-C(13)- H (13)1
C (14)- C (13)-H(13)
C (13) -C (14) - H (14)’
C(15)-C(14)-H(14)
C (14) r-C(15) ~H(15)
C (16)-C (15)-H(15)
C (15)-C (16)-H(l6)
C(Il)-C(16)- H (16)
C(Zl)-C(ZZ)-H(ZZ)
O(ZJ)-C(ZZ)-H(ZZ)
C(ZZ)-C(Z3)-H(23)
C(24)-C(23)-H(23)
C (23)- C (2 4 )-H( 2 4 )
C (25)-C(2 4 )-H(2 4 )
C (24)-C (25)-H(25)
C(26)-C(25)-H(25)
C (25)-C (26)-H(26)
C(Zl)-C(26)- H (26)
C (31) -C (32) -H(3’2)
C(33)-C(32)-H(32)
C (3 2 )-C (33.) - H (33)
C(34)-C(33)-H(33)
C(33)-C(34)-H(34)
C (35) -C (34) -H(34)
C (34)-C (35)-H(35)
C (3 6 )-C (J5) - H (35)
C (35)-C (3 6 )- H (3 6 )
C (31)- C (3 6 )-H(36)
angle
120.4(5)
120,4(5)
120.5(4)
117.5(4)
117. (2)
122, (2)
119; (2)
121. (2)
119. (3)
121. (3)
1 22 . (3 )
116. (3)
116. (2)
123. (2)
1,17. (2)
122. (2)
116. (3)
124. (3)
121. (3)
1 1 6 . (3)
127. (3)
113. (3)
1 20 . (2)
119. (2)
116. (2)
120. (2)
116. (2)
122. (2)
119, (3)
121. (3)
126. (3)
114. (3)
123. (2)
116. (2)
65
FIGURE 9
Stereographic packing diagram of
dicarbonylnitrosyltriphenylphosphinecobalt(0)
TABLE 20
Comparison of nitrosyl and carbonyl bond distances
(Distances are averaged where there are two or more equivalent bonds.)
Study
M-C
C-O
M-O
M-N.
N ——0
M ——0
Ni(CO ) 43
1.82(2)A
1 .1 5 (3 )
2.97
Ni(CO ) 413
1.84(3")
1 .1 5
2.99(3)
Co(CO) 3 (NO) 0
1.83(2)
1.14(3)
2.97
1.76(3)
1.10(4)
2.86
Fe(CO)2 (NO)2 0
1 .8 4 (2 )
1.15(3)
2.99
1.77(2)
1.12(3)
2.89
Co(CO)2 (NO)P(Ph)3d
1.732(4)
0
I
O
'M - N C
1 .1 4 2 (6 )
M-O
2.873(4)
a
Brockwell and Cross ( 7 )(electron diffraction study)
b
Ladell, Post and Fankuchen (23)(X-ray)
c
Brockway and Anderson ( 8 )(electron)
d
the present study (X-ray)
67
carbonyl groups by triphenylphosphine.
The shortening of the metal-carbon bond with increasing
substitution of the carbonyl groups by triphenylphosphine
may be explained qualatatively as follows: Phosphorus
(as in triphenylphosphine)
is less adept,at back bonding
. I''
to the transition metal than is the carbon of a carbonyl
group (77 -bonding between phosphorus and cobalt will be
examined .in Section II of this Part).
Substitution of
the carbonyl group by triphenylphosphine would cause the
loss of the back bonding attributed to the carbonyl group
and thereby one would expect an increase in the bond order
of the remaining metal-carbon (nitrogen) bonds.
In the three canonical forms for bhe bonding in the
carbonyl group ( M - O s = O , M = O - O , and M s e C — 0) as the
Cr-O bond order changes, the M-C bond order changes in the
opposite direction; thereby the C-O and N--O stretching
frequencies may be empirical monitors of the M-C and M-rC
bond orders.
Infrared spectra have been studied (21) to
give support to this explanation:
Cp(CO)3 (NO)
C-O v (a)
^(b)
N-Ov
Co(CO) 2 (NO)P(Ph)3 .
.6
2100 cm"1
2036
64
2035
1932
53
1305
1?60
45
In each case'the stretching.frequencies are lowered as the
carbonyl group is substituted by tripheny!phosphine.
' This
indicates a decrease in the C-O and N-O bond orders and
presumably an increase in .the M-C and M-N bond orders.
One would then expect a lengthening of the C-O and N-O bond
lengths and a shortening of the M-C and M-N bond lengths.
As in the study of the Mn(CO)^(NO)
series, the
Co(CO)^(NO) series shows a decrease in the M-C and M-N '. ■ •
bond lengths (observed as a decrease in the M-NG bond,
lengths) and shows essentially no change in the nitrosyl or
carbonyl bond lengthsv(observed as NG-O bond lengths).
As a continuation of a study of the bonding to the
cobalt(0), it would be interesting to.investigate the.
crystal structure of Co(CO)(NO)(P(Ph ) ^ ) 2 to verify the
explanation and prediction of the shortening of metalcarbop and metal-nitrogen bond lengths with increasing
substitution of carbonyl groups by triphenylphoephine.
SECTION II
THE ANALYSTS OF THE ANGULAR CONFIGURATION OF
DIGARBONYLNITROSYLTRIPHENYLPHOS PHINECOBALT(O )
Introduction
The empirical equations of Bartell ( 5 ) were used to
calculate the non-bonded repulsion energies.
They are (in
c .g . s . units):
V c_c (r) = 20.Sxl0~105r*12 - 22.6xl0"6°r"6
Vh-h(r) = 4.5dxl0-10[exp-(r/0.245x10-3)]
V c_h (r) = S.68x10-60
- 3 .42xlO-6 or ~6
5d[exp-(r/0.490x10-8)]
- ij r “6
Conversion to units of kcal/mole requires multiplication
by the factors:
2 • 6.02xl023 • 2.3^OxlO-11RcaI
mole
erg
For the purpose of calculating relative non-bonded
repulsion energies, all nitrogens and oxygens in the molecule
were assumed to be similar to carbon and the equations for
^c-c(r) and V c-h(r) were used regardless of ..whether the
non-hydrogen atoms were carbon, nitrogen, or oxygen.
This
appears to be a satisfactory approximation for calculating
relative energies.
The molecule in the crystal
The initial coordinates for all atoms in the molecule
70
were those observed in the X-ray determination of the
crystal structure. ' The molecule was translated to place
the phosphorus atom at the origin (the other molecules
were also translated by the same vector) and the four
rotation axes were defined as the vectors from the origin
(the phosphorus atom) to the cobalt atom and to the three
phenyl carbon atoms bound to the phosphorus.
The
appropriate atoms could then be rotated about these axes
((CO)2 (N0 ) about the P-Co vector and C
5 about each of
the P-C vectors).
Extremely short non-bonded distances represent an
improbable configuration for the molecule.
To conserve
on computing time, the calculation of the repulsion energy
was bypassed for a particular configuration if any of the
non-bonded distances were less than the following: I.SA
for H - H , 2.2A for C - H , and 2.6A for C - C .
The individual
repulsion energies (summed for the total interactions of
the molecule) were calculated only for pairs of atoms whose
relative positions could change with rotation about one
of the four axes and only when the separation between these
atoms was less than 5 .CA.
Taking the molecule imbedded in the crystal, the nonbonded repulsion energies were calculated in steps of 5°
71
over a range of 120° about the P-Co vector.
As this vector
approximates a three-fold rotation axis, this one part of
the plot of the energy vs. angle of rotation should closely
approximate the remaining two parts of the plot.
The plot
is shown in Figure 10 and indicates a maximum in energy at
an angle 60° from that in the crystal and a minimum in
energy at the angle found in the crystal.
It appears to be
smooth, uniform, and symmetrical about the angles of O0 and
60°=
-The relative energy scale of the plot has been
adjusted to place the lowest energy at zero.
The free molecule
The calculation of the non-bonded repulsion energies
for the free molecule as a function of rotation -about the
P-Co vector was similar to that for the molecule in the
crystal except that interactions were considered only within
the one molecule.
This plot is shown in Figure 10 super­
imposed on that for the molecule in the crystal.
The energy
maximum appears at an angle of approximately 82° relative to
that found in the crystal and the energy minimum at an angle
of approximately 20°„
This plot also appears to be smooth,
uniform and symmetrical about the angles of approximately
20° and 82°.
The non-bonded repulsion energies for the free molecule
72
_8
I500_
I400_
O
I300_
O
I200_
_6
IIOO_
IOOOJ
_5
900_
800_
kcal
O
kcal
700_
600_
_3
500_
400_
300_
200
,
I00_ .
°
*
0_ o o* ® Q o. °• * *
O O o O -0
60
degrees
FIGURE 10
Non-bonded repulsion energies
as a function of rotation
about the Co-P bond
120
73
were calculated with respect to rotation about all four
vectors with intervals of 15° and a range of 120° about the
P-Co vector and a range of 180° about each of the three P-C
vectors; interactions were considered only for separations
of less than 3 « 5A..
The calculation was repeated with the
rotation in the opposite direction giving a total of nearly
40,000 distinct angular configurations for the molecule»
A large majority of these configurations are improbable due
to extremely short non-bonded distances and the energies
were not calculated for them.
The non-bonded repulsion energies are listed in
Table 21 for the free molecule in the angular configuration
found in the crystal and for the free molecule in which the
phenyl rings have individually been rotated 15° or -15°
about the P-C vector.
In the cases of rotation of 15°
about the P-C vector and of rotation in the positive
direction about the P-Co vector, the energy minima appear
at about O0 and the maxima at about SO0 ; in the one case for
rotation of -15° about P-C which did not create non-bonded
distances less than the limits, the minimum appeared at
about 2$° (-95°) and the maximum at about 85 ° (-35°).
No angular configuration was found for the free
molecule which calculated a minimum non-bonded repulsion
74
TABLE 21
Non-bonded repulsion energies for configuration
(x^_ = increments of 15° about P-G(Il) ,
X 2 about P - C (21), x^ about P- C (31))
angle
Co-P
configuration
100
000*
_
001*
■
010*
100*
3 .9 8 9
ok
. ok..
1 .359 ..
ok ■
000
001
.433
.832
1.328
1.172
.559
.733
1.143
1.645
1.443
.914
30
1.202
1.498
1.808
1.800
1.298
1.018
45
'1.858
1.936
2.200
2.033
1.924
1.814
60
3.936
3.593
3,885
3.071
4.115
4.564
75
7.699
6.093
7.011
4.780
7.831 10.280
90
7.501
5.417
7.082
4.316
6.777 12.710
10$
2.853
2.149
3.168
1.632
2.647 ' 7.641
120
0.413
0.875
1.175
0.788
O .483
O
15 '
*
010
xxx
ok
xxx
2.095
denotes rotation in the negative direction about
C o - P ; 15° corresponds.to an actual angle of -105°.
ok
xxx
denotes no non-bonded distances less than limits. ■
denotes a non-bonded distance less than limits,and
the energy not calculated for this configuration.
75
energy less than that for the angular configuration found
in the crystal.
It is interesting to note that the
energy decreases when one rotates +120° about Co-P (by only
.070 kcal/mole) and increases when one rotates -120° about
Co-P (by only .076 kcal/mole) for the configuration found
in the crystal; these very small energy differences
help justify the assumption that the Co-P vector is
essentially a three-fold axis.
SUMMARY AND CONCLUSIONS
The.plot of the non-bonded repulsion energy as a
function of the angle of rotation about the Co-P vector,
Figure 10, indicates that the molecule in the crystal is,
■with respect to rotation about the Co-P vector, in the most
favorable configuration.
T h u s , there is no indication of
any forces within the molecule other than non-bonded
repulsions influencing the angular configuration of the
molecule in the crystal.
The plot and the tabulation of the non-bonded repulsion
energy as a function of rotation about the Co-P vector for
the free molecule, Figure 10 and Table 21, indicate that
the most favorable configuration in the absense of the
intermolecular forces in the crystal is that with an angle
approximately 20° greater than that in the crystal.
The
tabulation as a function of rotation about the four vectors,
Table 21, indicates that the most favorable configuration
for the free molecule is that with the same angles about the
three P-C vectors as in the crystal and with an angle about
the Co-P vector approximately 20° greater than in the crystal.
This analysis of the dependence of the non-bonded
repulsion«energy on the angle of rotation about the four
vectors has not ruled out the possibility of ir-bonding
77
between the cobalt and the phosphorus atoms; it has
indicated that it is not necessary to postulate ^-bonding
to explain the observed configuration in the crystal.
This analysis does indicate, in the absense of
^-bonding and presumably due to crystal packing forces,
that in going from the free to the crystalline state the
molecule is rotated approximately 20° about the bond
joining the cobalt and phosphorus atoms.
APPENDIXES
APPENDIX I
NORMAL PROBABILITY PLOT ANALYSIS OF ERROR IN
DERIVED QUANTITIES AND STANDARD DEVIATIONS
Introduction
.
Abrahams and Keve ( 2) have applied the normal
probability plot analysis method to independent X-ray
intensity data sets to check the validity of the assigned ■
standard deviations of the F 0^s and then to the
independently determined sets of atomic parameters with
their derived standard deviations to check for normal
error distributions and correct standard deviations.
This appendix presents the work of Abrahams and Keve
in condensed form and describes the probability plot and
the properties of a normal probability plot.
The probability p l o t '
A probability plot may be used to compare the
distribution of any set of magnitudes with any assumed
distribution; deviations from the assumed distribution
may be examined with great sensitivity.
Taking two
independent sets of magnitudes F(I) ^ and F(2)-j_ with their
standard deviations <yF(I )^ and o-F(2) -^ and the least-squares
scale factor K relating the two sets, the statistic <$p^
80
is defined as
dpi = ^F(I). - KF(2)J
The distribution of the
. + K2(*2p(2)^y^
is expected to be Gaussian if
the F(I)i and F(2)^ contain only random error and if the
O-F (I )i and(rF(2)j_ are correct.
To construct a normal probability plot, the set of
<fpj_ is rearranged in order of increasing magnitude -and
plotted against x^, the values expected for a normal
distribution.
The values of x^ are obtained from the
normal probability function
I
P(x) =
fx
I
-8^/2
e
dot
v2tr -f-x
where the i-th value of P(x) for the j-ordered statistics
(meaning there are j elements in the set of Jp ) is given
by
(j-2i+l)/j .
The sign of x is positive for i greater
than j/2 and negative for i less than j/2.
The construction of a half-normal probability plot
is similar except that Jjpi J are used and the i-th value
of P(x) is given by (2j-2i+l)/2j .
Properties of a normal probability plot
The ordering of the J p i in order of increasing
Si
magnitude necessarily places the largest at the extremes of
the array.
The density of points of this array represents
the distribution of the Jpi .
In the analysis of a normal
probability plot, the departure of individual
remainder of the array is less important
trends.
from the
than the overall
Hence, in judging a plot for linearity and slope,
in is important to give the greatest weight to the densily
populated central portion of the plot containing the
majority of the data.
If the assumed distribution is the same as that of the
set of magnitudes to be compared, the plot will be
recognizable as linear.
A non-zero intercept can be
attributed to an error in the value of the scale factor K
in the case of a normal probability plot and to a systematic
error (other than a scale factor between the sets) in the
case of a half-normal probability plot.
(This as a result
of using the normal probability plot for sets of elements
such as F0T3s which are relative and must be scaled, and
of using the half-normal probability plot for sets of
elements such as atomic parameters which are absolute.)
A slope different from unity (on a linear plot with
zero intercept) may indicate uniform misestimation of the
standard deviations by a factor of !/(slope).
APPENDIX II
DETERMINING THE EXTERNAL GEOMETRY AND
DIMENSIONS OF A SINGLE CRYSTAL
•
Introduction
The calculation of accurate corrections for the
absorption of X-rays by a crystal requires an accurate
knowledge of the external geometry and dimensions of
the crystal.
Tichy (30) proposed a method to obtain
this knowledge in terms of the coordinates of the apices
of the crystal and Alcock
(4 ) proposed a method in terms
of the equations describing the plane of each crystal face.
Another method determines the coordinates of three points
on each face from which the equation of the plane of that
face can be determined.
The method described below obtains this knowledge
easily and directly for a well-shaped crystal in terms of
the Miller indices of the faces and the thickness of the
crystal between parallel faces.
The method has been
developed for use with the General Electric XRD-5
diffractometer equipped with the General Electric single
crystal orienter.
instruments.
It may be adapted for use with other
Instrument modification
The cross-hair reticle in the alignment microscope
eyepiece is replaced by a nWhipple disc" (Bausch & Lomb
Cat. No. 31-16-13) which consists of a IOxlO square grid
with one grid unit near the center further subdivided into
a 5x5 grid.
The grid is aligned with one axis lying in
the plane of the 9-29 circle and the other axis normal to
this plane.
The grid may be calibrated by placing a
calibrated scale at the crystal position and observing the
image of the scale superimposed on the image of the grid.
The method
The alignment microscope line-of-sight is set normal
to the plane of the CHI circle of the single crystal ..
orienter,
(This is accomplished with the G.E. XED-5
diffractometer by setting 29 at 100.00°.)
When CHI and
PHI (but not 29 which is left set at 100.00°) are set for
a given reflection, h k l , the crystal face with the same
Miller indices,
(hkl), is viewed as lying parallel to the
line-of-sight and normal to the plane of the 9-29 circle
(i.e. , it is viewed as a line parallel to the vertical axis
of the grid).
Figure 11 is a graphical illustration of
this situation. . Whether the crystal face lies parallel to
the line-of-sight can be verified by rotating +10° about
84
(hkl) uIhki)
FIGURE 11
Graphical illustration of view through alignment microscope
of the diffractometer showing the image of the "Whipple
disc" grid superimposed on the image of the crystal.
PHI and observing that the grazing angle approaches zero as
PHI approaches the setting for that reflection.
Scale drawings (similar to Figure ll) are made on
graph paper for each face of the crystal at the CHI and PHI
settings of the corresponding reflection.
Taking the
intersection point of the a x e s .of the CHI, PHI, and the
0-29 circles of the diffractometer as the origin, the scale
drawings are measured to determine the origin-to-face
distance for each face of the crystal.
In Figure
11
the origin (indicated by a dot at the center of the
crystal)
is deliberately shown.as being displaced from the
center of the grid (a common occurrence!) and the distances
to the two parallel faces (hkl) and (hkl) are indicated.
It is essential to calibrate the grid to determine the
spacing between grid lines and to determine the location
of the origin with respect to the grid.
Summary
The indices and the origin-to-face distance for every
face, along with the unit cell parameters, constitute the
data set necessary to describe the external geometry and
dimensions of a single crystal.
This data set is easy to
obtain by the method' described above and the naturalness of
viewing and measuring the crystal optically and of
86
describing the external geometry of the crystal in terms of
the indices of its faces makes it less likely to make
mistakes in obtaining or in handling the data.
87
LITERATURE CITED
1.
Abrahams , S „ C ., (1970) «,
Private communication,
2.
Abrahams, S „ C., and K e v e , E, T,,
A 2 7 , 157.
3.
Ahmed, F. R., (1966). nNRC-IO Structure Factor Least
Squares (Block Diagonal)", National Research Council,
Ottawa, Ontario, Canada.
4«
Alcock, N. ¥.,
5.
Bartell, L.' S.,
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88
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Hamilton, W. C., and Ibers, J. A., (1968). "Hydrogen
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Ibers. J. A., Hamilton, W. C., and MacKenzie, E. R.,
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MacDonald, D„ J.,
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Stewart, R. F., Davidson, E. R., and Simpson, W. T.,
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S t o u t , G. H., and Jensen, L. H., (1968 ). "X-ray
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89
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Ward, D 0 L 0, and Caughlan, C, N., (1971)
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i
*
J 0 Appl0
M O N TA N A S T A T E U N IV E R SIT Y L IB R A R IE S
762 1001 1657
D378
W212
Ward,
cop. 2
Donald
Structure
bonding
metal
of
L
and
transition
complexes
NAMK ANO AOORgge
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bindery
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