The X-ray crystallographic determination of the structures of the CIS para-menthane thiourea adduct
and 1,2,4 trichlorobenzene-1,2,4 trimethylbenzene thiourea adduct
by Mark John Spinti
A thesis submitted in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE
in Chemical Engineering
Montana State University
© Copyright by Mark John Spinti (1986)
Abstract:
Thiourea's unusual ability to form adducts with hydrocarbons shows promise as a method of separating
hydrocarbon mixtures. In an attempt to better understand the forces which hold thiourea adducts
together, the crystal structure of two thiourea adducts were determined by x-ray crystallography A
diffractometer data set was collected on a crystal of the thiourea adduct with cis para-menthane. This
structure was solved in the space group R3bar in a hexangol unit cell with parameters of
a=b=15.935(2), c=12.489(2), α=β=90.0° and γ=120.0°. The disorder of the cis para-menthane molecule
was successfully modeled and refinement gave a R value of 0.0670.
Another diffractometer data set was collected on a crystal of the thiourea adduct containing a 50 mole
percent mixture of 1,2,4 trimethylbenzene and , 1,2,4 trichlorobenzene. This aromatic-thiourea adduct
was solved in the space group P2,/c in a monoclinic unit cell with parameters of a=9.886(7),
b=15.245(8), c=12.313(6), α=&gamma:=90. O° , and β=112.48° (4). The aromatic molecules in this
adduct are disordered and no model was found for them.
Both of these adduct structures are consistent with the structure of other similar thiourea adducts.
Evidence, in the form of interatomic distances, for an interaction between the sulfur atom of thiourea
and OH groups of the cis para-menthane molecule was found. It was concluded that a dipole-dipole
interaction exists between the sulfur atom of thiourea and C-H groups of the cis para-menthane
molecule. THE X-RAY CRYSTALLOGRAPHIC DETERMINATION OF THE STRUCTURES
OF THE CIS PARA-MENTHANE THIOUREA ADDUCT AND 1,2,4 TRI­
CHLOROBENZENE-1 ,2,4 TRIMETHYLBENZENE THIOUREA ADDUCT
by
Mark John Spinti
A thesis submitted in partial fulfillment
of the requirements for the degree
of
MASTER OF SCIENCE
in
Chemical Engineering
MONTANA STATE UNIVERSITY
Bozeman, Montana
February 1986
A/3??
Sp 4 7
CopS
ii
APPROVAL
of a thesis submitted by
Mark John Spinti
This thesis has been read by each member of the thesis
committee and has been found to be satisfactory regarding
content, English usage, format, citations, bibliographic
style, and consistency, and is ready for submission to the
College of Graduate Studies.
Date
Qi^airperson. Graduate Committee
Approved for the Major Department
Date
Approved for the College of Graduate Studies
/J Sr£
Date
Graduate Dean
iii
STATEMENT OF PERMISSION TO USE
In presenting this thesis in partial fulfillment of the
requirements
University,
available to
for
I
a
master's
agree . that
borrowers
Brief quotations
from
special permission,
degree
the
under
this
Library
the
rules
thesis
provided
at
Montana
shall
State
make
it
of the Library.
are allowable without
that accurate acknowledgment
of source is made.
Permission for extensive quotation from or reproduction
of this thesis may be granted
his absence, by
the
Director
by my major professor, or in
of
Libraries
when, in the
opinion of either, the proposed
use of the material is for
scholarly purposes. Any copying
or
use of the material in
this thesis for financial gain shall not be allowed without
my written permission.
Signature
iv
ACKNOWLEDGEMENT
The author would like to express his gratitude to Dr.
Charles Caughlan for his instruction in crystallography and
to Dr. F. P. McCandless for his help and ideas.
Also thanks to Dr. A. Fitzgerald, Ray Larson, Jim Fait
and Tom Wick for their help.
V
TABLE OF CONTENTS
Page
TITLE PAGE . . .........................
i
APPR O V A L ......................................
ii
STATEMENT OF PERMISSION TO USE . . ............... iii
ACKNOWLEDGEMENT..........
iv
TABLE OF CONTENTS..............
v
LIST OF T A B L E S ..........
vii
LIST OF FIGURES.
ix
A B S T R A C T......................................
x±
INTRODUCTION
Background.........................
Related Research...................
Research Objectives.............. ..
I
4
.
22
EXPERIMENTAL
Crystal Growth.....................
23
1,2,4 TMB-I,2,4 TCB Adduct. .
Cis para-Menthane Adduct.
..
Crystal Analysis. . . .................
Adduct Density.....................
25
Crystal Mounting...................
26
Photographic Film Studies ............
Diffractometer Data Collection.....
27
24
24
24
27
RESULTS AND DISCUSION
Discusion of X-ray Crystallography.
..
30
Cis para-Menthane Adduct. ............
32
49
1,2,4 TMB-1,2,4 TCB Adduct.........
SUMMARY........................................
59
CONCLUSIONS.............
62
vi
Page
RECOMMENDATIONS. . . ...........................
65'
LITERATURE C I T E D ............................ '.
67
APPENDICES
■
Appendix A- Additional Figures.......
71
Appendix B- Tables for Publication for
cis para-Menthane Adduct
Structure............
74
Appendix C- Atomic Coordinates for 1,2,4
TMB-I,2,4 TCB Adduct
Structure.................... 93
Appendix D- Explanation of Space Group
Labels ..................
95
vii
LIST OF TABLES
Page
TABLE I- Compounds which form adducts with
thiourea compared with compounds
which do not form adducts..............
5
TABLE 2- Lengths of the guest molecule plotted
against the molar ratio thioureajguest .
9
TABLE 3- Interatomic distances between sulfur
and carbon in the 1,2,4 TMB and 1,2,3
TCB a d d u c t ................
13
TABLE 4- Unit cell parameters, for cyclohexane
and carbon tetrachloride adducts . . . .
17
TABLE 5- Cyclohexane-thiourea adduct sulfuraromatic carbon distances. . . . . . . .
19
TABLE 6- Carbon tetrachloride-thiourea adduct
sulfur-chlorine distances................ 19
TABLE 7- Structural parameters for 1,2,4 TCB. . .
21
TABLE 8- Interatomic distances between sulfur
and carbon, or sulfur and hydrogen
atoms in the cis para-menthane
adduct structure......................... 47
TABLE 9- Van der Waal radii distances between
sulfur and carbon atoms in the cis
para-menthane adduct. .................... 47
TABLE 10- Gas chromatograph analysis of 1,2,4
TMB and 1,2,4 TCB adduct feed, mother
liquor after adduct formation, and
extract ....................
50
TABLE 11- Reflections absent and the symmetry
indicated for the 1,2,4 TMB-I,2,4 TCB
adduct........................
51
TABLE 12- Structural data for several
thiourea adducts......................... 60
I
viii
Page
TABLE 13- Atomic coordinates and isotropic
thermal parameters for cis
para-menthane adduct structure. . . . . . 75
TABLE 14- Anisotropic thermal parameters for
cis para-menthane adduct structure. . . . 76
TABLE 15- H-atom coordinates and isotropic
thermal parameters for cis paramenthane adduct structure ..........
TABLE 16- Bond lengths for cis para-menthane
adduct structure....................
TABLE 17- Bond angles for cis para-menthane
adduct structure....................
TABLE 18- F(obs) and sigma(F) for cis paramenthane adduct structure ..........
. . 80
TABLE 19- Observed and calculated structure
factors for cis para-menthane adduct
structures. .........................
TABLE 20- Atomic coordinates for 1,2,4 TMB1,2,4 TCB adduct structure..........
. . 94
TABLE 21- Symbols for one-, two-, threedimensional cells ..................
. . 96
TABLE 22- Symbols for symmetry elements and for
the corresponding symmetry operations in
one-, two-, and three-dimensions. . . . . 97
ix
LIST OF FIGURES
Page
FIGURE I- Lattice of urea and
thiourea adducts...................
11
FIGURE 2- 1,3,5 TMB, 1,2,3 TMB and 1,2,4 TMB
in the channel of a thioureaadduct . .
15
FIGURE 3- Trichlorobenzene-thiourea adduct
structure viewed down the c-axis
offset by 2 0 ° .....................
18
FIGURE 4- Cis para-menthane adduct without the
model for the hydrocarbon viewed
down the c - a x i s ...................
34
FIGURE 5- Constrained cis para-menthane molecule
with 50% probability ellipsoids. . . .
36
FIGURE 6- Space-filling plot of constrained
cis para-menthane molecule.........
37
FIGURE 7- Packing plot of cis para-menthane
molecule showing it's three
orientations about the three
fold center of symmetry............ ..
.
38
FIGURE 8- Hydrogen bonding scheme in the
thiourea network of the cis paramenthane adduct viewed down the
sulfur-carbon bond of a thiourea
molecule..............................
40
FIGURE 9- Stereoview of the hydrogen bonding
in the thiourea network of the cis
para-menthane adduct structure, viewed
down the c-axis offset by 2 0 ° ........
41
FIGURE 10- Stereoview of the cis para-menthane
adduct structure with a model for the
cis para-menthane molecule, viewed down
the c-axis offset by 20°.............
43
FIGURE 11- Space-filling plot of three thiourea.
molecules with planar sulfur atoms and a
cis para-menthane molecule viewed down
the c-axis.........
44
X
Page
FIGURE 12- Three thiourea molecules with planar
sulfur atoms and a cis para-menthane
viewed down the S-C bond of a thiourea
molecule. . ...........................
46
FIGURE 13- Stereoview of 1,2,4 TMB-I,2,4 TCB
thiourea adduct viewed down the
c-axis................................
54
FIGURE 14- Stereoview of the 1,2,4 TMB-I,2,4 TCB
thiourea adduct viewed down the c-axis
offset by 2 0 ° ........................
55
FIGURE 15- Three thiourea molecules with planar
sulfur atoms and two benzene rings
from the 1,2,4 TMB-1,2,4 TCB adduct
structure vieweddown the c-axis. . . .
57
FIGURE 16- Two thiourea molecules with planar
sulfur atoms and two benzene rings
from the 1,2,4 TMB-1,2,4 TCB adduct
structure............................
58
FIGURE 17- Stereoview of. model for cis
para-menthane molecule.......... ..
72
FIGURE 18- Thiourea molecules in the channel
wall, viewed in at a sulfur pointing
into the channel. . ..............
. .
73
ABSTRACT
Thiourea's unusual ability
to form adducts with
hydrocarbons shows promise as a method of separating
hydrocarbon mixtures. In an attempt to better understand
the forces which hold thiourea adducts together, the
crystal structure of two thiourea adducts were determined
by x-ray crystallography.:
A diffractometer data set was collected on a crystal
of the thiourea adduct
with cis para-menthane. This
structure was solved in the space group R3bar in a hexangol
unit cell with parameters of a=b=15.935(2), c=12.489(2)r
a=p=90.O0 and 7=120.O0. The disorder of the cis paramenthane molecule was successfully modeled and refinement
gave a R value of 0.0670.
Another diffractometer data set was collected on a
crystal of the thiourea adduct containing a 50 mole percent
mixture
of
1,2,4
trimethy!benzene
and
, 1,2,4
trichlorobenzene. This aromatic-thiourea adduct was solved
in the space group P2_/c in a monoclinic unit cell with
parameters
of
a=9.886(7),
b=15.245(8),
c=12.313(6),
<x =y =90. O0 , and (3=112.48° (4). The aromatic molecules in this
adduct are disordered and no model was found for them.
Both of these adduct structures are consistent with
the structure of other similar thiourea adducts. Evidence,
in the form of interatomic distances, for an interaction
between the sulfur atom Of thiourea and O H groups of the
cis para-menthane molecule was found. It was concluded that
a dipole-dipole interaction exists between the sulfur atom
of thiourea and C-H groups of the cis para-menthane
molecule.
I
INTRODUCTION
Background
Pure compounds
are
often
required
synthetic processes. Requirements
in polymeric and
for pure compounds cause
pure compounds to be of greater value than mixtures. If the
separation and purification
of
the cost of the separation
high costs of separating
the compound is difficult,
process can be prohibitive. The
hard-to-separate systems leads to
the demand for new separation techniques.
The separation
■industrial
of
process.
Most
advantage
of
example,
distillation
volatility.
makes
the
nearly
separation
in
is
often
the
mixtures
separation
differences
Quite
formula have
hydrocarbon
physical
based
isomers
same
on
of
is a common
processes
take
properties:
for
differences
a
given
in
empirical
physical properties, which
of
isomers
very
difficult. Other
hydrocarbon mixtures which
contain
compounds with similar
physical properties also pose separation problems.
One
novel
crystallization.
compound
separation
In
selectively
technique
extractive
forms
compound. Isomers and some
an
is
extractive
crystallization
adduct
classes
with
a
given
the desired
of hydrocarbons can be
separated using extractive crystallization.
2
An adduct is
compounds. When
compounds
are
a
an
crystal
which
adduct
crystal
released
contains
unchanged.
is
two or more
dissolved
The
structure
,
the
of an
adduct contains "host" molecules in a cage-Iike arrangement
which.traps the "guest" molecule.
Urea and thiourea will act
some adducts. These
adducts
"guest" molecules.
A
will ' only form with suitable
suitable
appropriate chemical properties
will form adducts
will form
and
adducts
cyclohexane
compounds such as
cyclic
with
thought that
their
benzenoid
and
compounds
proper adducting structures
I ,2,4,5
with the
certain
chloro
tetrachloride, some branched and
thiourea adducts unless they
as
one
molecular shape. Urea
derivatives,
alcohols,
buty!benzene, or other
and
is
branched paraffins, cyclopentane
carbon
aldehydes,
"guest"
straight chain paraffins. Thiourea
with:
and
as the "host" molecules in
ketones
would
(1,2).
not
It was
form stable
contain side groups which are
(e.g. benzylcyclohexane, tert-
highly
substituted structures such
tetramethy!benzene)(I).
Recent
studies
have
shown that o-xylene, pseudocumene (1,2,4 trimethylbenzene),
and all three isomers of trichlorobenzene will adduct (3).
The reason for
that will adduct
the
with
difference
urea
and
the
between the compounds
compounds that will
adduct with thiourea ‘
is the size of the channel which traps
3
the guest molecule. Since the
than the oxygen in urea,
trap
guest
molecules.
sulfur in thiourea is larger
thiourea
An
has a larger channel to
interesting
characteristic of
thiourea is that it is selective for some geometric-isomers
(5).
Some
compounds
adducts can be
which
induced
to
by
themselves
form
will
not form
adducts if an additional
compound is present (4). This additional compound is termed
an inductor.
Normally difficult separations
induced extractive crystallization
reported that Cg alkylbenzenes
separated
using
induced
Different inductors are
can
be made easier if
is used. McCandless has
and aromatic isomers can be
extractive
crystallization (6).
selective for different compounds.
The role of the inductor is not fully understood.
4
Related Research
Urea
adducts
Bengen in 1940
(I).
determining
fat
alcohol to
reduce
crystals
Further
were
He
content
paraffins
showed
and
discovered
was
using
urea
in
milk.
Bengen
frothing
characteristic
study
accidently
of
that
other
and
in
by
M. F.
a method of
added n-octyl
observed the needle-like
urea
and
higher
thiourea
alcohols,
straight-chained
adducts.
acids,
hydrocarbons
n-
form
adducts with urea.
Thiourea adducts were
discovered
(7) and independently in 1949
tellurourea have
also
been
in 1947 by Fetterly
by Angla (2). Selenourea and
found
to
form
adducts with
organic compounds (I). Thiourea will form adducts with some
compounds that will
which will adduct
paraffins,
not
adduct
with
with
urea. The compounds
thiourea include: branched-chained
naphthenic
compounds,
some
ketones,
carbon
tetrachloride and a few
other chloro-carbon compounds, and
some compounds
terpene,
of
classes (I). Table
number of carbon
the
I
shows
atoms,
some
comphene and cyclohexane
some
compounds with the same
of
which
will adduct with
thiourea and some of which will not.
Pure thiourea has at
phases, depending on the
phase contains
three
least five different crystalline
temperature. The room temperature
groups
of
S— N
interactions which
5
Table I
Compounds which form adducts with thiourea compared
with compounds which do not form adducts
[reproduced from Mandelcorn (1)3
Adducting
Adducting
Nonadducting
Benzene
Cyclohexane
O
O
Hethylcyclohexane
Toluene
O=
O=
0
4
n-Buty!cyclohexane
n-Bu'tylbenzene
0
=
4
O-=
6
O
=
3
n-Hexylbenzene
n-Octy!benzene
O
OO
O==O
I-Pheny1-2-cyclohexylethane
1,2-DiphenyIethane
'
n-Hexy!cyclohexane
Phenylcyclohexane
0=20
2-Phenyleicosane
O
s
-
O
2-Cyclohexyleicosane
< 0 = 2 0
2-Cyclohexyleicosane
C
O
O - ^ - cIS
I1A-Diphenylbutane
n-octy!cyclohexane
1•2-DicyclohexyIe thane
cr O
I-Phenyleicosane
O 6
O
=
S
i-Sa
I,A-Dicyclohexylbutane
0=4-0
0=40
Decalin
6
involve hydrogen atoms
(8).
These distances are—
3.394A,
3.526A, 3.696A.
X-ray crystallographic studies of urea adducts with nhydrocarbons of lengths varing from
Cg to C 50 were made by
Smith (9) and
Schlenk (4). These adducts crystallized in
2
space group C6^2-Dg
with 18 urea molecules per unit cell
r
and hexagonal lattice parameters a=8.230 A, c=ll.005 A. The
urea molecules
form
three
interpenetrating spirals which
are the walls of
the
hexagonal
are held together
by
hydrogen
channels (I). The spirals
bonds between the nitrogen
hydrogens and the oxygen atoms.
The hydrocarbon
molecule
is
formed by the honeycomb walls.
the channel. The
carbon
crystalographic studies have
some
adducts.
The
determined, but the
Analysis suggests the
channel
occurs
urea
to
positions about 120° apart
the c-axis length. X-ray
molecule
of
of the hydrocarbon
determined
disorder
molecule around its long
(I) .
length
hydrocarbon
because
in the channel
The c-axis is parallel to
chain
molecules roughly corresponds
located
the structures of
positions
are
well
molecules are disordered.
of
the hydrocarbon in the
rotation
of
the hydrocarbon
axis. Three fixed, yet equivalent
have
been proposed by Fetterly
7
In the
urea
network
each
oxygen
atom
is hydrogen
bonded to four nitrogen
atoms,
is bonded to two oxygen
atoms. These hydrogen bonds are of
two types; one about 2.93 A
and each nitrogen hydrogen
long and the other 3.04 A long
(1 0 ).
Thiourea adducts with non-aromatic hydrocarbons show a
structure similar to
molecules form a
that
of
urea
adducts. The thiourea
rhombohedral
unit
cell,
hexagonal cell similar to
that
group is R3bar 2/C,
hexagonal
with
with a pseudo-
of urea adducts. The space
axis
of a=b= 15.8 A,
c=12.5 A and eighteen thiourea molecules per unit cell (I).
Tlie
c-axis
roughly
parallels
adducts, the thiourea
the
molecules
channel.
As
in urea
form the honeycomb-shaped
walls of the channel.
The unit
cell
larger than those
and
of
channel
urea
of
adducts
thiourea adducts are
because of the larger
size of the sulfur atom in thiourea than the oxygen atom in
urea. The channel diameter
(I), that for
thiourea
of
is
larger channel explains
urea
reported
why
is reported as 5.25 A
as
6.1
A (2).
The
thiourea forms adducts with
different compounds than urea.
Schlenk found that as
the mole ratio of
organic
increases
urea
(4).
the
guest molecule gets longer
molecules or thiourea molecules to
This
increase
causes
the
non-
8
stoichiometric relationship between
molecules
and
the
number
of
the number of thiourea
guest
molecules.
Table 2
presents the length of
the
the molar ratio of the
number of thiourea molecules to the
number of guest molecules.
to
guest
molecules
molecule length.
guest molecule plotted against
The ratio of thoiurea molecules
increases
This
with
increase
molecule occupying a longer
is
increasing
caused
section
by
guest
the guest
of the channel as it,
the guest molecule, gets longer in length.
Schlenk
suggested
an
molecule's oxygen atom and
2800 cal per CH2
the
urea
the
between
the urea
guest hydrocarbon of about
group (11). Fetterly discounted Schlenk's
suggested interaction
and
interaction
oxygen
between
atom
the
(I).
hydrogen bonding occurs between
hydrocarbon CH2 groups
In
Fetterly's
view no
hydrocarbon groups and the
V
urea
oxygen
atom.
Fetterly
hydrogen bonds in the urea
adducts together. This bond
claimed
that
the
H-H••••0
structure is enough to hold the
is
shorter in the urea adduct
(2.93 A) than a similar bond in pure crystalline urea (2.99
A). The shortening
of
this
bond
energy state. Fetterly proposes
bonding, the "supported
hydrogen bond"
supported
by
a
an
a
hydrogen
corresponds
to a lower
new concept in hydrogen
bond". In his "supported
stronger
hydrogen
bond
exists only if
otherwise
inert
surface,
(the channel
hydrocarbon) which exerts only weak dispersion forces.
r
$
1
molecules thiourea / molecule guest
^
Lm
<T\
x
O*
VO
I
P) cn
I
O)
rj M
f6
£ S?
O
i i r
0 CD
•X
T
3T CTV
OS
*m4
V
O o*
CZta
C
VO
rhiO
^Cyc/opcntanc
? C
H-(
D
'•Pinacolonc
Ul O M
T elrahydrodicyc/opcntadiene
B
I
ro (c g
,D ecalin
^p-McnlIianc
Cyc/ohexylbenzene
^DicycfohcxyIaminc
D
••
H
ID
O
^
(T)
C
M
ft (Tl
U
PTTJ
1 H
(D O
p-Dicyc/ohcxylbcnzenc
1TJ ft
I ft
0 (D
p. a
n P
, Dihydrocitroncllyl pivalate
(Tl U9
O- Pi
,CitroneIIyI ISOvaIerate
•-h3
H-
1a
B^
ft
£
g
H
CD
Ul
10
The differences in
the
arrangement
thiourea molecules in their
in Figure I. The
arrows
From the
thiourea
the urea and
respective adducts can he seen
point
atom to the carbon atom
of
of
from
the oxygen or sulfur
the urea or thiourea molecule.
adduct
structures
Schlenk
found that
three sulfur atoms are coplanar (4). The sulfur atoms point
straight into the center
12.5A apart in
the
c
of
the channel. These planes are
direction;
this
dimension along the c-axis. Figure
is
the unit cell
I shows these planes as
hatched areas.
The
variation
in
the
arrangement
of
the thiourea
molecules in relationship to the channel causes a variation
in the interaction
forces
and the guest molecules.
between
Schlenk
the thiourea molecules
predicted that.the sites
of maximum attraction correspond to the plane formed by the
sulfur atoms (4). Regardless of
interaction are located
will
only
include
in
ratios of 3:1, 6:1,
depending on the
the
one
Therefore, the thiourea
where the sites of maximum
site
unit
of
molecules
cell
r the
maximum
unit cell
interaction.
to guest molecules mole
9:1
or
some other multiple of three,
length
of
the
guest
molecule, will be
favored. This is even true for some molecules which are not
a
multiple
of
c/2
in
length.
Schlenk
claimed
that
hydrocarbon molecules fold or "slide together inside of the
channel
to
give
the
multiples
of
three
11
Figure I
Lattice of urea (left) and thiourea (right) adducts
Top:
Each circle represents a urea or thiourea
molecule, the arrrow points from the
oxygen or sulfur atom towards the carbon
atom. The filled circles represent a
spiral of urea molecules in the urea
lattice and the coplanar sulfur atoms in
the thiourea lattice.
Bottom: cross section with included hydrocarbons
[reproduced from Schlenk (4)3
12
for the
mole
ratio
(4).
Guest
"slide together" give mole
three.
Based
on
determined that
ratios
measured
the
which can not
other than multiples of
crystal
favored
results of this "sliding
molecules
mole
densities,
ratios
together"
he
also
are always the
process and not due to
empty gaps in the channel (4).
Schlenk
reported
that
some
hydrocarbons. ;which
by
themselves do not form adducts will form adducts if certain
adduct formers,'termed inductors, are present (4). Included
in these non-adduct formers which
can be induced to adduct
are benzene, toluene and the xylenes (6).
Gorton determined
will adduct by itself
that
and
1,2,4
trichlorobenzene (TCB)
serves
as , an inductor for the
xylenes and other aromatics (12).
Welling reported that
adducts with thiourea, and
trimethy!benzene (TMB)
all
the
that
will
TCB isomers will form
only
adduct
diffractometer data was collected
the 1,2,4 isomer of
by
itself (3). X-ray
by Welling on a thiourea
adduct containing a mixture of 1,2,3 TCB and 1,2,4 TMB. The
space group was found to be P2^/c with unit cell parameters
of a=12.64 A, b =15.3 A,
c=9.8
A, cx=^=90 and 3=113.85. The
Molecular Structure
Corporation
the thiourea adduct
of
parameters a=12.3
A,
1,2,4
b=15.1
obtained
TMB
A,
(3).
c=10.0
a structure for
A unit cell with
A,
cx=y=9.0..0,
and
13
p=112.7°
was
concerning
found.
the
Welling
interaction
hydrocarbon carbons from
found
for
the
of
this
existence
of
shortening of the non-bonded
and a sulfur atom. The Van
of Vhn der
Waal
radii
several
the
conclusions
thiourea
sulfur and
structure. The evidence she
a
hydrogen
distance
bond
is
the
between' a C-H group
der Waal distance, i.e. the sum
for
C-H-- S ,
distances between a C-H group
than this Van der Waal
drew
and
is 4.08A (13). Four
a sulfur atom were less
distance. These distances are given
in Table 3.
Table 3
Interatomic distances between sulfur and
carbon in the 1,2,4 TMB and 1,2,3
TCB thiourea adduct
om I
Atom 2
SI
SI
SI
S2
Distance
3.90A
3.65A
3.81A
3.91A
CU
C12
C13
C13
These distances are less
than
4.08A and may indicate
hydrogen bond interactions. Angla suggested the presence of
a strong coordination bond between
hydrocarbon molecule
adduct (2).
in
the sulfur atom and the
the thiourea-carbon tetrachloride
14
An explanation for 1,3,5 TMB and 1,2,3 TMB not forming
an adducts can be
found
in geometric considerations. From
the drawing in Figure 2 it
may
situate in the channel
such
in
be seen that 1,2,4 TMB can
a
manner that the methyl
groups lie in the channel. However, 1,3,5 TMB and 1,2,3 TMB
can not be situated such
that
all three methyl groups are
in the channel (3).
Welling suggested
some
possible
explanations of the
action of adductors and non-adductors based on the electron
configuration of the
molecules
benzene will not adduct
TCB will.
Therefore,
with
the
(3). As mentioned earlier,
thiourea, but the isomers of
size
or
planar
nature of the
benzene molecule can not
be responsible for inhibiting the
formation of an
In
adduct.
thiourea
both the sulfur and
nitrogen atoms have lone pairs of electrons. The electronic
structure of benzene contains pi clouds which lie above and
below the plane of the carbon atoms. These pi electrons are
delocalized and form a "donut" of electron density. Welling
suggested
that
the
electrons of benzene
repulsion
and
the
forces
lone
between
the
pi
pairs of electrons in
nitrogen and sulfur are too great to allow the formation of
the thiourea lattice. The
influence the
formation
chlorines
of
the
of
TCB
must somehow
adduct. Welling asserted
that the chlorine atoms are involved in hydrogen bonding.
■
«%»i
H
Ul
Figure 2
1,3,5 T M B , 1,2,3 TMB and 1,2,4 TMB in the channel
of a thiourea adduct
16
"Chlorine is an electronegative atom
and it is recognized as a hydrogen bond
acceptor. Chlorine is able to withdraw
electron energy from the pi clouds around
benzene and is receptive for hydrogen
bonding with the N-H group in thiourea."
In related work
Fait
the crystal structures
and
Fitzgerald (14) determined
for the cyclohexane-thiourea adduct
V
and the carbon tetrachloride-thiourea adduct. The unit cell
parameters reported for
these
Table 4. Both of
structures
R3bar,
which
these
is
typical
exhibit the honey-comb
thiourea with the
structures are presented in
of
non-aromatic
type
adduct
are in the space group
adducts,
and
channel structure formed from
molecule
occupying the channel.
The channel structure is illustrated in Figure 3 which is a
stereoview of
the
carbon
tetrachloride structure looking
down the c-axis.
The
thiourea
positions
were
easily
found
in
the
refinement of both of
these structures. More difficult was
the determination
a
of
model for
the
molecule
in the
channel. In Figure 3 the sulfur atom of the thiourea can be
seen
pointing
into
channel
at
the
enclosed
carbon
tetrachloride molecule. This sulfur atom is hydrogen bonded
to other thiourea atoms and
molecule for Van
der
Waals
is close enough to the channel
interactions.
Tables 5 and 6
present contact distances between the sulfur atom and
Table 4
Unit Cell Parameters for Cyclohexane and Carbon
Tetrachloride Adducts Cfrom Fait and Fitzgerald
(14)3 (all distances in A, numbers in
parentheses are standard deviations)
H
I Hydrocarbon
(Cyclohexane
I
ICCl4
I
-
■ : ____
—
r ~
f
i
i
I A
I
B
l
C
I
a
(15.708(1)(15.708(1)112.431(2) | 90.0
I
I
I
I
15.539(1)" 15.539(1) (12.529(2) I 90.0
I
I
I
-I----------------------
I
I
B
I 90.0
I
.
I 90.0
I
V
I 120.0
I
I 120.0
I Space
I Group
I R3bar
I R3bar
I
I
I
I
I
18
Figure 3
tetrachloride molecule.
Cfrom Fait and Fitzgerald (14)3
19
Table 5
Cyclohexane-thiourea adduct sulfur-aromatic carbon
distances. Cfrom Fait and Fitzgerald (14)I
Atom I
SI
SI
SI
SI
Atom 2
C13
C12
C14
CU
Distance
3.7918A
3.8306A
3.8697A
3.9577A
Table 6
Carbon tetrachloride-thiourea adduct sulfur-chlorine
distances [from Fait and Fitzgerald (14)3
Atom I
SI
SI
SI
SI
Atom 2
CL5
CL3
CL2
CLl
Distance
3.583IA
3.7588A
3.9808A
3.9856A
20
channel molecules for each
arrangement is seen in
From these
of
all
distances
these structures. This same
of
and
the thiourea adduct walls.
special
oreintations, Fait and
Fitzgerald suggest that there is an interaction between the
thiourea sulfur atom and atoms of the enclosed molecule.
Also in related
work
Wick
the crystal structure of 1,2,4
and Fitzgerald determined
TCB (15). This structure is
in the space group P2^/c, which is the same as the aromatic
structures
reported
by
Welling
structural
information
for
this
walls of this structure
are
similar to the wall structure
seen in the non-aromatic
(3).
Table
structure.
7
contains
The channel
structures, except that the walls
•are no longer hexagonal. The
allow the bulkier aromatic
channel has been distorted to
molecule
to fit in. This shows
the flexibility of the thiourea channel structure to change
its shape under the influence of the guest molecule.
An
interesting
selectivity
for
selectively
form
some
isopropyl, 4-methyl
(5).
characteristic
an
of
thiourea
geometric-isomers.
adduct
with
cyclohexane)
cis-para
is
Thiourea
its
will
menthane (1-
over trans-para menthane
Table 7
Structural parameters for 1,2,4 TCB-thiourea adduct
structure [from Wick and Fitzgerald (15)3
I Hydrocarbon
IAdducted with
11,2,4 TCB
I
I
l
l
l
I A
I
B
I
C
I
a
I 9.779(1)|15.355(1)|12.293(2)I 90.0
I
l
l
l
I
I
I
B
I
V
I 111.85 I 90.0
I
I
I Space
I Group
I P2./c
I
I
I
I
I
22
Research Objectives
The
objective
of
this
research
crystal structures of thiourea
explain the behavior
of
was
to
determine
adducts which would help to
thiourea
adducts.
This would be
accomplished by:
1) Determination of the crystal structure of the 1,2,4
TCB-I,2,4
TMB
thiourea
adduct
structures found by Welling
and
comparison
to
the
(3), Fait and Fitzgerald (14),
and Wick and Fitzgerald (15).
2)
Obtaining
an
adduct
structure
in
which
the
hydrocarbon is sterically hindered enough to allow use of a
model for
the
hydrocarbon
molecule
in
the channel with
minimal disorder.
3) From
the
characteristics of
adduct
the
structures
interaction
determination of the
between
molecules and the hydrocarbon molecules.
the thiourea
23
EXPERIMENTAL
Crystal Growth.
Obtaining crystals satisfactory
for x-ray diffraction
proved difficult. The quality and size of crystals obtained
depended on
the
and on the rate
thiourea
of
behaved differently
and hydrocarbon concentrations,
cooling. Each hydrocarbon investigated
when
forming
methanol was saturated with
of methanol and
solid
any adduct that formed.
removed from the heat
to cool to room
thiourea
thiourea.
added. After stirring, the
In
all cases
by heating a mixture
Then the hydrocarbon was
mixture
When
and
adducts.
the
was heated to dissolve
mixture cleared, it was
sealed.. The mixture was allowed
temperature.
The crystals best suited for
x-ray diffraction study appeared in 12 to 24 hours.
Adducts
crystals.
form
Pure
long,
clear,
thiourea
crystals
hexagonal plates, but also
are sometimes difficult
crystals.
to
hexagonal,
are
needle-like
typically
clear,
form odd shapes crystals. These
tell
apart
from short adduct
24
1,2,4 TMB and 1,2,4 TCB adduct
A 50-50 weight percent mixture
TCB was prepared. About
added
to
thiourea.
20
5
milliliters of this mixture was
milliliters
This
of 1,2,4 TMB and 1,2,4
procedure
of
methanol
saturated
with
gave
crystals
of satisfactory
quality.
Cis para-menthane adduct
Three milliters of cis
milliters
of
methanol
para-menthane were added to 20
saturated
with
thiourea.
These
crystals were of better quality than the aromatic adducts.
Crystal Analysis
Crystals containing
analyzed
using
Chromatograph
a
a
mixture
Varian
with
of . hydrocarbons were
Aerograph
strip
chart
Series
recorder.
A
1400
batch
Gas
of
crystals to be analyzed was vacuum filtered from the mother
liquor and then
spread
Prolonged exposure to
out
air
on
paper
causes
towels to air dry.
most adduct crystals to
deteriorate and
become an opaque white color. After drying
for a couple of
hours,
the
crystals
were dissolved in a
minimum amount of boiling water. When all the crystals were
dissolved the solution was
allowed
formed. The organic
was
phase
to cool and two phases
separated from the aqueous
25
phase in a separatory funnel. A sample of the organic phase
was then analyzed using
the
gas chromatograph. Helium was
used as the carrier gas.
A
5%
diisodecylphthalate
Chromasorb N column
aromatic mixtures.
at
150°
C
and
5%
was
used
Known
samples
were
relationship between area
percent
and
known samples of 1,2,4 TMB
and
determined that"for
compounds
these
bentone
34
on
to analyze the
used
to find the
mole percent. From
1,2,4 TCB solutions it was
area percent exactly
corresponds to mole percent.
A method for
analyzing
adduct crystal was developed.
in a minimum amount
of
the
hydrocarbons in a single
A
single crystal was placed
solvent
nitrile or a heavy alcohol)
(2
ml of acetone, aceto­
and allowed to dissolve for an
hour. A sample of this solution was then analyzed using the
gas chromatograph. The best
solvent
to use depends on the
gas chromatograph column used and for what hydrocarbons the
analysis is being done
to
single phase when
adduct
the
detect.
is
interfere with the hydrocarbon peaks
desired.
A solvent that forms a
dissolved
and does not
on the strip chart is
26
Adduct Density
A floation method was used to determine the density of
adducts.
Adducts
were
suspended
miscible liquids, one more
less dense. A mixture
was used to
suspend
a
than
mixture
of
two
the adduct and one
of carbon tetrachloride and methanol
adducts.
just suspend an adduct,
sink nor float, was
dense
in
that
When
is
obtained,
10
a mixture which would
the adduct would neither
ml
of the solution was
removed and weighed and the density calculated.
Crystal Mounting
Crystals
were
removed
from
the
mother
liquor and
placed in a drop of Paratone-N on a microscope slide. Under
the microscope the crystals
were
cut across their length.
It was difficult to get a clean cut on the adduct crystals,
as they often fractured
resembled a bundle of
along
their length. Some crystals
smaller
needle-like crystals, a few
were even hollow tubes. Pieces of crystals that were of the
right size, shape and showed no signs of twinning (multiple
crystal growth) were
under
polarized
checked
light.
to
Those
see if they extinguished
that
did
extinguish,
indicating a single crystal, were selected for mounting.
To prevent
sealed
glass
deterioration,
capillary
tubes.
crystals
The
were
cis-para
mounted in
menthane-
27
thiourea crystal used, for
data collection was cylindrical
with a diameter of 0.8 millimeters
The 1,2,4
TMB-I,2,4
collection was
TCB
also
and a length of 1.2 mm.
adduct
that
was
cylindrical
with
a
millimeters and a length of
larger crystal, such as
0.8
used for data
diameter of 0.7
mm. It was found that a
those
used, were desired in order
to give observable reflections
out to larger angles, since
the
disorder
within . the
crystal
made
the
high
angle
reflections weak.
Photographic Film Studies
Weissenburg photographs
were
select satisfactory crystals.
Once
was found, oscillation, zero
nickel
filter
photographs. These
was
and
used to
a satisfactory crystal
level, first level and second
level Weissenberg photographs
with a
collected
were taken. Copper radiation
used
photographs
to
take the Weissenburg
were
used
to
determine
crystal quality and to estimate unit cell parameters.
I
Diffractometer Data Collection
Intensity data for both
Nicolet R3mE four
technique,
graphite
with
crystal
circle
MoK2
compounds were collected on a
diffractometer
radiation
monochromator.
using the w scan
monochromated
Both
data
with
sets
a
were
28
collected at room temperature.
reflections were
collected
In each case three standard
every
one hundred reflections
throughout the course of the
data collection. There was no
decrease in these
over
collection
on
standards
either
crystal.
menthane adduct was collected
Data was collected on both
Only
unique
25
selected from the data
for
the
the
cis-para
the
sphere
were collected.
were obtained from a
reflections which were
and then recollected. These 25
the
1,2,4
TCB-1,2,4 TMB adduct
220<2©<28°. The 25 centering reflections
cis-para
270<2©<34°.
for
from 3° to 50° on 20.
crystals
set
course of the data
the hexagonal unit cell.
centered
centering reflections for
were in the range
on
in
Lattice parameters for both
of
Data
crystals
reflections
least-squares fit
the
menthane
Asmuithal
adduct
were
adsorption
in
correction
the
data
range
was
collected for both structures, but the transmittance varied
so little
that
no
correction
absorption factors used were:
was
for
necessary. The linear
the 1,2,4 TMB-1,2,4 TCB
-I
adduct
Jj(MoK2 )=
6.53
cm
,
for
the
cis para-menthane
adduct p (MoK2 )= 3.95 cm
The two data
with
appropriate
sets
were
Lorentz
and
Scattering factors for Cl, S,
scattering terms for
all
reduced
in the usual manner
polarization
0,
types
corrections.
N, C and H and anomalous
except
H were taken from
29
International Tables, for
atoms were assumed to be
1,2,4
TCB-I,2,4
TMB
direct methods. Since
X-ray
Crystallography (16); all
in the zero ionization state. The
structure
the
was
thiourea
solved
initially by
molecules in the cis-
para menthane structure are isostruetural with the thiourea
molecules in the
Fitzgerald
cylcohexane
(14),
sulfur
positions
tetrachloride structure were
the cis-para menthane
were
refined
structure
used
structure.
using
a
found by Fait and
from
the
carbon
for
initial phasing of
Both
of these studtures
blocked
cascade
least-squares
refinement program in which the minimized function is:
M=EWeight(IFobsI-IFcalcI)2
(17),
in which Weight is a weighting factor, Fq 1js is the observed
structure factor
factor.
The
and
Fcalc
thiourea
is
model
in
the
calculated structure
both
adducts
was
well
defined, and in the final stages of refinement the thiourea
portion of the model was refined anisotropically. The major
problem with both of these structures was with generating a
model which described
the channel. As the
the
disorder
of the hydrocarbon in
model
improved
the hydrogen atoms of
the thiourea molecules
began
appearing
maps and were added to the structure.
in the difference
30
RESULTS AND DISCUSSION
Discussion of X-ray Crvstallocrraphv
When x-rays pass through a crystal they are diffracted
by the electrons of the
atoms
diffraction pattern. This
with Bragg's
Law
(nx=
incident radiation,
0= angle between
the
diffraction occurs in accordance
2d
sin©
incident
or reflected radiation and
intensities of
these
m=l,2,3,...).
diffracted
diffractometer collects this
intensity
a
of
positions and
accurate
scattering
in
x-rays
x-ray
the
positions and
are
recorded. A
with a radiation
intensity measurements. The
factor
is
determined
(related
to
by the
the atomic
crystal. The angles at which
the diffraction occurs depends
of the crystal. Thus, the
The
information
diffracted
number) of the atoms
wavelength of
X=
between reflecting planes,
surface,
gives
where
d=distance
the reflecting
counter which
in the crystal, creating a
upon the lattice parameters
intensities of the diffracted x-
rays depend on this structure. Information about the phases
of the diffracted x-rays is
diffraction pattern. The
not directly observable in the
solution . of
a crystal structure
involves the development of sufficient phase information so
that an adequate model for
the arrangement of the atoms in
31
the crystal
agreement
factors.
can
be
between
observed
Initial
syntheses and
obtained
models
refined
can
by
which
and
be
least
lengthy calculations involved are
refines to produce
calculated
extended
squares
made
structure
using Fourier
procedures. The
possible by use of
computers.
The systematic
absences
of reflections (extinctions)
are determined by space group symmetry. Thus observation of
systematic absence reflections
symmetry of the crystal.
allows determination of the
However,
the space group may not
be uniquely defined by the systematic extinctions.
The probable correctness of a model can be measured by
the R value.
observed
and
The
R
value
calculated
measures the agreement between
structure
factors:
different
methods of weighting the structure factors give different R
values. One R value is given by the equation:
R=
m F 0lzJFcU _ ,
SIf0I
other R's are:
1/2
Rw=ZC M F ^ I- IF^ II*(weicrht)
3
ECFq A (weight)1/2J
7
1/7
Rg =----------------CE(weicrht*C IIF
I-IF m z)3±/z
— O u— — C-1-1---------ECweight*Fo2]
R =R (calculated for the scale factor which
g minimizes R ),
g
where
If q I
is the scaled observed structure factor and
is the calculated structure factor (17). A further
If c I
32
explanation of x-ray crystallography
can be found in Stout
and Jensen (18).
Cis para-Menthane-Thiourea Adduct
As
adducts
mentioned
with
. earlier
cis
methyl cyclohexane)
was
found
selectively
para-menthane
over
trans
selectivity for a geometric
It
thiourea
that
forms
(1-isopropyl,
para-menthane
di­
(5).
This
isomer prompted further study.
cis
para-menthane
crystalline adducts that are of
easily
forms
fairly good quality for x-
ray diffraction study.
The crystal density
g/ml. From this value
para-menthanes
was
consistent with
determined
the
mole
value
of
floation was I.16
ratio of thioureas to cis
calculated
the
by
to
be
about
4.8
4.62.
This
is
obtained from
Schlenk's graph (Table 2).
A diffractometer data set was collected on a cis paramenthane -thiourea
adduct.
intensities,
which
of
This
969
data
were
set
contained 3480
considered
observed
reflections.
Laue group symmetry suggested
A least squares fit
of
25
a space group of R3bar.
selected reflections gave unit
cell parameters of a=b=15.935(2)A, c =12.489( 2)A , ot=p=90.0°
and
y =120.O0
deviations).
(numbers
in
parentheses
are
standard
33
Indications of a super-lattice
photographs
taken
collection. The
on
the
axial
diffractometer
photographs
axis contained spots that
layer lines. These
were seen in the axial
do
not
fourteen
prior
taken
line
to data
on rhombohedral
up with the other
reflections
in between layer
lines were seen on all three rhombohedral axial photographs
and were about one-third
of
the distance in between layer
lines. These indications prompted
shell of 20=3.0° to 20=12.0°
indications of
a
the collection of a thin
with
super-lattice
sets. In retrospect it
might
hk21 and then 2h2kl. No
were
have
seen
in these data
been best to collect a
thin shell with hk31.
After initial phasing
the isostructural
with
carbon
the
sulfur position from
tetrachloride
thiourea molecules were easily
adduct
(14), the
located on difference maps.
At first any peaks that showed up in the channel were added
to the model
and
gave a solution
were
with
allowed
a
low
carbon atoms in the channel
search for a cis
to refine. This procedure
R
value (R=0.0427) , but the
made no chemical sense. In the
para-menthane
molecule in the channel it
was noticed that if the channel were viewed down the c-axis
a repeating pattern could be seen.
As Figure 4 shows, the
atoms in the channel appear to
form a small circle ringed by a larger circle. The 3-fold
34
Figure 4
Cis para-menthane adduct without the model for the
hydrocarbon molecule, viewed down the c-axis
35
axis of symmetry runs down the middle of the channel in the
c-direction. This suggests that some of the atoms of the
cis para-menthane molecule lie
and the others are
were the case, it
molecule is
located
would
disordered
on
on
the larger circle. If this
appear that the cis para-menthane
because
itself about the 3-fold
or near the 3-fold axis
axis
it
in
carbon atoms in the channel
ten
para-menthane molecule were
found
is
free to orientate
the channel. From the 19
that roughly formed a cis
and then constrained to
form an idealized cis ; para-menthane molecule. In the final
stages of
refinement
weighting
factor
a
was
weighting
factor
was
used. The
Weight=I/(sigma**2(F)+G*F*F)
G=O.00040. Refinement of
this
model
gave
where
a reasonable R
value (R=0.0670, Rw =O.0707,
R^=O.0986, Rm=O.0986, goodness
of fit=3.341).
was
This
model
used
to find interatomic
distances which would characterize the interactions between
the
thiourea
sulfur
molecule. Appendix B
atom
and
contains
the
tables
cis
para-menthane
for publication for
this structure.
Figure
5
shows
molecule. Figure 6
the
also
menthane molecule but . is
generated
hydrogens.
The
disordered about the three
constrained
shows
a
the
space
cis
fold
cis
para-menthane
constrained cis parafilling plot with four
para-menthane
molecule is
axis, which runs parallel
to the center of the channel, with three equivalent
Cp2
Figure 5
Constrained cis para-menthane molecule with 50%
probability ellipsoids
37
Figure 6
Space-filling plot of constrained cis para-menthane
molecule
38
f
Figure 7
Packing plot of cis para-menthane molecule showings it's
three orientations about the three fold, center
of symmetry
39
positions 120° apart. This disorder can be seen in Figure 7
which contains only the cis para-menthane molecule.
Interatomic distances
calculated using the
between
graphics
package (17) and from
the
non-bonded
package
atoms were
in SHELXTL program
XTAL system of crystallographic
programs (19).
Figure 8 shows a single sulfur atom hydrogen bonded to
four other thiourea molecules
bonds).
These
hydrogen
3.4022(0.0096)A,
3.4579(0.0058)A
(numbers
channel offset by 20°;
lengths are
bonds
are
3.4054(0.0043)A,
deviations). Figure 9
bonds are drawn
(the open lines are hydrogen
in
longer
is
a
in
as
than
crystalline thiourea at
(8), although the
in
room
not
be
lengths in
the
thiourea
are
and
standard
some of the hydrogen
lines.
All of these bonds
shortest
hydrogen
temperature
bond in
which is 3.394A
between 3.4022A, 3.4054A and
significant.
network
significantly shorter than the
lengths:
view looking down the
plot
dotted
difference
3.394A may
parentheses
the
four
3.4375(0.0040)A
stereo
the
of
The
of
four
hydrogen bond
the
adduct are all
remaining two hydrogen bond
lengths in crystalline thiourea at room temperature, 3.526A
and 3.696A (8).
These
shorter
hydrogen
bonds
indicate
that
thioureas are more closely packed in the walls of the
the
40
Figure 8
hydrogen bonds.
41
Figure 9
Stereoview of the hydrogen bonding in the thiourea
network of the cis para-menthane adduct
structure, viewed down the c-axis
offset by 20*. Some hydrogen
bonds are drawn in
as dotted lines.
42
adducts than in
crystalline
As Fetterly pointed out in
thiourea at room temperature.
his
tighter packing and shorter
a
lower .energy
study of urea adductsr the
hydrogen bond lengths indicate
state.
These
strong
hydrogen
bonds
contribute to the formation of the adducts > but contrary to
Fetterlys opinion they by
themselves probably do not hold
the adducts together. This
is
evident ' from the fact that
some hydrocarbons form adducts
while other hydrocarbons of
the same geometry will not form adducts. An example of this
is cyclohexane which will form
will not
form
an
of
an
indication
molecule and the
adduct
the
(see
interaction
thiourea's
vary so widely in
air, but
an abduct and benzene which
Table
between
sulfur
stability.
I). Another strong
the
atom
hydrocarbon
is that adducts
Most adducts are unstable in
adduct, containing
bicycloC2.2.23 octane is
stable in air (14).
Schlenk ■ found
that
in
occurs three coplanar sulfur
the
thiourea
atoms
network there
every unit cell length
in the c-direction (12.5A), and
all three of these Sulfurs
are pointing
of
pattern was
into
found
the
center
in
the . cis
relationship between the
the. channel (4). This
para-menthane adduct. The
sulfur 'atoms and the hydrocarbon
molecules can be seen in Figure 10. The three planar sulfur
can be seen pointing in at
the cyclohexane ring of the cis
para-menthane. Figure 11 shows three thiourea molecules
43
Figure 10
Stereoview of the cis para-menthane adduct structure
with a model for the cis para-menthane molecule,
viewed down the c-axis offset by 20°.
44
Figure 11
Space-iiliing Plot of three thiourea molecules with planar
sulfur atoms and the cis para-menthane molecule with eight
generated hydrogen atoms viewed down the c-axis
45
with coplanar sulfur atoms
to the cis para-menthane
and
their position in relation
molecule;
equivalent positions is shown.
only
one of the three
The orientation of the ring
carbons and the sulfur atoms
is evident. One of the sulfur
atoms is pointing in between
the
center of the ring while
the other two sulfur are pointing
in at the two carbons on
each side of the ring.
This
relationship can also be seen
in Figure 12 which is a view looking down the sulfur-carbon
bond of thiourea molecule
which
the ring. The distances from
points into the middle of
each of these sulfur atoms to
the ring carbons are in Table 8.
The distances between SI, the sulfur pointing into the
center of the cyclohexane
ring,
all too long for
strong interaction to occur (see
a
very
Table 8). The other two sulfur
carbons on the sides of
the
and
the ring carbons are
atoms, SlA and SIB, and the
ring
are close enough for an
interaction to take place (see Table 8). A hydrogen bond is
possible if the atoms are closer
der Haal
radii.
The
van
der
1.76+0.04A and that for hydrogen
than the sum of their van
Waal
which
the
of sulfur is
is 1.20A (20). The radius
for the carbon-hydrogen covalent bond
hydrogen bond in
radius
hydrogen
is 1.08A (13). For a
atom is linearly in
between the carbon and sulfur atom, the shortest non-bonded
distance is the sum of these three radii, which is 4.04A.
Figure 12
Three thiourea molecules with planar sulfur atoms and a
cis para-menthane molecule with eight generated
hydrogens, viewed down the S-C bond of a
thiourea molecule with the NHg
group removed
47
Table 8
Interatomic distances between sulfur and carbon,
or sulfur and hydrogen atoms in the cis paramenthane adduct structure. Numbers in
parentheses are standard deviations.
I Atom I
I
I
I
I
I
I
SI
SI
SI
!_ SI
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
SI
I Atom 2 I Distance (in A)
I
CRl
I
I
I
I
I
I
I
I
4.6946(0.0231)
I
CR2
I
4.6392(0.0263)
I
4.9911(0.0030)
I
CR 4
I
CR5
SI
I
SlA
I
4.8403(0.0505)
I
4.8973(0.0454)
CR6
I
4.5926(0.0177)
I
CRl
I
3.9073(0.0279)
SlA
I
CR 2
I
4.0637(0.0273)
SlA
I
SlB
SlB
SlB
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
HRlB
HR2A
I
I
3.342
I
I
I
I
3.7429(0.0276)
I
3.8925(0.0321)
I
I
I
I
J.
3.105
I
CR 5
I
I
CR 4
I
HR5A
I
SlB
I
I
I
I
CR 3
I
SlA
I
I
I
I
I
3.018
I
HR4A
I
3.177
Table 9
Van der Waal radii distances between sulfur and carbon atoms
in the cis para-menthane adduct
I
I
I
I
CO
r-~
Atom 2 I Distance (in A) I
CRl
I
3.87
I
CR 2
I
3.78
I
CR5
I
3.79
I
CR4
I
ro
Atom I
SlA
SlA
SlB
SlB
48
From the distances in Table 8
SlB seem to
be
close
it
enough
can be seen that SlA and
to
the
ring carbons to be
hydrogen bonded, but the hydrogen atoms are not linearly in
between
the
sulfur
atoms
thehydrogen atoms are more
and
than
the
carbons.
All
of
2.96A (1.76A+ I .2GA) from
the closest sulfur atom.
Since the sulfur,
hydrogen
linear, they form a
triangle.
and the
two
distance
length
of
between
the
sulfur
carbon
angles of the triangle
the
and
van
der
hydrogen
distance
can
distances
carbon atoms. These values
the sulfur and
carbon atoms are not
Waal radii
and
the C-H
known. By trigonometry the third
sulfur-carbon
contains the calculated
The
sides,
covalent bond radius, are
side, the
and
be
found. Table 9
between
the sulfur and
represent the distance at which
atoms
overlap
thier
van der Waal
radii. Hie overlapping of van der Waal radii would indicate
the beginning of
a
hydrogen
bond.
Only
SlB and CR5 are
closer than this calculated distance.
Only this
interatomic
provides evidence of
atoms and
the
distance
hydrogen
cyclohexane
bonding
ring
C-H
sulfur atoms are close
enough
to
interaction. The
likely
form
most
between
SlB and CR5
between the sulfur
groups.
All of the
the C-H groups for some
of
interaction
is a
dipole-dipole attraction. The double-bonded sulfur atom has
49
two unshared pairs of . electrons
side of the sulfur atom
which are on the opposite
from
the double bond. It is quite
possible that these electrons
could induce an added dipole
in
the
C-H
group.
contributes to the
The
strength
lowering
of
of
the
this
energy
interaction
state of the
adduct.
Figures 7 and 11 provide
is
selective
for
cis
para-menthane
menthane. In Figure 11 the
right above
the
an insight into why thiourea
over
trans
para-
methyl group is in the channel,
cyclohexane
ring.
One
would expect the
trans para-menthane molecule to lie in the same location as.
the cis para-menthane
molecule.
would be in the
position
same
leaves only the methyl
it would be forced to
Also, the isopropyl group
because
of its size. This
group to be positioned differently;
stick
out above the ring carbon and
the
channel. In this position the
away from the center of
trans methyl group would be close
to one of the NH2 groups
of a thiourea molecule to which the sulfur atom is hydrogen
bonded.
This
proximity
might
molecule that is not present
cause
the
cis
of
the
with the cis methyl group and
cause the trans para-menthane adduct
in energy than
distortion
to be a little higher
para-menthane
adduct. This small
energy difference could be enough to account for thiourea's
selectivity for cis para-menthane.
50
1,2,4 TMB-I,2,4,TCB-Thiourea Adduct
Gas chromatography analysis of the 1,2,4 TMB and 1,2,4
TCB-thiourea adduct
indicated
for 1,2,4 TCB over 1,2,4 TMB
that
thiourea is selective
(Table 10). It was found that
a feed mixture of 50 weight percent 1,2,4 TMB and 1,2,4 TCB
gave crystals which were close
to
50 mole percent of each
aromatic compound (Table 10).
Table 10
Gas chromatograph analysis of 1,2,4 TMB and 1,2,4 TCB
adduct feed, mother liquor after adduct
formation, and extract
I 1,2,4 TMB
Feed
wt%
mole%
Mother
Liquor
mole%
Adduct
Extract
mole%
I 1,2,4 TCB
I
I
I
I
I
I
I
I
50
60.2
I
I
I
63.4
I
I
The measured density for the
the 1.3 g/ml reported
by
36.6
I
I
51.3
crystal was 1.28 g/ml. This
50
39.8
value
Welling
48.7
1,2,4 TMB and TCB adduct
is reasonably close to
(3).
The mole ratio of
thiourea to aromatics was calculated to be 4.43.
51
A x-ray diffraction data set
TMB and 1,2,4 TCB-thiourea
percent of
each
was collected on a 1,2,4
adduct
aromatic.
which contained 50 mole
This
data
set contained 3462
intensities, of which 1725 were considered to correspond to
observed reflections.
In
these
reflections the following
extinctions were found:
Table 11
Reflections absent and the symmetry indicated
for the 1,2,4 TMB-1,2,4 TCB adduct
Reflections Absent
UOO
UOG
UOU
0U0
A space
group
extinctions.
The
b-15.245( 8)A,
(numbers
in
determined
of
Symmetry Indicated
1 n glide perpendicular
^to b
2 fold screw axis on b
P2^/c
unit
was
cell
parameters
c=12.313(6) A,
parentheses
from
the
are
least
determined
from these
of
a-9.886(7)A,
(X=1Y=SO0
and
(3=112.48(4) 0
standard
deviations)
squares
fit
of
were
25 selected
reflections.
The
sulfur
positions
methods. Thiourea carbon
were
and
determined
nitrogen
by
direct
atoms showed up in
the difference maps. Initially, any peak which showed up in
the channel was
added
to
the
model,
but this failed to
52
produce any recognizable
molecule
not significantly lower the
idealized aromatic rings
density was used to
these rings.
geometry were
value. First two, then four
were
constrained. The calculated
the
site occupation factors for
map
constrained
atoms. Only two peaks
found. No model that
peaks
as
that
was
than 0.140. The disorder
the channel and did
R
find
Difference
in
with
methyl
the appropriate
groups
or chlorine
refined as chlorine atoms were
tried
in
almost any reasonable model
provided
the
channel is so great that
will
electron density, but will
not
model to allow determination
a R value lower
account
for some of the
provide an accurate enough
of interatomic distances with
any degree of accuracy. This prevents any conclusions about
the interactions
between
the
thiourea
molecules and the
channel hydrocarbons.
A model with four coplanar idealized benzene rings was
used in refinement. These benzene
and all four rings
were
rings were in two pairs,
coplanar.
were only shifted slightly from
The rings in each pair
each other. Only two peaks
refined as chlorine atoms.
Figure 13 is
a
stereoview
1,2,4 TMB- 1,2,4 TCB adduct.
down
plane
channel of the
The distortion of the channel
walls from the hexangonal arangement
group, can be seen. The
the
of
as in the R3bar space
the benzene ring can be
53
seen in the
molecules
channel.
can
Although
the
not
be
modeled
electron density is
in
a
it
plane
in
1,2,4
is
TMB- 1,2,4 TCB
evident
that the
the channel. This is
consistent with the aromatic adducts studied by Welling (3)
and Wick and Fitzgerald (15).
Even with the
disorder
in
the channel; the thiourea
molecules are fairly well defined. The thiourea network can
be seen in Figures 13 and
the thiourea network in
14.
the
This network is the same as
other aromatic structures (3,
18). Hydrogen bonding between the sulfur atoms and adjacent
NH2 groups is evident.
Four
different lengths of hydrogen
bonds were found. These lengths are 3.378A, 3.393A, 3.433A,
and 3.452A. Even though the
R
value is fairly high, these
lengths should be close enough to the actual values to give
an idea of the nature of the hydrogen bonding. The hydrogen
bond lengths in
are 3.394A,
crystalline
3.526A,
menthane adduct, the
packed in the
adduct
and
3.696A.
thiourea
than
tighter packing
contributes
adduct
structure
crystal
thiourea
with
molecules
in
the cis para-
are more tightly
crystalline thiourea. This
to
in
As
at room temperature
the
lower
comparison
energy of the
to
crystalline
thiourea.
The
spatial
relationship
between
the
thiourea
54
Figure 13
Stereoview of 1,2,4 TMB- 1,2,4 TCB thiourea adduct
viewed down the c-axis
55
"...
••)?•> ' V - 5 F - V ? ;
Figure 14
Stereoview of the 1,2,4 TMB- 1,2,4 TCB thiourea adduct
viewed down the c-axis offset by 20°
56
molecules and the plane of
Figures 15 and 16. Here
pointing
into
the
the
channel,
equilateral triangle as
Figure 16 shows
the
the
in
two
sulfur atoms pointing in
aromatic rings is shown in
three planar sulfur atoms are
but
the
at
adduct.
was
ring.
detected
are
not
in
an
cis para-menthane adduct.
aromatic
molecules are orientated such as
interaction that
they
ring locations and the
It is evident that the
to allow the same type of
in
the
cis para-menthane
57
Figure 15
Three thiourea molecule with planar sulfur atoms and two
benzene rings from the 1,2,4 TMB- 1,2,4 TCB adduct
structure viewed down the c-axis
58
Figure 16
Two thiourea molecules with planar sulfur atoms and two
benzene rings from the 1,2,4 TMB- 1,2,4 TCB
adduct structure
59
>
Summary
Thiourea has the unusual
a large number
of
ability to form adducts with
hydrocarbons.
the thiourea
forms
a
hydrocarbon
molecule
cage-like
in
a
selectively form adducts with
In these adduct crystals
network
channel.
of
extractive
will
is the basis for the
crystallization.
hydrocarbons and isomers of
Thiourea
some hydrocarbons over other
hydrocarbons. This selective property
process
which traps the
a
Classes
of
given empirical formula can
be separated by extractive crystallization.
If the
forces
which
were understood, then the
X-ray crystallographic
hold
selectivity might be understood.
studies
thiourea network is held
thiourea adducts together
have
determined
that the
together by hydrogen bonding, but
this does not explain the selectivity of thiourea.
Structural data for
for this thesis and in
thiourea
related
adducts studied in work
work is presented in Table
12. As can be seen the 1,2,4 TMB-1,2,4 TCB adduct is in the
same space group and has
as the
other
aromatic
menthane adduct structure
a
unit cell nearly the same size
adduct
is
aromatic adducts. One problem
structures.
quite
The cis para-
similar to other non­
that has been encountered is
the disorder of the hydrocarbon molecule in the channel. A
Table 12
Structural data of several thiourea adducts (all distances
in A, numbers in parentheses are standard deviations)
Hydrocarbon
Adducted w ith
C yclohexane
(14)
CCl4
c is
1
1
1
1
1
.2
.2
,2
.2
,2
(14)
p a ra -m e n th a n e
.3
.4
,4
.3
,4
TCB
and
TMB
TCB a n d
TMB
TCB
1 ,2 ,4
TMB
1 .2 .4
1 .2 .4
TCB a n d
TMB
(3)
(3)
I
I
I A
1 1 5 .7 0 8 (1
I
l
11 5 . 5 3 9 ( 1
I
l
11 5 . 9 3 5 ( 2
I
I 12.64
I
I
I
l
I
I
I
B
I
C
I
)|1 5 .7 0 8 (1 )| 1 2 .4 3 1 (2 )|
l
l
) 11 5 . 5 3 9 ( 1 ) 11 2 . 5 2 9 ( 2 ) |
l
l
) 11 5 . 9 3 5 ( 2 ) 11 2 . 4 8 9 ( 2 ) |
I
I
I
I 15.3
I 9.8
|
I
I
I
l
a
90.0
I
I
I
I
90.0
I
I
90.0
90.0
l
I
I
I
(15) I 9 . 7 7 9 ( 1 ) | 1 5 . 3 5 5 ( 1 ) |1 2 . 2 9 3 ( 2 ) |
I
I
I
I
(3)
|12.3
( I ) |15.1
(1 )|1 0 .0
(2)|
I
l
l
l
I 9 .8 8 6 (7 )|1 5 .2 4 5 (8 )|1 2 .3 1 3 (6 )I
I
I
I
I
I
I
I
I
90.0
90.0
90.0
B
90.0
Y
90.0
I
I
I
I
120.0
90.0
I
I
120.0
I
I
I
113.8
120.0
90.0
I
I
I
I
111.85
I
I
I
I
112.7
I
I
I
1112.48(4)I
I
I
I
I
I
I
I
I
I
I
I
Space
Groun
R3bar
I DENSITY
I (<r/cn? )
I
1.138
I
R 3bar
I
I
1.415
I
1.16
R 3bar
P2, / c
IP2I
IP2I
I P2I
,I
/c
90.0
90.0
90.0
I
I
1.27
I
I
1.3
/c
I
/c
I
P2I /c
I
I
I
1.11
1.28
61
model that takes into
account
this disorder was found for
the cis para-menthane
molecule.
Refinement
of this model
for the cis para-menthane adduct gave a R value of 0.067.
Schlenk was the
cell of the
first
thiourea
attraction (10). These
because of three
the
form
of
recognize
adducts
sites
coplanar
channel formed by the
to
contains
of
that every unit
a site of maximum
maximum attraction occur
sulfur
atoms pointing into the
the thiourea molecules. Evidence, in
interatomic
distances,
between these coplanar sulfur
the hydrocarbon molecule in
atoms
the
for
an interaction
and the C-H groups of
channel
was found in the
cis para-menthane adduct structure. This interaction is not
a hydrogen
bonding
interaction,
dipole-dipole interaction.
but
probably an induced
62
Conclusions
Thiourea's
hydrocarbons
hydrocarbon
usual
shows
ability
promise
mixtures.
It
to
as
is
a
form
method
not
fully
adducts
of
with
separating
understood what
forces hold these adducts together.
There are several strong indications of an interaction
between
the
sulfur
channel. As
has
atoms
been
and
pointed
the
hydrocarbon
out.
thiourea
in
the
will form
adducts with some compounds
while other compounds with the
same number of carbons and
a little different geometry due
to the presence of an
(see
Table
I)
and
aromatic
ring will not form adducts
adducts
hydrocarbons vary widely in
with
adduct
Waal
radii
at
enclosed
dipole-dipole
"supported
hydrogen
bond"
interaction. It
is
channel is
"an
not
exerting only weak
(I).
a
sulfur
atoms of
distance equal to the
sulfur atoms to the carbon
hydrocarbon
attraction.
the
distances from the hydrocarbon
molecule. This proximity of the
atoms of the
indication is that in the
structure
thiourea molecules are almost
sum of van der
included
stability are both indications
of an interaction. TTie strongest
cis para-menthane
different
is
Fetterly's
is
evident
that
otherwise
dispersion
not
an indication of a
postulation
consistent
the
inert
forces"
of
a
with this
hydrocarbon in the
surface
capable of
as Fetterly claims
63
The hydrocarbon molecule is
interaction with the sulfur
Hydrogen bonds are not
possible
dipole-dipole
between compounds such as
thiourea sulfur atoms, but an
attraction
interaction, along with the
in some form of
atom of the thiourea molecule.
carbon tetrachloride and the
induced
involved
is
possible.
This
hydrogen bonds in the thiourea
network, which are a lower
energy
bond than those in pure
crystalline thiourea, combine to
cause the adduct crystals
Lo be in a
than the pure crystalline
lower
energy
state
thiourea.
The geometry
of
responsible for its
the
molecule lies in the
sides of the
para-menthane
selectivity
para-menthane. The methyl
methyl group of the
cis
group
center
trahs
channel.
In
group would be sterically
thiourea molecule. This
of
of
this
the cis para-menthane
channel, were as the
would lie closer to the
position the trans methyl
hindered
steric
the trans isomer of
the
isomer
by
the NH2 group of a
hindrance
trans para-menthane molecule to
not to crystallize in a
over
is probably
could cause the
be distorted and therefore
thiourea
adduct as readily as the
cis isomer.
A diffractometer data set
was
collected on a crystal
containing a 50 mole percent mixture of 1,2,4 TMB and 1,2,4
TCB. Ttie thiourea molecule positions were well defined, but
64
bhe
hydrocarbon
molecules
model this disorder
found
were
no
disordered.
model
which
Attempts to
reduced the R
value below 14%. Even with such a high R value, it is clear
that the 1,2,4 TMB-I,2,4 TCB adduct structure is consistent
with the structures
Fitzgerald (15).
studied
by
Welling
(3) and Wick and
65
Recommendations
Thiourea
i
forms
hydrocarbons. This
characteristics
adducts
large
leads
questions is the
number
to
exact
the
other similar adducts
between
the
range
of
adducts with varying
One
of these
of the interaction between
the hydrocarbon in the channel.
tetrabromide
may
thiourea
wide
questions.
nature
carbon
a
of
many
the thiourea molecules and
A study of
with
further
sulfur
adduct structure and
define the interaction
atom
and
the
hydrocarbon
molecule. The bromide atoms of carbon tetrabromide might be
large enough
to
suggestion of a
reduce
the
possible
atoms of
TCB
and
deserves
further
the
disorder
problem. Welling's
interaction between the chlorine
thiourea
study.
A
NH^
less
groups
disordered
of thiourea
TCB
adduct
structure would be necessary to locate the chlorine atoms.
The role of inductors was not been clarified by any of
the adduct structures studied. It may be difficult to solve
any
adduct
structure
hydrocarbon in the
which
channel.
interest would be one
contains
An
adduct
more
than
one
which would be of
which contained carbon tetrachloride
and an aromatic molecule. The carbon tetrachloride-thiourea
adduct crystallizes in the space group R3bar. The aromaticthiourea adducts crystallize in
the
would be interesting to see
what space group an adduct
in
space group P2^/c. It
66
containing
aromatic
a
mixture
molecule,
of
carbon
probably
tetrachloride
ethyl
benzene
(6),
and
an
would
crystalize.
The 1,2,4 TMB-1,2,4 TCB adduct structure may refine to
a lower R value on a program package with full matrix least
squares. The XTAL system of crystallographic programs would
be the obvious choice.
On the next
diffractometer
data
set
collected on a
thiourea adduct the possibilities of a super lattice should
be studied closer.
The adduct
containing
trans
para-menthane should be
studied. Tliis structure could be compared to the cis isomer
structure to determine
if
the
explaination for thioureas
selectivity for the cis isomer is correct.
LITERATURE CITED
68
1. Mandelcorn, L . Mon-Stoichiometric Compounds.
(Academic Press, New York, 1964).
2. Angla, B. Ann, chim.. [12] 4, 639 (1949).
3. Welling, B . L. "Separate Aromatic Compounds by
Forming Adducts with Thiourea: How to
Select the Inductor." Masters Thesis in
Cehmical Engineering, Montana State
University, Bozeman, Montana (1982).
4. Schlenk, W., Jr., "Die Thioharnstoff-Addition
organischer Verbinduneng.", A n n . 573,
142 (1951)
5. McCandless, F. P., "Hydrogenated MonOterpenes:
Separation by Extractive Crystal­
lization." In d . Encr. Chem. Prod. Res.
Develop.. Vol 10, 4 406-409(1971).
6. McCandless, F. P. "Separation of the Cg
Alkylbenzenes by Induced Extractive
Crystallization." In d . Encr. Che m . Prod.
Res. D e v . . 19, 612-16 (1980).
7. U.S. Patent 2499820, 1950. "ThioureaHydrocarbon Complexes and Process
for Preparing Same." Lloyd C . Fetterly,
Shell Development Company.
8. Elcqmbe, M. M., and Tay l o r , J. C. "A
Neutron Diffraction Determination
of the Crystal Structures of Thiourea
and Deuterated Thiourea above and below
the Ferroelectric Transition.", Acta
Crvst.. A 2 4 , 410 (1968).
9. Smith, A. E. "The Crystal Structure of the
Urea-Hydrocarbon Complexes." Acta
Crvst.. 5, 224 (1952).
10. Smith, A. E. "The Crystal Structure of UreaHydrocarbon and Thiourea-Hydrocarbon
Complexes." J . C h e m . Phvs.. 18, 150
(1950).
11. Schlenk, W., Jr., "Die Harnstoff-Addition der
aliphatischen Verbindungen.", A n n . , 555
204 (1949).
69
12. Gorton, P.J. "The Separation of Hydrocarbon
Isomers by Extractive Crystallization
with Thiourea." Masters Thesis in
Chemical Engineering, Montana State
University, Bozeman, Montana (1980).
13. McClellan, A. L., and Macnab, W. K. Modeling
Chemical Structures.. Author's address:
576 Standard Avenue, Richmond, CA 94802
14. Fait, J., and Fitzgerald, A., Personal
communication.
15. Wick, T., and Fitzgerald, A., Personal
communication.
16. International Union of X-ray Crystallographers
International Tables for X-rav
Crystallography, V o l . 4,(Kynoch Press,
Birmingham, England 1974)
17. Sheldrick, G. M. SHELXTL Manual. Rev. 4,
(Nicolet XRD C o r p ., Madison, WI August
1983).
18. Stout, G., and Jensen, L . X-Ray Structure
Determination; A Practical G u i d e .
(Macmillan Company, London, 1968).
19. Stewart, J. M.., and Hall, S. R., XTAL User's
Manual, (University of Maryland,
Computer Science Center, College
Park, MD, 1983)
20. Bondi, A. "Van der Waal Volumes and Radii.",
J.. of P h v . Che m . . V b l . 68,3 441-451,
March (1964).
21. Hamilton, W. C . and Iber, J . A. Hydrogen
Bonding in Solids. (W. A. Benjamin,
Inc., New York, 1968)
70
APPENDICES
71
APPENDIX A
Additional Figures
72
Figure 17
Stereoview of model for cis para-menthane molecule
73
Figure 18
Thiourea molecules in the channel wall viewed in
at a sulfur pointing into the channel
74
APPENDIX B
Tables for Publication for
cis para-menthane adduct structure
75
Table 13
Atomic coordinates and isotropic thermal parameters
for cis para-menthane adduct structure
4
Atomic coordinates (xlO ) and isotropic
thermal parameters (S2XlO'"')
X
S(I)
Cd)
N(I)
N (2)
Cr(I)
Cr (2)
Cr (6)
Cp(I)
Cm
Cip
Cr (5)
Cr (4)
C p (2)
Cr (3)
-1(1)
0(3)
120(3)
-121(3)
-1026(4)
-1001(6)
17(3)
-284(23)
0
0
1051(2)
1036(4)
160(25)
0
Y
2998(I)
4071(3)
4553(3)
4426(3)
-297(15)
-220(18)
219(11)
735(17)
0
0
615(16)
674(17)
-821(16)
0
Z
2499(I)
2500(3)
1616(3)
3396(3)
2989(7)
1759(7)
3427(8)
-298(7)
4631(7)
114(7)
2989(7)
1759(7)
-298(7)
1347(7)
U
61 (I) *
59(1)*
83(1)*
81(1)*
73 (3)
123(3)
118(3)
172(3)
78(3)
84(3)
143(3)
107(3)
183(3)
37(3)
* Equivalent isotropic U defined as one third of the
trace of the orthogonal ised LI. ^ tensor
*,
• \l
• -y
'
76
Table 14
Anisotropic thermal parameters for cis para-menthane
adduct structure
A n isotropic
S(I)
Cd)
Nd)
N (2)
parameters
(S2 XlO3 )
' ljIl
U 22
U 33
U 23
U 13
U 12
75(1)
61 (2)
120(2)
1 16(2)
62(1)
63(2)
69(2)
75(2)
51(1)
56(2)
68(2)
67(2)
3(1)
-0(1)
5(2)
—6 (I)
6(1)
-1(1)
3(2)
3(2)
38(1)
34(1)
52 (2)
58(2)
The anisotropic
- Z tt2
thermaI
temperature factor exponent
j + ...
takes the form:
+ 2hka*b*U^.-))
Table 15
H-atom coordinates and isotropic thermal parameters for
cis para-menthane adduct structure
H-Atom coordinates
CxlO ) and
thermal
(S-^xIO^)
x
HClD
HC2D
HC22)
H C 12)
2 0 7 C22)
-
112 (21 )
-107(22)
■ 152(21)
parameters
y
5111(22)
4906(22)
4158(23)
4395(21)
isotropic
z
1719(23)
3389(23)
3978(25)
1202(22).
U
101(3)
86(3)
119(3)
62(3)
77
Table 16
Bond lengths for cis para-menthane adduct
Bond
S(I)-C(I)
C (I)-N (2)
N ( I ) - H (12)
N ( 2 ) - H (22)
Cr ( I ) - C r (6)
C r ( I ) - C r (6b)
Cr ( I ) - C r (5b)
C r (2)-Cr (3)
C r (2)- C r (5a)
C r (6)— Cm
C r (6)- C r (la)
Cr (6) -Cr (6a)
C r (6)- C r (5a)
Cp(I)-Cip
Cp(I)-Cp(Ic)
C p ( I ) - C ipa
C p (I)- C p (2b)
C p ( I ) - C r (3a)
C m - C r (6b)
C i p - C p (2)
C ip— C p (la)
Cip-Cp(Ic)
C i p-Cp(le)
C i p - C p (2a)
C i p - C p (2c)
C ip-Cp(2e)
Cr (5)-Cr (4)
Cr (S)-Cr(Ib)
Cr (5) -Cr (6a)
C r (4)- C r (3)
Cr (4)- C r (2c)
C p (2)- C p (la)
C p (2)- C p (Id)
C p (2 ) - C r (4b)
C p (2 ) - C p (2e)
C r (3)- C r (2a)
Cr(S)-Cp(Ia)
C r (3)-Cp(Ie)
C r (3)- C r (4a)
C r (3)- C p (2a)
C r (3)- C p (2e)
structure
lengths (R)
1.708(5)
1.311 (6)
0.588(31)
0.850(34)
1.540(8)
1.858(10)
I .859(23)
1.540(12)
I.785(17)
1.540(14)
I.859(24)
0.582(17)
I.335(26)
1.540(35),
1.631(38)
1.469(37)
1.601 (46)
I.956(29)
1.540(13)
1.540(33)
1.469(37)
1.469(27)
I.470(26)
1.470(35)
1.470(26)
1.470(24)
1.540(13)
I.014(23)
I.858(15)
I; 540(8)
0. 805(25)
0.
764(17)
1.601 (42)
1.984(17)
1. 631(27)
1.540(20)
1.956(29)
1.956(22)
1.540(25)
1.956(28)
1.956(20)
C(I)-N(I)
M (I)-H (Il)
N (2)- H (21)
C r ( I ) - C r (2)
Cr ( I ) - C r (6a)
Cr(I)-Cr(Sa)
Cr (I)-Cr (4a)
C r (2)-Cp(Ie)
C r (2)- C r (4a)
C r (6)- C r (5)
C r (6)- C r (lb)
C r (6)- C r (6b)
C r (6)- C r (5b)
Cp CI)- C r (2b)
Cp(I)-Cp(Ie)
C p ( I ) - C p (2a)
C p (I)- C p (2d)
C m - C r (6a)
C m -Cma
C i p - C r (3)
C i p - C p (lb)
Cip-Cp(Id)
C ip— C ipa
C i p - C p (2b)
C i p - C p (2d)
C i p - C r (3a)
Cr (S)-Cr(Ia)
C r ( S ) - C r (2c)
Cr ( S ) - C r (6b)
C r (4)- C r (lb)
C r (4)- C p (2e)
C p (2)- C p (lb)
C p (2 ) - C ipa
Cp (2)-Cp (2c)
C p (2)- C r (3a)
Cr (S)-Cr (2c)
C r (3)- C p (Ic)
C r (3)-Ci pa
C r (3)-Cr (4c)
Cr (3)-Cp (2c)
1.303(6)
0.837(38)
0. 757(39)
1.540(13)
I.335(20)
1. 014(21)
1.785(16)
I.827(13)
0.804(24)
1.540(8)
1.335(13)
0.
582(17)
1. 858(17)
1.827(13)
1.631 (30)
0.764(17)
1.297(44)
1.540(13)
0.923(19)
1.540(13)
I.540(26)
I.540(25)
0. 285(18)
I.540(25)
I.540(24)
1. 825(13)
1.859(22)
I. 786(17)
1.335(10)
I. 785(17)
I.985(19)
I.297(49)
I.470(35)
1.631 (39)
I.956(28)
I.540(9)
I.956(22)
1.825(13)
1.540(7)
1.956(21)
78
Table 17
Bond angles for cis para-menfchane adduct structure
Bond angles
S(I)-C(I)-M(I)
N(I)-C(I)-N (2)
C(I)-N(I)-H (12)
C (I)-N (2)-H (21)
H (21)-N (2)-H (22)
C r (2)—C r (I)- C r (6a)
C r (2)- C r ( I ) - C r (6b)
Cr(Z)-C r(I)-Cr(5a)
C r (2)- C r ( I)-Cr(5b)
C r (2)- Cr(I ) - C r (4a)
Cr (I)-Cr (2)-Cr (3)
C r (3)- C r (2)- C p (Ie)
Cr (3)-Cr (2)-Cr (5a)
Cr (3) -Cr (2) -Cr (4a)
Cr(I)- C r (6)- C r (5)
C r ( I ) - C r (6)- C r (la)
Cr (S)-Cr(6)-Cr(la)
C m - C r (6)- C r (lb)
C r (I)- C r (6)- C r (6a)
Cr (5) -Cr (6) -Cr (6a)
Cm— Cr (6) -Cr (6b)
Cr(I)- C r (6)- C r (5a)
Cr (5)-Cr (6)-Cr (5a)
C m - C r (6)-Cr (Sb)
C ip - C p (I)- C r (2b)
C ip - C p (I)- C p (Ie)
Ci p -C p (I)-C p (2a)
C i p -C p (I)- C p (2d)
C r (6)—Cm—C r (6a)
C r (6)—Cm— Cma
Cp(I)-CiP-Cr(3)
Cp(I)-Cip-Cp(la)
C r (3)- C i p - C p (la)
C p (2)-Ci p -C p (lb)
Cp(I)-Ci p - C p (Ic)
C r (3)-Cip-Cp(Ic)
C p (2)-Ci p - C p (Id)
Cp(I)-Cip-Cp(Ie)
C r (3)- C ip - C p (Ie)
C p (2)- C i p - C ipa
Cp(I)-Cip-Cp(Za)
C r (3)- C i p - C p (2a)
Cp(Z)-Cip-Cp(Zb)
C p (I)- C i p - C p (2c)
C r (3)- C i p - C p (2c)
C p (2)-Ci p - C p (2d)
Cp(I)-Cip-Cp(2e)
C r (3)-Cip-Cp(Ze)
Cp (2) —C ip— Cr (3a)
Cr (6) -Cr (5) -Cr (4)
(u )
121. I (4)
118.6(5)
120.6(33)
119.6(22)
121.8(34)
114.5(9)
107.0(7)
86.1(14)
92.9(13)
26.7(9)
109.5(9)
70.4(9)
98;0(9)
74.9(19)
137.7(9)
95.4(8)
65.6(12)
121.9(7)
58.8(18)
114.5(12)
7 9 . I (7)
40.5(9)
122.6(10)
95.0 (9)
109.4(19)
55. I (8)
' 70.3(36)
6 5 . I (14)
21.8(6)
167.4(7)
109.5(7)
169.5(7)
81.0(6)
49.8(18)
65.6(6)
SI. 0(5)
62.6(15)
65.6(4)
SI.0(5)
70.5(6)
29.3(8)
81.0(5)
109.4(7)
114.7(17)
81.0(5)
109.4(6)
127.7(16)
81.0(5)
70.5(6)
109.5(6)
S(I)-C(I)-N(Z)
120.3(3)
C(I)-N(I)-H(H)
113. I (21)
H(Il)-N(I)-H(IZ)
125.9(37)
C ( I ) - N (2)-H(22)
117.7(27)
Cr (Z)-Cr(I)-Cr(6)
109.5(6)
C r (6)- C r (I)- C r (6a)
21.9(7)
C r (6)- C r (I)- C r (6b)
16.6(7)
C r (6)-Cr (I)-Cr(Sa)
' 58.8(15)
C r (6)-Cr (I)-Cr(5b)
65.5(9)
C r (6)-Cr (I)-Cr(4a)
93.1(10)
Cr(I)-Cr(Z)-Cp(Ie)
173.I (22)
Cr (I)-Cr(Z)-Cr(5a)
34.5(8)
Cr (I)-Cr(2)- C r (4a)
93.9(15)
C r (I)- C r (6)—Cm
109.5(6)
Cm-Cr (6) -Cr (5)
109.5(7)
C m - C r (6)- C r (la)
95.0(9)
Cr (I)-Cr(6)-Cr(lb)
122.6(12)
C r ( S ) - C r (6)- C r (lb)
40.5(9)
Cm— Cr (6)-Cr (6a)
' 7 9 . I (5)
Cr (I).— Cr (6) -Cr (6b)
114.5(18)
Cr (5)-Cr (6)-Cr (6b)
58.8(12)
C m - C r (6)- C r (5a)
121.9(9)
Cr (I)-Cr (6)-Cr (5b)
65.5(10)
Cr (5) -Cr (6) -Cr (5b)
95.5(12)
Cip-Cp(I)-Cp(Ic)
5 5 . I (8)
10.5(7)
C ip -C p (I)-Cipa
Cip-Cp(I)-Cp(Zb)
58.7(19)
C ip - C p (I)- C r (3a)
61.6(13)
C r (6)- C m - C r (6b)
21.8(6)
Cp (I)— C ip— Cp (2)
140.4(11)
C p (2)-Ci P-Cr (3)
109.5(67
Cp(Z)-Cip-Cp(Ia)
29.3(8)
Cp(I)-Cip-Cp(Ib)
109.4(7)
C r (3)-Cip-Cp(lb)
109.5(6)
Cp (2) —C ip—Cp (Ic)
127.7(18)
'Cp(I)-Cip-Cp(Id)
109.4(6)
C r (3)-Cip-Cp(Id)
109.5(6)
C p (2)-Ci p -C p (Ie)
114.6(15)
Cp- (I)—C ip—C ipa
70.5(7)
C r (3)- C ip - C ipa
180.0(1)
C p ( Z )-Cip-Cp(2a)
169.5(7)
62.6(17)
Cp(I)-Cip-Cp(2b)
C r (3)-Cip-Cp(Zb)
109.5(6)
C p ( Z ) - C i p - C p (2c)
65.6(6)
C p (I)—C ip—C p (2d)
49.8(15)
C r (3)- C i p - C p (2d)
109.5(6)
C p ( Z ) - C ip -C p (2e)
65.6(3)
C p (I)-Cip-Cr(3a) '
70.5(7)
Cr (3) —C ip—Cr (3a)
180.0(1)
Cr (6) -Cr (5) -Cr (la)
65.5(11)
79
Table I7 (cont.)
C r (4)- C r (5)-Cr(I a)
Cr (4)-Cr CS)-Cr Clb)
Cr (4)- C r (5)- C r (2c)
Cr (4)-Cr CS)-Cr (6a)
Cr (4)-Cr ( S ) - C r (6b)
C r (5)- C r (4)- C r (lb)
C r (5)- C r (4)- C r (2c)
Cr CS) - C r (4)- C r (2e)
C i p - C p (2)- C p (la)
C i p — C p (2)—Cp(Id)
C i p - C p (2 ) - C r (4b)
C ip - C p (2)- C p (2e)
C r (2)- C r (3)- C ip
C ip—C r (3)- C r (4)
Ci P - C r (3)- C r (2a)
Cr (2) -Cr (3) -Cr ( 2 0
Cr (4)-Cr(3)-Cr(2c)
C i p - C r (3)- C p (la)
Cr (2)- C r (3)-Cp(Ic)
Cr (4)-Cr (3)-Cp (Ic)
C i P - C r (3)- C p (Ie)
Cr (2)-Cr (3)-Ci pa
C r (4)- C r (3)— C ipa
C i p —C r (3)— C r (4a)
C r (2)- C r (3)- C r (4c)
C r (4)- C r (3)- C r (4c)
Ci P - C r (3)- C p (2a)
C r (2)- C r (3)- C p (2c)
C r (4)- C r (3)- C p (2 c ) ■
C i p - C r (3)- C p (2e)
92.9(12)
8 6 . I (15)
26.7(10)
107.0(5)
114.5(7)
34.5(9)
93.9(16)
153.0(21)
70.2(35)
58.7(9)
102.0(13)
55. I (7)
109.5(5)
109.5(5)
109.5(5)
109.4(9)
30.3(10)
47.9(8)
122.3(14)
69.9(8)
47.9(6)
109.5(5)
109.5(5)
109.5(6)
81.7(10)
109.4(10)
47.9(7)
80.8(10)
146.8(11)
47.9(6)
C r (6)- C r (5)- C r (lb)
C r (6)-Cr (S)-Cr(2c)
C r (6)- C r (5)- C r (6a)
C r (6)-Cr (S)-Cr(6b)
C r (5)- C r (4)- C r (3)
C r (3)- C r (4)- C r (lb)
C r (3)- C r (4)- C r (2c)
C r (3)- C r (4)- C p (2e)
C i p —C p (2)—Cp(Ib)
C ip— C p (2)—C ipa
C i p - C p (2)- C p (2c)
C i p - C p (2)- C r (3a)
C r (2)- C r ( S ) - C r (4)-■
C r (2)- C r (3)- C r (2a)
Cr (4)-Cr (3)-Cr (2a)
C i p - C r (3)- C r (2c)
C r (2)- C r (3)- C p (la)
Cr (4)-Cr (3)-Cp (la)
C i p - C r (3)-Cp(Ic)
C r (2)- C r (3)- C p (Ie)
' C r (4)- C r (3)-Cp(Ie)
C ip - C r (3)- C ipa
Cr (2)- C r (3)- C r (4a)
C r (4)- C r (3)- C r (4a)
C i P - C r ( S ) - C r (4c)
C r (2)- C r (3)- C p (2a)
C r (4)- C r (3)- C p (2a)
C i p - C r (3)- C p (2c)
C r (2)- C r (3)- C p (2e)
C r (4)- C r (3)- C p (2e)
58.8(9)
9 3 . I (8)
16.6(4)
21.9(7)
109.5(6)
98.0(6)
74.8(8)
66.0(11)
6 5 . I (23)
10. 5(7)
5 5 . I (7)
61.6(12)
132.4(10)
109.4(5)
81.7(12)
109.5(5)
1 2 7 . 7 ( 1 1)
98.8(12)
47.9(6)
61.7(6)
149.5(12)
0.0(1)
30.3(11)
109.4(6)
109.5(5)
84.8(13)
1 0 2 . I (12)
47.9(6)
157.2(9)
68.0(10)
Table 18
F(obs) and Sigma(F) for cis para-menthane adduct structure
F (obs) and Sigwa(F)
h
k
-I
0
-2
-4
-I
-3
0
-5
-2
-7
-4
-I
—6
—3
0
2
3
4
5
5
6
6
7
7
8
8
8
9
9
9
10
10
10
11
11
11
11
12
12
12
12
13
13
13
13
14
14
14
14
-a
-5
-2
-10
-7
-4
-I
-9
-6
-3
0
-11
-8
-5
-2
-13
-10
-7
-4
I IOFo
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
959
4790
1694
1668
1669
316
1072
430
431
683
712
682
318
323
873
288
305
287
106
651
650
104
75
316
79
91
157
94
87
168
144
384
648
383
(-sigma = unobserved):
IOs
h
I:
-5
28
5
7
6
2
4
2
2
3
2
2
2
2
3
2
2
2
5
4
3
5
7
2
7
6
4
7
7
3
5
2
3
2
-I
-12
-9
—6
-3
0
-14
-11
—8
-5
-2
— 13
-10
-7
-4
-12
-9
—6
-I
-3
0
-5
-2
I
-7
-4
-I
2
-9
-6
-3
0
3
-11
14
15
15
15
15
15
16
16
16
16
16
17
17
17
17
18
18
18
I
2
2
3
3
3
4
4
4
4
5
5
5
5
5
6
I IOFo • 10s
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
148
193
222
224
193
103
26
79
198
91
38
224
382
385
220
159
166
156
43
403
- 63
2170
403
1990
237
68
1988
245
882
2750
2170
51
52
521
4
5
3
3
3
7
-21
7
4
7
-16
5
3
4
5
6
6
7
-2
4
2
20
3
4
2
12
17
2
5
14
9
10
12
2
CIS PARA-MENTHANE
h
k
I IOFo
—8
-5
-2
I
4
-13
-10
-7
-4
-I
2
5
-15
-12
-9
6
6
6
6
6
7
7
7
7
7
7
7
8
8
8
8
1974
2766
245
940
499
75
253
37
234
937
513
441
338
532
1515
1998
40
50
156
361
96
464
1095
1520
882
513
106
153
44
31
224
22
256
499
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
-6
I
-3 8 I
0 8 I
3 8 I
6 8 I
-17 9 I
-14 9 I
-I I 9 I
-8 9 I
—5 9 I
-2 9 I
I 9 I
4 9 I
7 9 'I
— 16 10 I
-13 10 I
I
. -io 10
-7 10 T
-4 10 I
10s
h
k
8
12
2
3
5
9
4
13
5
6
3
3
4
3
10
16
12
12
5
4
13
3
4
12
5
5
5
6
-20
-24
4
-25
4
5
-I
2
5
8
-18
-15
-12
-9
—6
-3
0
3
6
-17
-14
-11
10
10
10
10
11
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
12
13
13
13
13
13
13
13
13
14
14
14
14
14
-B
-5
-2
.I
4
-16
-13
-10
-7
-4
-I
2
’5
-18
-15
-12
-9
-6
I IOFo
10s
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
5
10
8
16
16
4
3
8
5
5
10
7
-20
13
4
3
7
3
13
4
10
-30
-29
4
9
6
4
8
7
20
5
4
4
3
119
66
99
72
57
311
736
1102
530
153
62
158
47
94
538
735
536
443
79
311
138
26
25
229
73
152
308
167
181
56
.281
533
462
357
h 'k
—3
0
. 3
-17
-14
-11
-8
-5
-2
I
-16
-13
-TO
-7
-4
-I
-15
-12
-9
-6
-3
-14
-11
-8
—5
0
-2
I
-4
-I
2
-6
-3
0
14
14
14
15
15
15
15
15
15
15
16
16
16
16
16
16
17
17
17
17
17
18
18
18
18
i
2
2
3
3
3
4
4
4
I IOFo
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
2
2
2
2
2
2
2
2
2
152
34
64
95
274
301
348
102
169
170
48
47
25
25
141
166
100
97
84
55
81
39
49
63
178
320
1332
484
289
484
888
110
290
1930
10s
6
-23
15
10
5
6
5
9
8
6
-21
-20
-29
-29
6
10
10
13
12
16
11
-24
-21
16
7
4
13
2
2
4
6
4
2
9
Table 18 (cent.)
F<obs>
and
s igm a (F )
h
k
I IOFo
3
4
S
5
5
5
6
6
6
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
-a
-2
I
4
-10
-7
-4
-I 6
2 6
5 6
-12 7
-9 7
-6 7
-3 7
0 7
3 7
6 7
-14 8
-I I 8
-8 8
-5 8
-2 8
I 8
4 8
7 8
— 1,6 9
-13 9
-10 9
-7 9
-4 9
-I 9
2 9
5 9
1622
894
885
1098
402
660
64
I 16
1113
1215
463
217
172
54
1628
2320
1381
645
118
217
50
897
1225
783
621
225
105
181
61
175
404
785
376
150
(-s ig m a
h
I;
54
9 2
73
10 2
52
10 2
87
10 2
52
10 2
10 2 663
10 2 1375
10 2 1035
10 2 703
10 2 188
79
11 2
72
11 2
11 2 162
11 2 219
-5 11 2 465
-2 ii 2 397
I 11 2 407
4 ii 2 220
27
7 ii 2
50
— 16 12 2
97
-13 12 2
96
-10 12 2
-7 12 2 219
-4 12 2 628
-I 12 2 410
2 12 2 276
78
5 12 2
-18 13 2 102
68
-15 13 2
92
-12 13 2
—9 13 2 187
-6 13 2 643
—3 13 2 704
0 13 2 575
16
14
18
9
12
3
15
4
3
-17
-14
-11
-8
-5
-2
I
— 16
-13
-10
-7
-4
-I
2
-15
-12
-9
-6
-3
0
-14
-11
-S
13
14
14
14
14
14
14
14
15
15
15
15
15
15
15
16
16
16
16
16
16
17
17
17
17
17
18
18
18
0
I
2
2
3
21
2
9
13
2
3
8
4
9
6
3
4
8
-18
-15
-12
-9
-6
—3
0
3
6
-17
-14
-11
-8
8
12
10
3
7
3
11
4
21
4
5
4
15
7
12
4
3
6
'5
8
k
3
5
11
12
5
4
3
14
3
9
-38
-20
8
9
4
5
4
4
11
10
14
9
4
4
3
3
-5
-2
-13
-10
-7
0
I
-I
2
-3
■Page
PARA-MENTHANE
IOs
h
7
C IS
I IOFo
IOs
5
= u n o b s e rv e d ):
I IOFo
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
254
209
285
39
124
141
284
155
177
58
40
234
212
164
73
166
73
102
191
257
136
232
93
54
39
81
92
73
47
41
3181
3197
2400
34
IOs
9
6
4
-21
6
6
6
6
6
16
-19
7
7
6
16
7
18
9
8
9
8
5
18
17
-23
12
12
15
-22
11
36
3
21
11
h
0
3
-5
-2
I
4
-7
-4
-I
2
5
-9
-6
-3
0
3
6
-11
-8
-5
-2
I
4
7
-13
-10
-7
-4
-I
2
5
8
-15
-12
k
3
3
4
4
4
4
5
5
5
5
5
6
6
6
6
6
6
7
7
7
7
7
7
7
8
8
8
8
8
8
8
8
9
9
I IOFo
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
'3
3
3
3
3
’3
3
3
3
3
3
3
3
3
3
3
3
49
82
1953
2434
1341
399
1019
1965
1365
569
44
272
18
60
31
.245
193
220
161
1025
571,
323
148
73
436
71
171
397
327
79
245
456
438
74
IOs
h
k
7
-9 9
—6 9
8
14
-3 9
3
0 9
2
3 9
6 9
3
7
9 9
-17 10
5
4
-14 10
2
-I I 10
12
-8 10
3
-5 10
-21
-2 10
6
I 10
-15
4 10
3
7 10
5
-16 11
3
-13 11
5
-10 11
-7 11
8
5
-4 11
2
-I 11
4
2 11
17
5 11
3
-1.8 12
-15 12
11
-12 12
6
4
-9 12
6
-6 12
16
-3 12
5
0. 12
4
3 12
4 ■
6 12
10
-17 13
I IOFo
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
IOs
57
15
269 ' 4
235
3
27 -20
252
4
328
6
322
5
27 -31
58
14
71
13
80
16
48
13
54
11
48
17
52
13
17
75
404
5
148
5
59
13
220
5
152
4
23 -26
179
5
267
5
6
268
237
5
36 -21
84
10
4
195
260
6
67
16
175
6
214
7
91
17
Table 18 (cont.)
F (o b s )
h
k
-14
-11
-8
-5
-2
I
4
-16
-13
-10
-7
-4
-I
2
-15
-12
-9
-6
-3
0
-14
-11
-8
-5
-2
-13
-10
-7
-4
-12
-9
—6
-I
—3
13
13
13
13
13
13
13
14
14
14
14
14
14
14
15
15
15
15
15
15
16
16
16
16
16
17
17
17
17
18
18
18.
I
2
and
s igm a (F )
I IOFo
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
4
4
47
141
436
244
190
104
45
147
60
60
46
59
82
128
35
233
440
335
191
26
133
395
450
269
152
64
43
55
47
267
330
227
532
286
10s
17
6
3
4
5
9
-20
9
15
15
-19
13
9
8
-26
6
4
6
6
-30
7
4
5
8
8
16
-20
17
-21
6
5
6
4
3 ■
(-s ig m a
h
k
0
-5
-2
I
-7
-4
-I
2
-9
—6
-3
0
3
-11
-8
-5
-2
I
4
-13
-10
-7
-4
-I
2
5
-15
-12
-9
-6
-3
0
3
6
2
3
3
3
4
4
4
4
5
5
5
5
5
6
6
6
6
6
6
7
7
7
7
7
7
7
8
8
8
8
8
a
8
8
= u n o b s e rv e d ):
C IS
I IOFo
IOs
h
k
22
2
3
6
5
4
9
4
3
3
2
16
10
3
3
4
7
4
5
4
7
5
8
3
3
13
9
4
5
3
8
6
5
10
-17
-14
-11
—8
-5
-2
I
4
7
-16
-13
-10
-7
-4
-I
2
5
8
-18
-15
-12
-9
-6
-3
0
3
6
-17
-14
-I I
-8
-5
-2
I
9
9
9
9
9
9
9
9
9
10
10
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
4
4
4
4
4
4
4
4
4
4
4
4
.4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
1867
339
288
928
965.
478
928
627
701
519
335
561
55
493
458
521
627
593
705
377
1327
1279
967
595
428
121
99
250
753
460
61
172
143
88
PARA-MENTHANE
I IOFo
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
43
239
782
754
706
425
278
56
63
200
714
1515
1326
707
270
87
84
116
148
271
461
786
498
148
132
98
114
67
96
465
253
105
75
57
Page
10s
h
k
-20
4
3
3
8
4
5
16
13
6
4
29
9
7
3
12
9
10
8
5
5
5
4
6
10
13
8
13
9
3
4
8
11
14
4
-16
-13
-10
-7
-4
-I
2
-15
-12
-9
-6
-3
0
3
-14
-11
12
13
13
13
13
13
13
13
14
14
14
14
14
14
14
15
15
15
15
15
15
16
16
16
16
16
17
17
17
17
18
18
I
2
-B
-5
-2
I
-13
-10
-7
-4
-I
-12
-9
—6
-3
-I I
-a
0
-2
I IOFo
4
4
4
4
4
4
4
4
4
4
4
4
4
44
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
IOs
h
k
76
12
125
11
434
4
716
5
382
6
61
12
51
14
154
8
147
7
106
7
235
5
106
10
129
6
192
6
233
8
146
6
266
6
116
12
88
9
141
6
135
11
128
11
191
5
' 65
14
84
11
127
14
67
13
54
20
130
10
233
10
143
8
129
9
22 -16
38
14
I
-4
-I
2
-6
—3
0
3
-8
-5
-2
I
4
-10
-7
-4
-I
2
5
-12
-9
—6
-3
0
3
6
-14
-11
—8
-5
-2
I
4
7
2
3
3
3
4
4
4
4
5
5
5
5
5
6
6
6
6
6
6
7
7
7
7
7
7
7
8
8
8
B
8
8
8
S
I IOFo
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
3
IOs
1059
8
1096
6
1063
18
407
4
649
2
1092
5
26 -16
292
4
1127
5
18 -21
406
3
411
2
975
4
174
6
393
5
645
5
413
3
1007
5
692
3
331
5
316
3
394
4
293
4
43
15
200
4
121
7
24 -28
177
9
43
14
I 121
6
1000
6
1271
4
861
5
78
10
Table 18 (cont,)
F (obs)
and
s i g m a CF)
(-s ig m a
h
k
I IOFo
IOs
h
k
-16
-13
-10
-7
-4
-I
2
5
S
-15
-12
-9
-6
-3
0
3
6
-17
■14
■11
-B
-5
-2
I
4
■16
■13
■10
-7
-4
-I
2
5
■15
9
9
9
9
9
9
9
9
9
10
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
12
13
5
83
5 154
5 185
5 317
5 974
5 1265
5 890
5 296
5 115
5
95
5 169
5 .189
5 165
5 201
34
5
5
98
5 132
5
77
5
90
5
24
5 179
5 694
5 889
5 717
5 196
5 156
5
39
5 153
5 331
5 864
5 710
5 315
5 167
5 201
11
6
4
3
11
10
4
5
8
9
8
4
5
5
-23
8
7
13
9
-28
5
5
5
4
6
6
-21
6
3
5
5
5
8
7
-12
-9
-6
-3
0
3
-14
-11
-B
-5
-2
I
-13
-10
-7
-4
-I
-12
-9
—6
—3
-11
-8
-5
0
I
-I
2
-3
0
3.
-5
-2
I
13
13
13
13
13
13
14
14
14
14
14
14
15
15
15
15
15
16
16
16
16
17
17
17
0
I
2
2
3
3
3
4
4
4
= u n o b s e rv e d )t
C I S PARA-MENTHANE
I IOFo
10s
h
k
I IOFo
IOs
h
k
-20
8
9
9
18
11
18
9
-19
8
7
13
5
11.
14
6
11
9
10
7
9
13
9
11
3
3
3
20
5
3
10
2
55
3
4
-7
-4
-I
2
5
-9
-6
-3
0
3
6
-11
-8
-5
-2
I
4
7
-13
-10
-7
-4
-I
2
5
8
-15
-12
-9
—6
-3
0
3
4
5
5
5
5
5
6
6
6
6
6
6
7
7
7
7
7
7
7
8
8
8
8
8
8
8
8
9
9
9
9
9
9
9
6 269
6 529
6 448
6 510
6 517
6 162
6
59
6 454
6 1421
6 602
6 102
6
48
6 '97
6
92
6 530
6 519
6
41
6 117
6 375
6 166
6
95
6
82
6 263
6
22
6 145
6 152
6 170
6 233
6
59
6 322
6 113
6 113
6 252
6
24
4
5
3
5
3
4
12
9
9
6
7
15
13
8
2
4
15
6
4
5
11
7
4
-25
5
7
10
5
13
4
27
19
5
-28
6
-17
-14
Ml
-8
-5
-2
I
4
7
-16
-13
-10
-7
-4
-I
2
5
-15
-12
-9
-6
-3
0
3
-14
-IT
-8
-5
-2
I
-13
-10
-7
9
10
10
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
13
13
13
13
13
13
14
14
14
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
6
6
44
143
117
101
56
83
61
93
44
305
315
123
199
93
74
198
129
154
86
129
105
84
129
165
1307
709
708
1719
2151
2218
1404
449
1713
514
Page
I IOFo
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
235
379
332
I 18
87
168
141
77
320
389
148
177
125
76
122
75
206
183
111
63
33
37
24
97
65
107
186
157
145
201
69
103
324
373
IOs
h
k
5
7
4
6
12
7
6
10
5
5
7
6
7
9
6
10
6
6
8
17
-23
-21
-28
10
12
10
5
5
6
6
13
16
4
5
-4
-I
-15
-12
-9
—6
-3
0
-I I
-8
-5
-10
-7
-I
-3
0
-5
-2
I
-7
-4
-I
2
-9
-6
-3
0
3
-11
-8
—5
-2
I
4
14
14
15
15
15
15
15
15
16
16
16
17
17
I
2
2
3
3
3
4
4
4
4
5
5
5
5
5
6
6
6
6
6
6
I IOFo
6
6
6
6
6
6
6
6
6
6
6
6
6
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
316
63
120
98
227
223
49
80
159
175
195
375
381
23
500
27
370
502
431
120
34
427
376
801
548
374
21
757
592
889
547
379
286
94
4
IOs
8
18
10
12
8
6
-21
16
7
9
6
4
6
-18
3
-18
2
3
4
5
-15
4
3
4
3
2
-24
a
6
5
4
3
3
9
CO
W
Table 18 (cont.)
F (obs)
and
s ig m a < F )
C -s ig m a
h
k
t IOFo
IOs
h
k
-13
-10
-7
-4-I
2
5
-15
-12
-9
7
7
7
7
7
7
7
8
8
8
7
35
7 128
7
23
7 128
7 286
7 179
7 248
7
63
7 631
7 1003
7 897
7 762
7
58
7 133
7
80
7 332
7 712
7 1005
7 805
7 176
7
90
7
73
7
96
7 134
7
26
7
37
7 114
7
86
7
90
7
77
7
57
7 176
7 520
7 719
-21
14
-27
5
3
4
4
14
3
5
5
4
11
6
10
5
5
8
5
5
8
10
10
7
-30
-23
7
12
8
16
17
6
5
—6
-3
0
3
-14
-11
-8
-5
-2
I
4
-13
-10
-7
-4
-I
2
-12
-9
-6
-3
0
-11
—8
-5
-2
-10
-7
-4
0
-2
I
-4
-I
11
11
11
11
12
12
12
12
12
12
12
13
13
13
13
13
13
14
14
14
14
14
15
15
15
15
16
16
16
I
2
2
3
3
—6
B
-3
0
3
8
8
8
8
9
9
9
9
9
9
9
6
-H
-11
-8
-5
-2
I
4
7
— 16
-13
-10
-7
-4
-I
2
5
-15
-12
-9
9
10
10
10
10
10
10
10
10
11
11
11
a
= u n o b served )i
C IS
I IOFo
IOs
h
I:
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
3
6
-20
15
8
3
4
5
15
17
8
-30
-30
-18
10
-30
13
5
5
13
14
-21
7
-23
15
7
10
9
8
4
3
5
4
3
2
—6
-3
0
3
-8
-5
-2
I
4
-10
-7
-4
-I
2
5
-12
-9
—6
-3
0
3
6
-14
-11
-8
-5
-2
I
4
7
-13
-10
-7
3
4
4
4
4
5
5
5
5
5
6
6
6
6
6
6
7
7
7
7
7
7
7
8
8
8
8
593
120
40
66
285
518
629
252
58
50
138
26
26
43
75
26
154
281
325
74
58
48
175
40
71
161
133
101
138
237
263
187
317
188
PARA-MENTHANE
8
8
8
8
9
9
9
I IOFo
Page
IOs
h
k
8 204
4
8 274
3
8 312
4
8 595
5
8 643
4
8 244
4
8 258
3
8 199
4
8 484
4
8 303
5
8 363
4
8 278
3
8 279
5
8 478
4
8 428
6
8 338
6
8
63
17
8
59
12
8 279
6
8 639 . 4
8 1017
6
8 776
4
8 254
5
8
91
12
8 167
6
8 313
3
8 248
5
8 429
3
8 512
7
8 173
5
8
56
16
8
96
9
8 158
5
8
55
12
-4
-I
2
5
-15
-12
-9
-6
-3
0
3
-14
-11
-8
-5
-2
I
4
-13
-10
-7
-4
-I
2
-12
-9
—6
-3
0
-I I
-8
-5
-2
-10
9
9
9
9
10
10
10
10
10
10
10
11
11
11
11
11
11
11
12
12
12
12
12
12
13
13
13
13
13
14
14
14
14
15
5
I IOFo
IOs
h
k
I IOFo
10 =
8
8
8
8
8
8
8
8
8
8
8
8
8
4
5
4
6
18
17
5
4
9
4
4
10
17
5
4
4
4
7
16
-20
17
5
5
12
13
14
8
5
6
12
11
12
14
11
-7
-4
0
I
-I
2
-3
0
3
-5
-2
I
4
-7
-4
-I
2
5
-9
-6
-3
0
3
6
-11
-8
-5
-2
I
4
7
-13
-10
-7
15
15
0
I
2
2
3
3
3
4
4
4
4
5
5
5
5
5
6
6
6
6
6
6
7
7
7
7
'7
7
7
8
8
8
8
56
8 171
9
26
9 1394
9 1384
9 987
9
58
9
58
9 206
9 494
9 986
9 625
9 143
9 328
9 489
9 627
9 455
9
33
9
90
9
54
9 204
9
42
9
74
9 210
9
89
9 229
9 325
9 449
9 207
9 . 64
9
68
9 203
9
44
9 234
20
8
-53
7
11
7
17
17
6
3
5
10
6
5
3
8
6
-23
13
13
4
-19
12
5
8
4
4
6
6
13
19
5
-20
9
a
8
8
8
8
8
8
8
8
8
8
8
8
B
B
8
8
8
8
8
8
307
511
424
153
50
50
157
362
772
921
436
93
54
175
334
426
309
169
54
40
67
173
312
80
63
83
252
427
309
87
83
152
67
83
Table 18 (cont.)
F (o b s )
h
k
-4
-I
2
5
12
-9
-6
-3
0
3
14
11
-8
-5
-2
I
4
13
10
-7
-4
-I
2
12
-9
-6
-3
0
11
-8
-5
-2
10
-7
8
8
8
8
9
9
9
9
9
9
10
10
10
10
10
10
10
11
11
11
11
11
11
12
12
12
12
12
13
13
13
13
14
14
and
B ig m a (F )
I IOFo
10s
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
5
4
11
5
6
-28
17
12
-21
8
-25
17
16
-21
14
13
-31
9
-22
9
13
14
15
18
7
5
9
-21
10
6
5
19
-19
-31
150
208
81
251
147
25
91
77
35
103
35
68
59
36
68
68
27
147
34
92
66
6469
53
150
212
109
46
158
210
253
85
44
27
(-s ig m a
h
k
= u n o b s e rv e d ):
C IS
I IOFo
IOs
h
k
19
11
8
4
4
4
-21
4
4
-27
13
5
3
4
14
4
9
4
4
13
12
6
8
7
3
5
13
11
7
4
4
6
8
10
3
-11
-8
-5
-2
I
4
-13
-10
-7
-4
-I
2
-12
-9
-6
-3
0
-11
-8
-5
-2
-10
-7
-4
0
-2
I
-4
-I
2
—6
-3
0
8
9
9
9
9
9
9
10
10
10
10
10
10
II
II
II
II
II
12
12
12
12
13
13
13
I
2
2
3
3
3
4
4
4
-4 14 9
-I I 10
-3 2 10
0 2 10
-5 3 10
-2 3 10
I 3 10
-7 4 10
-4 4 10
-I 4 10
2 4 10
-9 5 10
-6 5 10
-3 5 10
0 5 10
3 5 10
-I I 6 10
-8 6 10
-5 6 10
-2 6 10
I 6 10
4 6 10
-13 7 10
-10 7 10
-7 7 10
-4 7 10
-I 7 10
2 7 10
5 7 10
-12 8 10
-9 8 10
—6 8 10
-3 8 10
0 8 10
66
92
194
316
212
201
34
583
653
23
71
182
442
202
48
285
129
409
440
86
67
232
285
529
903
573
72
78
142
305
368
404
283
87
PARA-MENTHANE
I IOFo
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
11
77
144
370
175
90
67
116
331
477
533
237
43
59
213
139
144
SI
109
212
299
125
53
333
294
113
56
24
67
183
89
400
213
184
56
Page
IOs
h
k
10
10
4
5
17
16
9
5
7
6
6
-21
16
8
7
6
13
9
6
8
8
18
4
• 7
14
15
-28
11
5
8
5
5
5
16
3
-8
-5
-2
I
4
10
-7
-4
-I
2
5
12
-9
—6
-3
0
3
11
-8
-5
-2
I
4
10
-7
-4
-I
2
-9
-6
-3
0
11
4
5
5
5
5
5
6
6
6
6
6
6
7
7
7
7
7
7
8
8
8
8
8
8
9
9
9
9
9
10
10
10
10
II
I IOFo
11
11
11
II
II
11
11
11
11
11
11
11
II
II
11
11
11
11
II
II
II
II
II
Il
11
11
11
11
11
II
II
11
11
11
104
61
36
408
681
372
158
237
215
683
527
221
187
178
246
123
28
33
60
42
60
534
479
219
27
176
377
476
363
67
164
27
50
46
IOs
h
k
9
13
-21
3
5
4
9
4
5
5
3
'5
6
7
4
11
-33
-27
16
-21
15
5
4
5
-31
6
5
4
4
17
6
-31
-22
-20
-8
-5
-2
-7
-4
0
I
-I
2
-3
0
3
-5
. -2
I
4
-7
—4
-I
2
5
-9
-6
-3
0
3
-11
-8
-5
-2
I
4
-10
-7
11
11
11
12
12
0
I
2
2
3
3
3
4
4
4
4
5
5
5
5
5
6
6
6
6
6
7
7
7
7
7
7
8
8
I IOFo
6
IOs
11
53
17
11 222
5
11 366
6
11 187
6
11 232
5
12 1243
5
12 518
7
12 509
5
12 129
9
12 689
5
12 640
62
12 275
5
12 301
4
12 138
7
12 273
4
12 105
10
12
32 -26
12 305
4
12 274
7
12
26 -30
12
93
9
12
90
15
12 302
7
12 276
4
12 287
5
12 118
13
12 107
10
12 115
9
12
64 . 14
12
26 -30
12
96
9
12 133
12
12
27 -31
12 107
a
00
LH
Table 18 (cont.)
F (obB) and Bigma(F)
h
k
I IOFo
-4 8 12
-I 8 12
2 8 12
-9 9 12
-6 9 12
-3 9 12
0 9 12
-8 10 12
-5 10 12
-2 10 12
IOs
107 • 8
116
8
107
10
105
9
88
10
119
8
182
6
18
82
10
83
109
12
(-sigma = unobserved):
h
k
I IOFo
-7 11 12
-4 11 12
-I
I 13
-3 2 13
0 2 13
-5 3 13
-2 3 13
I 3 13
-7 4 13
-4 4 13
108
123
50
87
44
265
84
86
44
27
CIS PARA-MENTHANE
IOs
h
k
9
8
17
10
-20
4
13
11
-22
-31
-I
2
-9
—6
-3
0
3
-8
-5
-2
4
4
5
5
5
5
5
6
6
6
I IOFo
13
13
13
13
13
13
13
13
13
13
85
121
194
353
265
35
109
353
355
123
Page
IOs
h
k
I IOFo
IOs
h
k
10
14
10
5
5
-24
9
4
7
7
I
-7
-4
-I
—6
-3
-5
0
-2
I
6
7
7
7
8
8
9
I
2
2
13
92
29
13
13
51
13
82
13 356
13 . H 2
13 195
14
54
14
72
14
61
14
-33
18
11
4
11
6
19
11
16
-4
-I
2
—6
—3
0
-5
-2
-4
3
3
3
4
4
4
5
5
6
I IOFo
14
14
14
14
14
14
14
14
14
88
63
136
60
106
223
100
140
37
7
IOs
11
16
10
17
8
8
10
8
-25
Table 19
Observed and calculated structure factors for cis
para-menthane adduct structure
Observed and calculated structure factors:
h
k
0
-2
-4
-I
-3
0
-5
-2
-7
-4
-I
-6
-3
0
-S
-5
-2
-10
-7
-4
-I
-9
—6
-3
0
-11
-S
-5
-2
-13
-10
-7
-4
-I
3
4
5
5
6
6
7
7
S
8
8
9
9
9
10
10
10
11
11
11
11
12
12
12
12
13
13
13
13
14
14
14
14
14
I IOFo IOFc
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
h
I:
-12 15
3221 2481
-9 15
1139 644
1122 1088
—6 15
—3 15
1122 1096
0 15
213 241 .
-IT 16
721 774
-8 16
289 342
-5 16
290 365
-13 17
460 421
-10 17
479 375
-7 17
458 411
214 222
-4 17
-12 18
217 234
-9 18
587 563
—6 18
- 193 225
-3 2
205 199
0 2
193 214
-5 3
71
15
-2 3
438 394
437 429
I 3
-7 4
70
35
-4 4
51
96
-I 4
213 266
2 4
53 104
-9 5
61
104
105
76
—6 5
99
—3 5
63
0 5
59
89
3 5
113
71
-11 6
97
75
—8 6
258 197
435 398
—5 6
257 228
-2 6
I 6
100
77
130
149
151
130
70
53
133
61
150
257
259
148
107
112
105
271
43
1459
271
1338
159
46
1337
165
593
1849
1459
34
35
350
1327
1860
164
632
h
k
Page
I IOFo IOFc
h
k
4 6 I 336 320
141
-13 7 I
50
36
168
172
-10 7 I 170 166
-7 7 I
25
135
10
—4 7 I 157 167
62
58
-I 7 I 630 602
153
2 7 I 345 339
66 .
5 7 I 297 304
153
-15 8 I 227 225
-12 8 I 358 348
257263
-9 8 I 1018 960
150
-6 a . I 1344 1301
97
-3 8 I
27
16
94
0 8 I
34
4
3 8 I 105 114
91
339
6 8 I 243 257
65
52
-17 9 I
71
-14 9 I 312 332
1282
244
-11 9 I 737 751
1341
-8 9 I 1022 980
-5 9 I 593 566
143
-2 9 I 345 346
12
I 9 I
72
58
1322
4 9 I 103
97
175
152
560
-13 10 I 151
1817
-7 10 I 172 177
-4 10 I 335 325
1393
80
56
49
-I 10 I
2 10 I
45
32
68
66
366
5 10 I
73
1255
8 10 I
48
29
38
7
1797
-18 11 I
139
-15 11 I 209 203
-12 11 I 495 495
562
-9
—6
—3
0
3
-17
-14
-11
-8
-5
-2
I
4
-10
-7
-4
-I
2
5
-18
-15
-12
-9
—6
-3
3
-17
-14
-11
-8
-5
-2
I
-4
11
11
11
11
11
12
12
12
12
12
12
12
12
13
13
13
13
13
13
14
14
14
14
14
14
14
15
15
15
15
15
15
15
16
I IOFo IOFc
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
CIS PARA-MENTHANE
I IOFo IOFc
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
741
356
103
41
106
63
361
494
360
298
53
209
93
154
49
103
207
112
122
37
189
359
311
240
102
43
64
184
203
234
69
114
114
95
736
364
92
18
107
73
364
510
353
301
33
204
92
154
50
95
209
129
119
I
192
353
314
254
105
44
65
191
206
221
83
102
106
72
h
k
-I
-15
-12
-9
-6
-3
-8
-5
0
-2
I
-4
-I
2
-6
-3
0
3
-8
-2
I
4
-10
-7
-4
-I
2
5
-12
-9
-6
-3
0
3
16
17
17
17
17
17
18
18
I
2
2
3
3
3
4
4
4
4
5
5
5
5
6
6
6
6
6
6
7
7
7
7
7
7
I
I IOFo IOFc
I
I
I
I
I
I
I
I
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
112
67
65
57
37
55
42
119
215
896
325
194
326
597
74
195
1298
1091
601
595
738
270
444
43
78
749
817
311
146
115
36
1095
1560
928
112
70
64
52
3
47
30
HO
287
922
310
163
320
563
33
150
1242
1069
560
527
709
288
443
23
29
718
799
303
149
121
8
1087
1464
913
Table 19 (cont.)
O bserved
h
k
6
7
8
8
8
B
8
8
8
8
9
9
9
9
9
9
9
9
9
10
10
10
10
10
10
10
10
10
11
11
11
11
11
11
11
-14.
-11
-8
-5
-2
I
4
7
-16
-13
-10
-7
-4
-I
2
5
8
-18
-15
-12
-9
-6
—3
0
3
6
-17
-14
-11
-8
-5
-2
I
and
c a lc u la te d
I IOFo IOFc
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
434
80
146
33
603
824
526
418
151
71
122
41
118
272
528
253
101
36
49
35
59
35
446
924
696
473
127
53
49
109
147
313
267
273
432
90
172
41
548
795
537
432
155
64
117
48
116
273
515
262
94
20
39
23
41
39
450
898
680
464
121
34
16
71
167
298
266
278
s tru c tu re
h
k
4
-13
-10
-7
-4
-I
2
5
-18
-15
“ 12
-9
—6
-3
0
3
-17
-14
-8
-5
,-2
I
— 16
-13
-7
-4
-I
2
-15
-12
-9
—6
-3
0
11
12
12
12
12
12
12
12
13
13
13
13
13
13
13
13
14
14
14
14
14
14
15
15
15
15
15
15
16
16
16
16
16
16
fa c to rs !
I IOFo IOFc
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
148
66
65
147
422
275
186
53
69
46
62
126
432
474
387
171
140
192
83
95
191
105
119
39
157
142
HO
49
112
49
68
128
173
92
148
80
34
151
423
290
190
35
56
49
84
109
429
480
385
172
141
180
81
98
184
111
111
52
158
156
108
35
112
43
64
136
174
91
C I S PARA-MENTHANE
h
k
-14
-11
-8
-2
-13
-10
0
I
-I
2
-3
0
3
-5
-2
I
4
-7
-4
-I
2
5
-9
—3
3
6
-I I
-8
-5
-2
I
4
7
-13
17
17
17
17
18
18
0
I
2
2
3
3
3
4
4
4
4
5
5
5
5
5
6
6
6
6
7
7
7
7
7
7
7
8
I IOFo IOFc
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
5
3
156
63
36
54
62
49
28
2139
2149
1614
23
33
55
1313
1637
902
269
685
1321
918
382
30
183
40
165
130
148
108
689
384
217
100
49
293
149
42
18
44
59
43
63
2212
2030
1507
43
42
30
1274
1531
897
284
638
1263
866
357
19
174
51
152
134
135
108
636
342
204
100
23
279
Page
h
k
-10
-7
-4
-I
2
5
8
-15
-12
-9
—6
-3
3
6
.9
-14
-11
-8
-5
-2
I
4
7
-16
-13
-10
-7
-4
2
- 5
-18
-15
-9
—6
8
8
8
8
8
8
8
9
9
9
9
9
9
9
9
10
10
10
10
10
10
10
10
11
11
11
11
11
11
11
12
12
12
12
I IOFo IOFc
3
47
3 115
3 267
3 220
53
3
3 165
3 307
3 295
3
50
3
39
3 181
3 158
3 169
3 221
3 217
39
3
48
3.
3
54
3 ' 32
3
36
3
32
3
35
3
50
3 272
3 100
3
40
3 148
3 102
3 .120
3 179
3 181
3 160
3
56
3 131
39
102
269
206
17
156
300
306
62
9
187
162
171
231
227
21
35
17
28
10
3
22
26
267
93
37
137
107
114
177
179
166
45
139
2
h
k
I IOFo IOFc
-3
0
3
6
-17
-14
-11
-8
-5
-2
I
-16
-13
-10
-4
-I
2
-12
-9
-6
—3
-14
-11
-8
-5
-2
— 13
-7
-12
-9
-6
-I
-3
0
12
12
12
12
13
13
13
13
13
13
13
14
14
14
14
14
14
15
15
15
15
16
16
16
16
16
17
17
18
18
18
I
2
2
3 175 185
3
45
11
3 118 120
3 144 144
3
61
37
3
32
27
3
95
95
3 293 280
3 164 160
3 128 132
3
70
69
3
99
93
3
40
29
3
40
22
3
39
22
3
55
57
3
86 101
3 156 152
3 296 292
3 225 230
3 129 123
3
90
88
3 265 270
3 302 303
3 .181 180
3 103
98
3
43
28
3
37
18
3 180 175
3 222 224
3 153 148
4 358 582
4 193 H O
4 1256 1019
Table 19 (cont.)
O tfserved
h
-5
-2
I
-7
-4
-I
2
-9
-6
-3
0
3
-11
-a
-5
-2
I
4
-13
-10
-7
-4
-I
2
5
-15
-12
-9
-6
-3
0
3
6
-14
and
c a lc u la te d
k
i IOFo IOFc
3
3
3
4
4
4
4
5
5
5
5
5
6
6
6
6
6
6
7
7
7
7
7
7
7
4
4
4
4
4
4
4
4
4
4
4
4
a
a
a
a
a
a
a
a
9
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
228
194
624
649
321
624
421
471
349
225
377
37
332
308
350
421
399
474
253
892
860
650
400
288
81
66
168
506
309
41
116
96
59
161
h
s tru c tu re
fa c to rs :
C I S PARA-MENTHANE
k
I IOFo IOFc
h
k
236
-11 9
84
-8 9
650
-5 9
596
-2 9
379
I 9
618
4 9
466
7 9
494
— 16 10
382
-13 10
211
-10 10
431
-7 10
21
-4 10
332
-I 10
329
2 10
396
5 10
442
8 10
356 . -18 11
464
-15 11
263
-12 11
857
-9 11
835
-6 11
595
—3 11
360
0 11
315
3 11
SI
6 11
79
-17 12
164
-14 12
521
-11 12
319
-8 12
.a
-5 12
150
-2 12
101
I 12
43
4 12
146
-16 13
4 526 519
4 507 527
4 475 498
4 286 310
4 187 176
4
38
44
4
42.
34
4 134 137
4 480 475
4 1018 1018
4 891 847
4 475 478
4 181 191
4
59
45
4
59
56
4
78
75
4
99 102
4 182 184
4 310 305
4 528 524
4 335 337
4 100 101
4
89
94
4
66
82
4
77
81
4
45
46
4
65 ■ 72
4 313 315
4 170 164
4
71
68
4
50
35
4
17
38
4
51
55
4
84
92
-13
-10
-7
-4
-I
2
-15
-12
-9
-6
-3
0
3
-14
13
13
13
13
13
13
14
14
14
14
14
14
14
15
15
15
15
15
15
16
16
16
16
16
17
17
17
17
18
18
2
2
3
3
-11
-8
-5
-2
I
-13
-10
-7
-4
-I
-12
-9
—6
-3
-11
-8
-2
I
-4
-I
I IOFo IOFc
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
292 298
482 477
257 256
41
5.0
34
14
103
92
99
94
71
68
158 154
71
46
86
81
129 141
157 153
98
95
179 186
78
69
59
46
95
87
90
79
86
92
129 135
44
29
57
51
85
78
45
50
36
9
87
74
157 150
96
98
87
65
26
31
712 714
737 686
715 705
h
k
2
-6
-3
3
-8
-2
I
4
-10
-7
-4
3
4
4
4
5
5
5
5
6
6
6
6
6
6
7
7
7
7
7
7
7
8
8
8
-I
2
5
-12
-9
—6
-3
0
3
6
-11
-8
-5
-2
I
4
7
-16
-13
-10
-7
-4
-I
8
8
8
8
9
9
9
9
9
9
I IOFo IOFc
5 273
5 437
5 734
5 196
5 757
5 273
5 276
5 656
5 117
5 264
5 434
5 278
5 677
5 465
5 222
5 213
5 265
5 197
5
29
5 134
5
81
5 119
5
29
5 754
5 673
5 854
5 579
5
53
5
56
5 104
5 125
5 213
5 655
5 850
261
469
729
190
740
259
287
669
113
256
456
286
662
467
225
224
236
180
8
150
72
123
4
746
665
850
564
38
55
97
121
206
660
847
h
k
2
5
8
-15
-12
-9
—6
■ -3
3
6
-17
-14
-8
-5
-2
9
9
9
10
10
I IOFo IOFc
5 598 603
5 199 217
5
77
76
5
64
62
5 113 109
10 5 127 119
10 5 111 111
10 5 135 143
10 5
66
60
10 5
89
90
11 5
52
35
11 5
61
66
11 5 120 124
11 5 467 488
11 5 598 614
I 11 5 482 478
4 11 5 132 130
-16 12 5 105 104
-10 12 5 103 101
-7 12 5 223 215
-4 12 5 581 562
-I 12 5 478 475
2 12 5 212 227
5 12 5 113 116
-15 13 5 135 127
-9 13 5
96
96
-6 13 5
79
73
—3 13 5
68
65
0 13 5
37
.4
3 13 5
56
69
-14 14 5
41
3
-11 14 5
63
65
-5 14 5 205 224
-2 14 5 212 225
y
Table 19 (cont.)
Observed and calculated structure factors:
h
I
-13
-10
-7
-4
-I
-12
-9
-6
-3
-11
-S
-5
0
I
-I
2
-3
0
3
-5
—2
I
4
-7
-4
-I
2
5
-9
-6
-3
0
.3
k
14
15
15
15
15
15
16
16
16
16
17
17
17
0
I
2
2
3
3
3
4
4
4
4
5
5
5
5
5
6
6
6
6
6
I IOFo IOFc
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
82
134
63
50
'133
87
104
58
87
71
57
87
111
879
477
476
1156
1446
1492
944
302
1152
346
181
356
301
343
348
109
40
305
956
405
68
81
126
68
32
126
80
104
61
96
66
39
85
122
701
562
570
1137
1345
1392
936
281
1141
326
146
344
300
340
339
96
39
324
928
418
72
h
6
-11
-8
-5
-2
I
4
7
-13
-10
-7
-4
2
5
8
-15
-12
-9
—6
-3
0
6
-17
-14
-11
-8
-5
-2
I
4
7
— 16
-13
-10
I:
I IOFo IOFc
Page
CIS PARA-MENTHANE
h
k
-7 11
24
32
6 6
-4 11
45
65
7 6
-I 11
62
7 6
57
2 11
7 6 356 350
5 11
7 6 349 359
-15 12
5
28
7 6
-12 12
85
79
7 6
0 12
7 6 252 244
3 12
8 6 112 116
-14 13
50
64
8 6
-I I 13
43
55
8 6
-8 13
8 6 177 158
94
-5 13
97
8 6
-2 13
94
8 6 102
I 13
8 6 114 121
-13 14
9 6 157 152
-10 14
43
40
9 6
-7 14
9 6 216 214
-4 14
40
76
9 6
-I 14
49
76
9 6
-15 15
9 6 170 181
9 6 158 157 . -12 15
-9 15
10 6 255 255
-6 15
10 6 223 224
0 15
73
80
10 6
-11 16
58
62
10 6
-8 16
95
10 6 113
-5 16
78
95
10 6
-10 17
38
10 6 . 51
-7 17
10 6 215 208
-3 2
10 6 261 261
-5 3
11 6 100 109
-2 3
11 6 119 123
I 3
68
84
11 6
I IOFo IOFc
6
6
6
6
6
6
6
6
6
•6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
7
7
7
7
51
82
51
139
123
74
43
65
44
72
125
105
98
135
47
69
218
251
213
46
81
66
153
150
54
107
118
131
252
256
336
249
338
290
56
78
38
135
125
72
6
52
34
69
115
106
111
142
35
68
223
250
219
46
77
67
155
153
29
102
124
129
253
260
372
236
334
283
h
-7
-I
2
-9
“6
—3
3
-11
-8
-5
-2
I
4
-10
-4
-I
2
5
-15
-12
-9
—6
-3
0
3
6
-14
-11
—8
-5
-2
I
4
7
k
I IOFo IOFc
81
4 7
4 7 287
4 7 253
5 7 538
5 7 369
5 7 252
5 7 509
6 7 398
6 7 597
6 7 368
6 7 255
6 7 192
63
6 7
86
7 7
86
7 7
7 7 193
7 7 120
7 7 167
42
8 7
8 7 425
8 7 674
8 7 603
8 7 512
8 7
39
89
8 7
54
8 7
9 7 223
9 7 479
9 7 676
9 7 542
9 7 119
61.
9 7
49
9 7
65
9 7
84
285
266
558
386
244
485
394
582
393
292
183
65
67
93
188
126
176
49
430
686
583
493
I
82
50
220
479
678
551
120
44
40
69
h
-16
-7
-4
-I
2
5
-15
-12
-9
-6
-3
3
-14
-11
-8
-5
-2
I
4
-4
2
-12
-9
—6
-3
-11
-5
-2
-10
-7
-4
0
-2
I
I;
10
10
10
10
10
10
11
11
11
Il
11
11
12
12
12
12
12
12
12
13
13
14
14
14
14
15
15
15
16
16
16
I
2
2
4-
I IOFo IOFc
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
8
8
8
90
77
58
60
52
38
118
349
484
399
SI
45
192
348
423
170
39
34
93
50
104
189
219
50
39
118
48
108
89
68
93
159
177
126
95
78
54
62
36
35
115
352
489
412
96
32
190
345
411
164
35
19
87
61
103
194
222
50
32
102
42
114
89
65
86
125
210
137
U)
O
Table 19 (cont.)
O bserved
h
-4
-I
2
-6
-3
0
3
-8
-5
-2
I
4
-10
-7
-4
-I
2
5
-12
-9
—6
-3
0
3
6
-14
-11
-8
-5
-2
I
4
7
-13
k
and
c a lc u la te d
I IOFo IOFc
3 8
3 8
3 a
4 8
4 B
4 -8
4 8
5 8
5
8
8
5
5
8
5
8
6
8
8
6
6
8
6 8
6
8
6 8
7 8
7 8
7 8
7 8
7 8
7 8
7 8
8 8
8 8
8 8
8 8
8 8
8
8
8 8
8 8
9 8
213
126
137
184
210
400
432
164
173
134
326
204
244
187
188
321
288
227
42
40
187
429
684
522
171
61
112
210
167
288
344
I 16
37
65
237
143
111
166
224
431
478
137
149
116
2^4
197
254
215
179
310
266
217
14
24
216
456
715
533
171
56
117
202
150
269
338
121
33
52
s tru c tu re
h
k
-10
-7
-4
-I
2
5
-15
-12
-9
—6
-3
0
3
-14
-11
-8
-5
-2
I
4
-13
-7
-4
-I
2
-12
-9
-6
—3
9
9
9
9
9
9
10
10
10
10
10
10
10
11
11
11
11
11
11
11
12
12
12
12
12
13
13
13
13
13
14
14
14
14
0
-11
-8
-5
-2
fa c to rs :
I IOFo IOFc
8
8
8
8
B
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
a
8
8
8
8
8
8
8
8
8
8
106
37
206
344
285
103
33
34
106
244
519
619
293
63
36
118
225
286
208
113
36
45
117
209
54
42
56
170
287
208
58
56
102
45
108
29
206
350
287
97
29
24
115
254
525
631
304
53
27
112
225
285
210
114
15
10
118
203
48
18
56
170
294
215
68
49
92
46
C IS
h
PARA-MENTHANE
k
-10 15
-7 15
-4 15
I I
-I 2
2 2
-3 3
0 3
3 3
-5 4
-2
4
I 4
4 4
-7 5
-4 5
-I 5
2 5.
-9 6
—6 6
-3 6
3 6
6 6
-11 7
-8 7
-5 7
-2 7
I 7
4 7
7 7
-13 a
-7 8
-4 8
-I 8
2 8
I IOFo IOFc
8
88
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
56
37
115
937
930
663
39
39
139
332
663
421
96
221
329
422
306
61
36
137
50
141
60
154
219
302
139
43
46
137
158
101
140
54
33
41
112
940
927
661
11
7
135
318
633
419
91
216
340
445
306
53
17
159
52
135
49
142
181
279
126
23
25
139
153
109
140
45
Page
h
I;
5
12
-6
-3
3
11
-8
-2
I
13
-7
-4
-I
2
12
-9
-6
-3
11
-8
-5
-2
-4
-I
-3
0
-5
-2
-7
-4
2
-9
—6
-3
8
9
9
9
9
10
10
10
10
11
11
11
11
11
12
12
12
12
13
13
13
13
14
I
2
2
3
3
4
4
4
5
5
5
I IOFo IOFc
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
10
10
10
10
10
10
10
10
10
10
10
169 162
99 103
61
42
52
60
70
66
46
7
40
9
46
37
46
35
99
95
62
57
44
15
43
43
46
29
36
8
101
95
143 138
73
69
107
91
141 133
170 167
57
38
44
10
62
48
131 122
212 192
143 •127
135 126
392 415
439 440
48
40
122 119
297 272
135 128
h
k
0
3
-11
-8
-5
-2
I
4
-13
-10
-7
—4
-I
2
5
-12
-9
-6
-3
0
3
-I I
-8
-5
-2
I
4
-13
-10
-7
-4
2
-12
-9
5
5
6
6
6
6
6
6
7
7
7
7
7
7
7
8
8
8
8
8
8
9
9
9
9
9
9
10
10
10
10
10
11
11
5
I IOFb IOFc
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
32
191
87
275
296
58
45
156
192
356
607
385
48
52
95
205
247
272
190
59
52
97
249
118
60
45
78
222
321
358
160
40
143
93
46
175
96
274
281
50
49
168
189
370
623
407
52
55
88
208
240
272
187
53
48
97
246
121
50
I
72
217
327
372
164
27
145
87
Table 19 (cont.)
O bserved
h
k
-6
-3
0
-11
-8
-5
-2
-10
-7
-4
0
I
-4
-I
2
—6
-3
0
3
-8
-2
I
4
-10
11
11
11
12
12
12
12
13
13
13
I
2
3
3
3
4
4
4
4
5
5
5
5
6
and
c a lc u la te d
I IOFo IOFc
10
10
10
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
11
11
11
11
11
11
97
54
73
142
201
84
35
224
198
76
38
45
123
60
269
143
124
37
70
41
274
458
250
106
97
50
66
144
205
90
26
219
193
68
I
50
121
52
276
145
128
2
72
44
280
466
255
108
h
-7
-4
-I
2
5
-12
-9
-6
—3
-11
-5
-2
I
4
-7
-4
-I
2
-9
-6
-8
-5
-2
-7
s tru c tu re
k
fac to rs :
I IOFo IOFc
6 11
6 II
6 II
6 11
6 11
7 11
7 11
7 II
7 II
8 II
8 11
8 II
8 II
8. 11
9 11
9 11
9 11
9 II
10 II
10 II
11 I I
It II
11 11
12 It
159
145
459
354
148
126
120
165
83
41
40
359
322
147
118
253
320
244
45
HO
35
149
246
126
159
149
468
368
152
123
126
153
67
37
35
366
332
153
125
247
333
254
30
99
37
149
255
120
C I S PARA-MENTHANE
h
k
I IOFo IOFc
-4 12 11
0 0 12
I I 12
-I 2 12
2 2 12
-3 3 12
0 3 12
3 3 12
-5 4 12
-2 4 12
I 4 12
4 4 12
-4 5 12
-I 5 12
5 5 12
-9 6 12
-6 6 12
-3 6 12
0 6 12
3 6 12
-11 7 12
-8 7 12
-5 7 12
156
836
349
342
87
464
430
185
202
93
183
70
205
184
63
60
203
185
193
80
72
77
43
153
824
362
356
95
456
445
176
191
94
186
73
203
195
58
49
196
189
188
64
78
75
10
Page
h
k
I
4
-7
-4
-I
7
7
8
8
8
8
9
9
9
9
10
10
10
11
11
I
2
3
3
3
4
4
5
-9
-6
-3
0
-8
-5
-2
-7
-4
-I
-3
-5
-2
I
-I
2
-9
I IOFo IOFc
12
65
12
90
12
72
12
72
12
78
12
72
12
70
12
59
12
80
12 122
12
55
12
56
12
73
12
73
12
82
13
34
13
58
13 179
13
57
13. 58
13
57
13
81
13 130
77
81
74
81
75
67
70
55
69
107
38
60
79
84
85
6
56
175
63
49
57
82
140
h
k
—6
—3
3
-8
-5
-2
I
-4
-I
—6
-3
-5
0
-2
I
-4
-I
2
—6
-3
0
-5
-2
5
5
5
6
6
6
6
7
7
8
8
9
I
2
2
3
3
3
4
4
4
5
5
6
I IOFo IOFc
13
13
13
13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
14
14
238
178
73
237
239
83
62
34
55
239
75
131
36
49
41
59
42
91
41
71
150
67
94
249
180
74
245
256
83
52
10
53
242
73
138
21
2?
29
51
34
97
19
56
155
52
92
93
APPENDIX C
Atomic Positions for 1,2,4 TMB-I,2, 4 TCB
Thiourea Adduct Structure
94
Table 20
Atomic positions from 1,2,4 THB-1,2,4 TCB thiourea
adduct structure (B1-B6, T1-T6, R1-R6 and
C20-C25 are idealized benzene rings)
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
Atom
SI
Cl
Nil
N12
S2
C2
N21
N22
S3
C3
N31
N32
BI
B2
B3
B4
B5
B6
Tl
T2
T3
T4
T5
T6
Rl
R2
R3
R4
RB
R6
C2 0
C21
C22
C23
C24
C25
I
X
Y
1-0.00556
0.63838
I 0.09079
0.70967
I 0.03603
0.74909
I 0.23024
0.72774
I 0.39843
0.64885
I 0 127982
0.68994
I 0.32437,
0.77146
I 0.13921
0.69558
I 0.31607
0.30130
I 0.27668
0.40610
I 0.33151
0.44722
I 0.18305
0.45126
I 0.25286 -0.06582
I 0.22353
-0.02192
I 0.32826
0.03401
I 0.46228
0.04602
I 0.49159
0.00209
I 0.38686
-0.05384
I 0.24322
-0.05515
I 0.19261
-0.02086
I 0.28183
0.03472
I 0.42167
0.05601
I 0.47227
0.02171
I 0.38305
-0.03386
I 0.07651
0.00423
I 0.21150
0.03270
I 0.26164
0.00324
I 0.17678 -0.05468
I 0.04179
-0.08314
I-0.00835
-0.05369
I 0.24572
-0.02592
I 0.10526 -0.04961
I 0.05007
-0.01840
I 0.13535 . 0.03649
I 0.27581
0.06018
I 0.33100
0.02897
Z
I
I 0.13959
I 0.09028
I -0.01069
I 0.15538
I 0.43859
I 0.49538
I 0.60626
I 0.43244
I 0.20406
I 0.22302
I 0.32590
I 0.13518
I
I
I
I
I
I
I
I
I
I
I
I
I
I 0.39206 I
0.28610 I
0.27349 I
0.36685 I
0.47283 I
0.48544 I
0.39206
I 0.25271 I
I 0.21913 I
I 0.29918 I
I 0.41281 I
I 0.44639 I
I 0.05436 I
I 0.13533 I
I 0.25133 I
I 0.28635 I
I 0.20538 I
I 0.08938 I
I 0.29482 I
I 0.21830 I
I 0.10305 I
I 0.06431 I
I 0.14083 I
I 0.25609 I
I
I
I
I
95
APPENDIX' D
Explanation of Space Group Labels
96
Table 22
Symbols for symmetry elements and for
the corresponding
symmetry operations In one-, two-, and
three-dimensions
[reproduced from (16)3
Printed symbol
m
o.6,ore
a
b
Reflection plane, mirror plane
Reflection line, mirror line
(two dimensions)
Reflection point, mirror point
(one dimension)
‘Axial’glide plane
I [010] or ![001]
1[00I] or ±[100]
f ±[100] or ±[010]
±[IT0] or ±[110]
I I [100] or ±[010] or ±[TT0]
I ±[ ITO] or ± [1 2 0 ] or ±[2T0]
‘Diagonal’glide plane
110011: ±[ 100]: ±[010]
I [ITO] or ±[Oil] or ±[T0l]
I
c
n
d-
±|II0]: ±[011]: ±[101]
"Diamond' glide plane
± | 0 0 l ] : ±[100]: ±[010]
± IITO]; ±[011]: ±[T01]
±[110]: ±[011]; ±[101]
Glide line (two dimensions)
9
±[01]; ±[10]
1
None
" fold rotation axis, n
2,3.4.6
" fold rotation point. /1
(two dimensions)
Centre of symmetry, inversion centre
Rotoinversion axis, n
T
2= ,2.4,6
tii
2,
3|,3;
4i.42,4j
,63,63,64,65
Generating symmetry opera'mn with glide or
screw vector
Symmetry element and itsorientation
n-fold screw axis,",
Reflection through a plane
Reflection through a line
Reflection through a point
Glide reflection through a plane, with glide vector
ic
h
U hexagonal coordinate system
jc
Glide reflection through a plane, with glide vector
J(a + b):](b + c):](a + c)
l(a f b + c)
](- a + b + c);](a - b f c);](a + b - c)
Glide reflection through a plane, with glide vector
i(a ± b);](b + c);]( ±a f c)
I(a + b + c):](±a + b f c);](a ± b + c)
j(- a + b ± c);](+ a - b + c);](a + b - c)
Glide reflection through a line, with glide vector
Ja;]b
Identity
Counter-clockwise rotation of .160/« degrees
around an axis
Counter-clockwise rotation of 360/» degrees
around a point
Inversion through a point
Counter-clockwise rotation of 360/« degrees
around an axis, followed by inversion through a
point on the axis
Right-handed screw rotation of 360/m degrees
around an axis, with screw vector (pitch)(p/«) t;
here Iisthe shortest lattice translation vector
parallel to the axis in the direction of the screw
Printed
symbol
C e n t r i n g t y p e o f cell
N u m b e r of
lattice po in ts
p e r cell
M
C o o r d i n a t e s o f lattice points
w i t h i n cell
T
Primitive
w o
T h re e d im e n s io n s
P
F
R
H
1
nS
I i
Primitive
Centred
Hexagonally centred
I
2
3
tw o -,
ro d u c
h
B
I
O
d im e n s io n s
C
C
I
O
P
A
O
H
tn
M1
0
O ne d im e n s io n
>
I
Primitive
C-face centred
X -face centred
B-face centred
B o d y centred
All-face centred
Rhombohedrally
(description with
Primitive
(description with
HexagonaIly cent
I
2
Mi PI
o 2
0,0
0,0;j,7
-S '
P- p>
2
2
2
4
centred
‘h e x a g o n a l a x e s ’)
3
I
‘r h o m b o h e d r a l a x e s ’)
red
3
0,0,0
0,0,0;1,1,0
0,0,0;0,i,l
0,0,0;1.0,i
0,0,0;4,
0.0,0;j,l,0;0,l,l;l,0,l
f 0 , 0 , 0 ; f , j , ^ ; } , | , | ( ' o b v e r s e s e t t i n g ’)
10 , 0 , 0 ;
^ ; f , £,§ ( ‘ r e v e r s e s e t t i n g ’ )
0,0,0
0,0,0;f,$,0;i,f,0
— (6
tn i
w Qt
U HI
3
tn
H-
I
H
O
(I
H
tn
UD
'U
Main I,IM .
N378
SpU?
cop.2