The X-ray crystallographic structure study of the 1,2,4 trimethybenzene thiourea adduct and 1,2,4
trichlorobenzene thiourea adduct
by Thomas Albert Wick
A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in
Chemical Engineering
Montana State University
© Copyright by Thomas Albert Wick (1986)
Abstract:
Many hard-to-separate aromatic mixtures can be separated by adduct formation with thiourea. Thiourea
adduction can be very selective even between aromatic isomers. In order to better understand the
selectivity mechanism and the forces which hold thiourea complexes together, an x-ray
crystallographic structure study was performed on two aromatic, thiourea adducts.
A diffractometer data set was collected on a 1,2,4 trichlorobenzene-thiourea adduct crystal and on a
1,2,4 trichlorobenzene—thiourea adduct crystal. Both adducts were solved in the space P21/c in a
monoclinic unit cell with parameters of a = 10.037(2), b = 15.155(1), c = 12.255(1), &alpha = γ =
90.0°, β = 112.77°(3), and a = 9.779(1), b = 15.355(1), c = 12.293(2), α = ^gamma; = 90.0°, β =
111.85&degj(4) for the 1,2,4 trimethybenzene adduct and 1,2,4 trichlorobenzene adduct respectively. A
disorder model for each adduct was proposed and the resultant R values were 0.0951 and 0.1053 for the
1,2,4 trichlorobenzene adduct and 1,2,4 trimethylbenzene adduct, respectively.
The general characteristics of these two structures are consistent with other similar thiourea adduct
structures. The possibility of a hydrogen bond between the aromatic ring C-H group and the thiourea
sulfur was found in both structures. From the non-bonded distances between the thiourea sulfur atoms
and the disordered aromatic, evidence for a dipole-dipole interaction exists. THE X-RAY CRYSTOLLOGRAPHIC STRUCTURE STUDY OF THE
1,2,4 TRIMETHYBENZENE THIOUREA ADDUCT AND
1,2,4, TRICHLOROBENZENE THIOUREA ADDUCT
by
Thomas Albert Wick
A thesis submitted in partial fulfillment
of the requirements for the degree
of •!
Master of Science
in
Chemical Engineering
MONTANA STATE UNIVERSITY
Bozeman, Montana
May, 1986
ii
APPROVAL
of a thesis submitted by
Thomas Albert Wick
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
Chairperson, Graduate Committee
Approved for the Major Department
S - M Date
-Xio
' VlO jSi
Head.^4 /Major Department
Approved for the College of Graduate Studies
Dat%
Z~~n(LGraduate
Dean
---
K 37 S
(jd
iii
STATEMENT OF PERMISSION TO USE
In presenting this thesis in partial fulfillment of the
requirements for a master's degree at Montana State University, I
agree that the Library shall make it available to borrowers under
rules of the Library.
Brief quotations from this thesis are allowable
without special permission, provided that accurate acknowledgment of
source is make.
Permission for extensive quotation from or reproduction of this
thesis may be granted by my major professor, or in his/her absence, by
the Director 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.
iv
ACKNOWLEDGMENTS
Special thanks is extended to Dr. Charles Cauglan for his
guidance in x-ray crystallography and to Dr. F.P. McCandless for his
ideas and support.
The author would also like to thank Dr. A. Fitzgerald, Jim Fait,
and Mark Spinti for their extensive personal communications.
In
addition, the author would like to gratefully thank my friend Robert
Pace and my wife Kitsy for all their moral support.
V
TABLE OF CONTENTS
Page
1.
LIST OF TABLES............................................
vii
2.
LIST OF FIGURES...........................................
ix
3.
ABSTRACT................
xi
4.
INTRODUCTION..............................................
Background........
Historical Review..............
*............... .
Research Objectives...............
I
I
3
17
5 . EXPERIMENTAL..... ........................................
19
Crystal Preparation............
Crystal Analysis.............
Adduct Density............. ........................
Crystal Mounting................
Photographic Film Studies.................
Diffractometer DataCollection, ......................
Solution of Structure andRefinement...............
“■
!
RESULTS AND DISCUSSION..... ............................ .
19
19
21
21
22
23
25
6.
Discussion of X-rayCrystallography...................
Aromatic—Thiourea Complexes..........................
7.
CONCLUSIONS... ............................................
27
27
31
59
8 . RECOMMENDATIONS...........................................
61
9.
LITERATURE CITED.... ".....................................
63
10.
APPENDICES................................................
66
Appendix A
Explanation of SpaceGroup Symbols...............
Appendix B
Elemental Analysis of the 1,2,4, TCB- Thiourea
Adduct, 1,2,4 TMB-Thiourea Adduct and
Pure Thiourea
67
72
vi
TABLE OF CONTENTS— Continued
Page
Appendix C
Tables for Publication for the 1,2,4 TCB
Thiourea Adduct..... ........................
Appendix D
Tables for Publication for the 1,2,4 TMB
Thiourea Adduct
74
112
vii
■ LIST OF TABLES
Table
Page
1.
Bond distances in urea....................................
5
2.
Lengths of the guest hydrocarbon plotted against the molar
ratio thiourea: guest for compressible and noncompressible guest.......
10
Compounds which form adducts with thiourea compared to
similar compounds which do not form adducts.... ..... .
12
Interatomic distances between sulfur and carbon in the
1.2.4 TMB-thiourea adduct.................................
14
Unit cell parameters for cis-paramenthane, cyclohexane
and carbon tetrachloride adducts........
16
Sulfur—carbon double bond distances in the thiourea for
various non-aromatic adducts.............................
17
Extinctions and associated symmetries of the 1,2,4 TMBthiourea complex and the 1,2,4 TCB-thiourea complex.......
24
8.
Structural data for related thiourea complexes.............
33
9.
Center-to-center intermolecular bond distances and
angles for the three coplaner sulfur atoms in the 1,2,4
TMB and 1,2,4 TCB adducts......... ;......................
37
Interactomic distances between sulfur and carbon in the
1.2.4 TCB-thiourea adduct structure.......................
51
Interatomic distance, between sulfur and carbon in the
1.2.4 TMB-thiourea adduct structure.......... ............
52
12.
The seven possible crystal systems........................
68
13.
Symbols for one-, two-, and three-dimensional cells.......
70
14.
Symbols for symmetry elements and for the corresponding
symmetry operations in one-, two-, and three-dimensions....
71
Elmental analysis for the 1,2,4 TCB-thiourea adduct, the
1.2.4 TMB-thiourea adduct, and pure thiourea..............
73
3.
4.
5.
6.
7.
10.
11.
15.
viii
LIST OF TABLES— Continued
Table
16.
17.
18.
Page
Atomic coordinates and isotropic thermal parameters for
the 1,2,4 TCB-thiourea adduct structure................. ..
75
Anisotropic thermal parameters for the 1,2,4 TCB-thiourea
adduct structure................. .............. .
76
H-atom coordinates and isotropic thermal parameters for
the 1,2,4 TCB-thiourea adduct structure....... ............
77
19.
Bond lengths for the 1,2,4 TCB-thiourea adduct structure...
78
20.
Bond angles for the 1,2,4 TCB-thiourea adduct structure....
79
21.
F(obs) and sigma (F) for the 1,2,4 TCB-thiourea adduct
structure........ ............................ ...........
- 80
Observed and calculated structure factors for the
1.2.4 TCB-thiourea adduct structure........ ..............
99
Atomic coordinates and isotropic thermal parameters for
the 1,2,4 TMB-thiourea adduct structure.... ...... .......
113
Anisotropic thermal parameters for the 1,2,4 TMB-thiourea
adduct structure.... ....................... ....... .
114
H-atom coordinates and isotropic thermal parameters for
the 1,2,4 TMB-thiourea adduct structure........ ...........
114
26.
Bond lengths for the 1,2,4 TMB-thiourea adduct structure...
115
27.
Bond angles for the 1,2,4 TMB-thiourea adduct structure....
115
28.
F(obs) and sigma (F) for the 1,2,4 TMB-thiourea adduct
structure.............. ........ .........................
116
Observed and calculated structure factors for the
1.2.4 TMB-thiourea adduct structure........ ...............
130
22.
23.
24.
25.
29.
ix
LIST OF FIGURES
Figure
Page
1.
Tetragonal urea showing the relatively open structure.....
7
2.
Lattice of urea and thiourea complexes..........
9
3.
Cis-paramenthane adduct viewed down the a-c diagonal.......
18
4.
1,2,4 TMB-thiourea complex viewed down the a-c diagonal....
35
5.
1,2,4 TCB-thiourea complex viewed down the a-c diagonal....
36
6 . Hydrogen bonding scheme in the thiourea lattice of the
7.
8.
1,2,4 TMB-thiourea adduct. The open lines are hydrogen
bonds. The view is down the carbon = sulfur double bond...
38
Stereoview, down the carbon = sulfur double bond, of the
hydrogen bonding network within the thiourea Lattice.
Open lines are hydrogen bonds................ ............
39
Stereoview of the thiourea hydrogen bonding network
viewed down the a—c diagonal. Hydrogen bonds are
drawn as dotted lines....... .............................
40
»..
9.
10.
'11.
12.
13.
Space filling plot of the three coplaner sulfur atoms of
the 1,2,4 TCB-thiourea adduct pointing directly into
the channel......... ..... .............................. .
42
Three coplaner sulfur atoms of the 1,2,4 TCB-thiourea
adduct with open lines defining the triangle formed
by the sulfur atoms.................
43
Electron density difference map of the 1,2,4 TCB-thiourea
adduct........................................
44
Electron density difference map of the 1,2,4 TCB-thiourea
adduct with an idealized 1,2,4 TCB molecule super­
imposed.......................................
45
Model of the 1,2,4 TMB molecule in the 1,2,4 TMB-thiourea
adduct........................ .........................
47
X
LIST OF FIGURES— Continued
Figure
14.
15.
16.
17.
18.
19.
20.
Page
Model.of the 1,2,4 TCB adduct in the 1,2,4 TCB-thiourea
adduct. The open lines indicate that it is not known
to which ring carbon the chlorine is bonded...............
48
View of the 1,2,4 TCB model in the region of the
three coplaner sulfurs......
53
Two thiourea molecules with planer sulfur atoms
pointing into the sides of the 1,2,4 TCB model. View
in looking down the sulfur = carbon double bond of the
third coplaner sulfer............................
54
One of the four model rings of the 1,2,4 TMB shown
in the region of the three coplaner sulfurs..... .......
55
One of the four model rings of the 1,2,4 TMB shown
in the region of the three coplaner sulfurs...............
56
One of the four model rings of the 1,2,4 TMB shown
in the region of the three coplaner sulfurs...............
57
One of the four model rings of the 1,2,4 TMB shown
in the region of the three coplaner sulfurs
58
xi
ABSTRACT
Many hard-to-separate aromatic mixtures can be separated by
adduct formation with thiourea. Thiourea adduction can be very
selective even between aromatic isomers. In order to better
understand the selectivity mechanism and the forces which hold
thiourea complexes together, an x-ray crystallographic structure study
was performed on two aromatic, thiourea adducts.
A diffractometer data set was collected on a 1,2,4
trichlorobenzene-thiourea adduct crystal and on a 1,2,4
trichlorobenzene—thiourea adduct crystal. Both adducts were solved in
the space P21/c in a monoclinic unit cell with parameters of a =
10.037(2), b = 15.155(1), c = 12.255(1), a = Y = 90.0°, 3 =
112.77°(3), and a = 9.779(1), b = 15.355(1),, c = 12.293(2), a =y =
90.0°, 3= 111.85°(4) for the 1,2,4 trimethybenzene adduct and 1,2,4
trichlorobenzene adduct respectively. A disorder model for each
adduct was proposed and the resultant R values were 0.0951 and 0.1053
for the 1,2,4 trichlorobenzene adduct and 1,2,4 trimethy!benzene
adduct, respectively.
The general characteristics of these two structures are
consistent with other similar thiourea adduct structures. The
possibility of a hydrogen bond between the aromatic ring C-H group and
the thiourea sulfur was found in both structures. From the non-bonded
distances between the thiourea sulfur atoms and the disordered
aromatic, evidence for a dipole-dipole interaction exists.
I
INTRODUCTION
Background
Frequently in industrial chemical processes mixtures of hard-to—
separate aromatic compounds turnup.
Since the compounds in these
mixtures have similar physical and chemical properties, separation is
often times difficult and economically poor.
Although conventional
separation techniques for these systems are diverse, they typically
require large amounts of energy to effect a minimal degree of
separation.
Distillation has been the standard technique for making such
aromatic hydrocarbon separations, but in some cases it is impractical
since the mixtures may pyrolize, may have close boiling isomers and/or
form azeotropes.
A n .alternative separation technique useful for
aromatic, isomeric hyocarbon mixtures is extractive crystallization.
Extractive crystallization, by its analogy to the nonideal
extractive distillation, is a selective process wherein a given
compound preferentially forms an adduct crystal with another component
thus effecting a separation (I).
Adduct complexes are a class of non—
stoichiometric compounds in which "guest" molecules are entrapped in
channels or cagelike structures formed by "host" molecules.
Adduct
crystals will form only with suitable "guest" molecules since the
spatial characteristics of the channel places structural constraints
on the guest molecules which can be accommodated.
When an adduct is
2
decomposed, the "host" and the "guest" molecules are returned
unchanged.
The most prevalent of "host" molecules are urea and thiourea.
It
is hypothesized that urea and thiourea form complexes easily because
of their large dipole moment and zwitterion characteristics (I).
Urea
forms crystalline adducts with normal hydrocarbons, but usually not
with branched or cyclic compounds unless the straight chain portion is
sufficiently long enough.
Thiourea forms channel adducts similar to
the urea adducts, however, due to the larger sulfur atom the channel
which entraps the "guest" is larger and thus can accommodate a larger
"guest".
On the other hand, a straight chain alkane would leave too
much of the channel unfilled producing an unstable structure.
The hydrocarbons which can be adducted with thiourea include the
branched paraffins, cyclohexyl-paraffins, certain chlorocompounds and
some branched cyclic aldehydes, alcohols, napthalenes, and ketones
(2).
Recent research has shown that substituted aromatics can be
complexed with thiourea.
Substituted aromatics known to adduct are o—
xlene, 1,2,4 trimethylbenzene, and the isomers of trichlorobenzene.
Certain aromatics can be induced to adduct if an additional compound,
referred to as an inductor, is present.
The inductors' contribution
to the complexing is not well understood, yet the inductor appears to
be selective with regard to certain aromatics.
Numerous organic compounds have been separated by adduct
formation with urea and thiourea by batch or continuous methods.
The
continuous method uses a fluidized, fixed or moving bed of urea or
thiourea with which the organic components are brought into contact.
3
The adduct crystals are filtered or decanted, then decomposed usually
by steam distillation or by heat.
Historical Review
The words complex and adduct came into common use during the
formative years of synthetic organic chemistry to designate substances
which do not appear to be held together by classical chemical bonds.
These substances were designated by early German investigators as
"Einschlussuerbindungen" or inclusion compounds.
The discovery of
urea adducts w a s .made accidently in 1940 by Bengen while studying the
action of urea on proteins in pasteurized milk.
In these studies
frothing and formation of an emulsion were causing difficulties, so
Bengen added a small amount of n-octyl alcohol as a defnothing agent.
Bengen observed the formation of long crystals at the interface of the
liquid layers.
On attempting to reproduce these crystals, Bengen
discovered that they also form when a saturated aqueous urea solution
was mixed with n-octanol.
Further investigation extended the urea
adduct formation to include higher alcohols, acids, n-paraffins, and
other straight chained compounds (2).
Bengen's work came to Lloyd Fetterly's attention in the Technical
Oil Mission publications of 1946.
Fetterly was attempting to improve
the octane ratings of gasoline by using a complexing agent which would
readily react with the low octane branched paraffins.
Although urea
would not complex with these hydrocarbons, he discovered that thiourea
would complex with the branched-chained paraffins as well as with
naphthenic compounds, some ketones, carbon tetrachloride, and some
4
other chloro compounds.
His studies also showed complex formation
with selenourea and tellurourea.
Concurrently in 1947 Angla, in
France, independently reported similar complexes between thiourea and
organic compounds of the terpene, camphene, cyclohexane, and
chloroparaffin classes (3).
In 1950 Redlick contributed to the current knowledge of thiourea
channel adducts by conducting thermodynamic studies at equilibrium
conditions.
Using Gibbs free energy relationships and a chemical
equilibrium equation, Redlich reported the composition and equilibrium
constants for the decomposition of thiourea complexes of various
isoparaffins, naphthenes and carbon tetrachloride.
He concluded that
equilibrium appeared to be that of a normal chemical reaction (4).
The indeterminate structure of the channel adducts prompted Smith
(5) and Schlenk (6) to conduct x-ray analysis on urea and thiourea
complexes in 1949.
Smith examined a number of urea complexes of n—
hyrdocarbons, alcohols, acids and esters of'various chain length CgC50 by the powder method.
Results indicated essentially identical
powder patterns for all complexes.
The extinctions and symmetry of
the Weissenburg patterns established the space group as C6^2-Dg2 or
its enantiomorph C6^2-Dg3 (See Appendix A). The unit cell for the
complexes is hexagonal with lattice parameters a = 8.230 A and c =
11.005 A.
The urea molecules were shown to form three interpenetrating
helical spirals with the hydrocarbon situated in the center.
The urea
molecules are held together by spirals of hydrogen bonds between an
oxygen atom and a nitrogen atom of adjacent molecules turned 120° with
5
respect to one another.
Each oxygen is hydrogen bonded to four nitro­
gen atoms and each nitrogen to two oxygen atoms.
The hydrogen bonds,
which are essentially coplanar with the urea molecules to which the
nitrogens are attached, are of two types.
The N....0 distances are
2.93 A for the shorter and 3.03 A in length for the longer.
The C-N-
H...0 bond angles are 136° and 116° respectively for the strong and
weak bonds.
The hydrocarbons located inside the channel, are at the special
positions (o,o,z) in a zigzag planar configuration with the long axis
of the molecule parallel to the c-axis.
The hydrocarbon molecules
show a disorder parallel to the c-axis. Rotation of the hydrocarbon
about the c-axis appears to cause this disorder.
Stability of channel adducts involves several physical and chemi­
cal phenomena.
Pure urea forms tetragonal crystals, whereas urea
adducts are hexagonal.
The bond distances between the two forms are
in Table I.
Table I.
Bond distances (A) in urea.
Urea-Hydrocarbon Complexes
C-O
C-N
N-H...0
N-H...0
1.28
1.33
2.93 A
3.03 A
-Pure Tetragonal Urea
C-O
C-N
N-H...0
N-H...0
1.25
1.37
2.99 A
3.03 A
The shortening of the N-H...0 bond yields a lower energy value which
indicates more stability in the hexagonal vs tetragonal form (9).
The
complexes are further stabilized by-the urea-hydrocarbon van der Waals
6
bonds.
Schlenk calculates a value of 2.8 kcal per CH2 group in urea
complexes.
Smith, however, refuted any unusually strong interaction
between the hydrocarbons and the urea such as that indicated by
Schlenk.
Smith suggests that the closest possible approach between a
carbon atom of the hydrocarbon and an oxygen atom of the urea is
approximately 4.1 A which is as large as or larger than normal van der
Waals distances for these atoms.
Fetterly (2) points out a new concept that a stronger hydrogen
bond can exist only when it is supported by an otherwise inert surface
(i.e., the channel hydrocarbon) capable of exerting only weak
dispersion forces.
Without the presence of a hydrocarbon, urea or
thiourea complexes cannot exist.
Fetterly referred to these
additionally stabilized bonds as "supported hydrogen bonds."
It was
this phenomenon that Fetterly claimed stabilized urea and thiourea
adducts.
Another factor that may contribute to 'the stability of the
complexes is that the van der Waals forces in the tetragonal urea may
be less than normal because of the relatively open structure
(Figure I), while those in the complex would appear to be normal (5).
This is also indicated by the smaller volume occupied by the complex
compared to the same number of urea molecules and guest hydrocarbon
molecules in their standard, pure crystalline states.
The complexes of non-aromatic thiourea discovered by Fetterly and
Angla are similar to urea complexes in almost every respect.
The
arrangement of thiourea molecules in the adducts is rhombohedral,
forming a pseudohexagonal but similar cell to that of urea complexes.
7
-C
NHz
■*—
Figure I.
a
= 5 67 A —*•
Tetragonal urea showing the relatively open structure.
There are 18 thiourea molecules per unit cell with space group R3 2/C
and a = b = 15.8 A, c = 12.5 A along the channel length (3).
As with
urea, the crystal structure of thiourea in an adduct is different from
that of the pure reagent. Pure reagent thiourea crystalizes in space
group Pbnm and is orthorhombic.
The unit cell constants of the
thiourea adducts apparently vary slightly with the nature of the
adducted hydrocarbon, hence, so will the channel dimensions vary
slightly.
The larger size of the sulfur atom in thiourea, compared with the
%
oxygen in urea, results in a channel of larger dimensions capable of
adducting larger cross-sectional guest hydrocarbons.
In Figure 2 the
cross-sections show the thiourea adduct schematically containing the
larger guest molecule.
The distance between two molecules lying one
above another is 4.2 A, and the edge length of the cell is 5.4 A,
8
these values compare with 3.7 A, and 4.8 A respectively for the urea
adduct.
Figure 2 shows only the oxygen or sulfur atoms with arrows
pointing toward the carbons.
The dotted lines in the urea hexagonal
prism connect oxygen atoms of the same elementary cell and indicate
the helical structure.
The three shaded regions in the thiourea
adduct represent planes formed by three coplaner sulfur atoms pointing
directly into the channel.
Schlenk suggested that because of the
optimal positions of the three coplaner thiourea molecules and their
strong dipole moments that these planes were regions of maximum
attraction (6).
Coplaner sulfur atoms occur every third sulfur along
an edge and since each atom is approximate 4.2 A apart, the distance
between planes is 12.5 A which is the c-axis unit cell dimensions.
A number of researchers conducted composition studies on urea and
thiourea complexes.
In urea and thiorea complexes the ratio of urea
or thiourea molecules to guest hydrocarbon"molecules increases
linearly with the length of the guest hydrocarbon (Table 2).
Exception to this relationship is with guest hydrocarbons which
exhibit what Schlenk referred to as compressibility. Table 2 uses ww'- methylene bridged dicyclohexyls as an example of compressible
guest hydrocarbons.
Schlenk (6) recognized that dicyclohexylmethane, I, 2
dicyclohexylethane and I, 3 dicyclohexylpropane showed an almost con­
stant mole ratio of 6:1.
Their x-ray patterns shows a compression of
the slender paraffinic portion of the guest molecule in the channel.
In this way several w,w - dicyclohexyl derivatives can fit into the
9
\
Figure 2.
L --—■ /
Lattice of urea (left) and thiourea (right) adducts. Top:
each circle represents a urea or thiourea molecule, the
arrow points from the oxygen or carbon atom toward the
sulfur atom. Bottom: cross-section with included
hydrocarbons [reproduced from Schlenk (6)].
10
same channel space.
Thus, if the fully extended length of the guest
hydrocarbon exceeds an integral multiple of c/2 only slightly, there
is a tendency for the enclosed molecule to take up a somewhat less
extended form whenever possible to fit the repeating half unit of the
thiourea complex.
In this way the terminal cyclohexyl rings coincide
with the zones of maximum attraction (12).
Since only one site of
maximum attraction occurs per unit cell, molecule ratios of muliples
three (i.e. 3:1, 6:1, 9:1 etc) will preferentially occur when the
guest hydrocarbon can compress.
ratio
In Table 2 the plateaus at molecule
6:1 and 9:1 exhibit this behavior.
Guest molecules which
cannot compress will form complexes of multiples other than three.
Table 2.
Lengths of the quest hydrocarbon plotted against the molar
ratio thiourea: guest for compressible and noncompressible
guest.
Num bers = No. C
Atom s in Chain
Urea
Thiourea
A U rea - n - Paraffin
O Thiourea - Highly
Branched P araffins
n Thiourea —u - u ' - Methylene
Bridged D icycloh exyis
Length of Extended M olecule
11
McLaughlin compiled a comparison list (Table 3) of organics, of
similar size and shape, that will or will not adduct with thiourea.
Although the dimension of the benzoid ring is very close to those
of the cyclohexyl ring, no adduction occurs.
This suggests that
adduction with thiourea requires the guest hydrocarbon to have other
properties besides the appropriate cross-sectional dimensions.
Some compounds which are non adducting by themselves can be
induced to form a thiourea complex when mixed with certain adduct
formers called "inductors".
Examples of induced compounds are
toluene, benzene, the xylenes, neptane, decane, dipentene, and I, 3 dimethycyclohexane.
Some examples of inductors are, cyclohexane,
dicyclohexyl, 2, 2, 4 trimethylpentane and decahydronaphtholene (2).
McCandless (10) reported the inductors which would adduct Cg and
Cg alkylbenzenes.
His work exemplified the ability of extractive
crystallization with thiourea to be an effective separation technique
for aromatic isomers and aromatics of close boiling points.
For
example CCl^ as an inductor exhibited a selectivity of ethylbenzene >
o-xylene > p-xylene > m-xylene while the use of 1,2,4 trichlorobenzene
(inductor) resulted in a selectivity of o-xylene > p-xylene > m-xylene
> ethylbenzene.
With the Cg alklybenzenes, CCl^ as an inductor was
selective for n—propylbenzene while 1,2,4 trichlorbenzene was selec­
tive for 1,2,4 trimethybenzene.
Similarly o-xylene and 1,2,4 tri-
methybenzene exhibited the same selectivity as 1,2,4 trichlorobenzene
when used with mixtures of the Cg and Cg aromatics, respectively.
of the inductors mentioned above also form complexes alone.
All
12
Table 3.
Compound which form adducts with thiourea compared to
similar compounds which do not form adducts.
Nonadductinft
A dd ucting
A dd ucting
Benzene
C ycloh exan e
T olu e n e
Methylcyclohexane
O=
O=
n - B u ty lb e n z en e
n-Euty!cyclohexane
y
n -H e x y I benzene
o
n-Hexy!cyclohexane
P h o n y !cy clo h e x a n e
O O
0-6
l-Phcnyl-2-cyclohexylethane
n-octylcyclohexane
O-Ss
n - O c ty ! b e n z e n e
> -C .
Z'
-=8
-Cr
I,2-Diphenylethane
r\
1,2-Dicyclohexylethane
1-
2-Cyclohexyleicosane
O O
Phenyleicosane
O
"
=
2
0
2-
/ C20
2-Cyclohexyleicosane
Pheny]eicosane
O
=
'
I,4-Diphonylbutane
I,4-Dicyclohexylbutane
O-=O
O-=
4
0
T e tr a lin e
Decalin
/
♦Reproduced from M a n d e l c o m
(2J
13
Welling measured the unit cell dimensions of the binary 1,2,4
TCB/1,2,4 TMB thiourea adduct and found a=12.64A, b=15.3A,
= 90.0° and 8 = 113.85°.
c=9.8A, a = y
Welling also enlisted the Molecular
Structure Corporation to obtain a structure for the 1,2,4 TMB thiourea
adduct.
Unit cell dimensions obtained were a=12.3A, b=15.1A,
c=10.0A, a = Y =90.0,
and 8 =112.7° (12).
Due to the disordered
arrangement from a translational view as well as through the inversion
center, a conclusive structure was not obtained from the Molecular
Structure Corporation.
However, Welling did postulate some ideas
about the thiourea lattice and 1,2,4 TMB interactions from intermolecular distances.
Initially Welling reasoned that benzene did not adduct because
the pi clouds, which lie both above and below the plane of the carbon
atoms, form a repulsive force with the lone pairs of electrons on the
nitrogen and sulfur of thiourea.
With this idea Welling speculated
that 1,2,4 TMB adducted because of an interaction between the methyl
groups and the thiourea lattice.
The isomers of 1,2,4 TMB (ie 1,3,5
TMB and 1,2,3 TMB) did not adduct indicating a steric hinderance
toward adduction.
The methyl groups on 1,3,5 trimethylbenzene are
symmetrically dispersed about the benzene ring and the methyl groups
on 1,2,3 trim ethylbenzene are concentrated to one side of the ring.
Both isomers are larger in diameter than that permitted by the
thiourea lattice and hence no adduction occurs.
In 1,2,4 TMB the benzene ring increases the electron density of
the carbon atom on the methyl group (13).
The methyl groups become
slightly acidic, or partially positive, through this resonance effect
U
and will induce weak hydrogen bonding with the sulfur atom in the
thiourea molecules.
Welling reasoned that if a hydrogen bond were to
be possible, the distance between the C-H group and sulfurs must be
closer than the non-bonded van der waal distance.
Since the covalent
radii for a C-H group is 1.08 A, the van der Waals radii for hydrogen
is 1.15 A, and the van der Waals radii for sulfur is 1.85 A, the nonbonded distance is the sum of these radii, or 4.08 A.
The Molecular
Structure Corporation reported the observed contacts between sulfur
and carbon.
These distances are tabulated in Table 4.
All of the
distances are less than the non-bonded distance (4.08 A) and thus
hydrogen bonding is a possibility (12).
Table 4.
Interatomic distances between sulfur and carbon in the 1,2,4
TMB-thiourea adduct;
Atom I
Atom 2
CU
C12
C13
C13
SI
SI
SI
S2
Distance A
v'
3.90
3.65
3.81
3.91
At Montana State University researchers Fait and Spinti, et al,
have conducted structural analysis on.non-aromatic isostructural
thiourea adducts.
Fait reproduced Lennes1 crystal structure for the
cyclohexane-thiourea adduct and independently determined the crystal
structure of the carbon tetrachloride-thiourea adduct and the bicyclo
(2.2.2) octane-thiourea adduct.
Spinti obtained a crystal structure
for the cis-paramenthane thiourea adduct.
All three complexes
crystallize in the rhombohedral space group, R3bar, as is
15
characteristic for non-aromatic complexes.
In addition, the honey­
comb shaped thiourea lattice formed with all three complexes.
lattice parameters are tabulated in Table 5.
The
The guest hydrocarbon
was disordered translationaly as well as around the axis of symmetry
in all three adducts.
Figure 3 shows the thiourea lattice with the
guest hydrocarbon, cis-paramenthane,
channel.
(Fig. 4) disordered in the
Fait reported sulfur atoms pointing into the channel and
hydrogen bonded to other thiourea molecules.
He concluded that
dipole-dipole interactions between the three coplaner thiourea sulfurs
and the CCl^ carbon and between the three coplaner thiourea sulfers
and cyclohexane hydrogens are responsible for binding of the substrate
hydrocarbon in these complexes.
Fait recognized that the sulfur-
carbon double bond distance for thiourea in these non—aromatic com­
plexes was lengthed in comparison with that of pure thiourea.
shows the magnitude of these bond distances.
Table 6
If a linear relationship
between bond strength and the c = s bond distance is assumed then the
conclusion which can be- drawn is that the dipole interaction between
the coplaner sulfurs and the guest hydrocarbon is stronger than the
hydrogen bonding interaction in pure, thiourea.
Table 5.
Unit cell parameters for cis-paramenthane, cyclohexane and carbon tetrachloride
adducts. All distances and angstroms.
Hydrocarbon
Adducted with
Space
Group
A
B
C
a
Y
S
Cyclohexane
15.708(1)
15.708(1)
12.431(2)
90.0
90.0
120.0
R3bar
^l4
15.539(1)
15.539(1)
12.529(2)
90.0
90.0
120.0
R3bar
Cis-paratnenthane
15.935(1)
15.935(1)
12.489(2)
90.0
90.0
120.0
R3bar
17
Table 6.
Sulfur-carbon double bond distances in the thiourea for
various non-aromatic adducts.
Thiourea Sulfer = Carbon
. Bond Distance
Crystal
Cydohexane-Thiourea Adduct
CCl^-Thiourea Adduct
Bicyclo [2.2.2] Octane Thiourea Urea Adduct
Pure Thiourea
1.725
1.744
1.731
1.708
(9)
(8)
(5)
(5)
Research Objectives
The purpose of this research was to continue the investigation of
the selectivity mechanism of aromatic thiourea adducts begun at
Montana State University.
1.
This objective would be facilitated by:
Obtaining a crystal structure of a 1,2,4 TMB-thiourea complex
using a more correct model than that employed by Welling and
the Molecular Structure Corporation.
2.
Obtaining a crystal structure of a 1,2,4, Trichlorobenzene*t
thiourea adduct in order that the heavier chlorine atoms
might resolve the disorder problem associated with the guest
hydrocarbons in thiourea complexes.
3.
From the intermolecular distances and positions yielded from
these structures, ascertain the interactive forces between
the thiourea honeycomb lattice and an aromatic guest
hydrocarbon.
18
B
Figure 3.
i
Cis para-menthane adduct viewed down the a-c diagonal.
19
EXPERIMENTAL
Crystal Preparation
The preparation of 1,2,4 trimethlybenzene-thiourea adducts and
1.2.4 trichlorobenzene-thiourea adducts has already been reported
(10,11,12).
However, an alternative technique was employed to avoid
twinning and enhance slow crystal growth.
A 20 ml saturated solution
of pure reagent thiourea and methanol was heated in a constant
temperature bath of 40°C.
Approximately three to four milliliters of
1.2.4 TMB or 1,2,4 TCB was added to this solution and the mixture was
sealed to avoid evaporation.
After one-half hour the mixture was
taken from the 40°C bath and placed in a 17°C constant temperature
bath.
Crystals from each aromatic system formed within 24 hours.
The
adduct crystals formed were long, cldar, hexagonal, and needle-like.
Any white, flat or plate-like crystals were known to be pure thiourea
crystals and were avoided when crystals were selected for x-ray
analysis.
Crystal Analysis
To ensure the reagent 1,2,4 TCB was not contaminated with its
isomers, a distillation was performed.
At the time of distillation
the barometric pressure was 638 mm Hg and the reflux ratio was 20:1.
In addtion, both adduct systems were analyzed by an elemental analysis
and by using a Varion Aerograph Series 1400 Gas Chromatograph.
20
Elemental analysis was conducted on the 1,2,4 TCB adduct 1,2,4 TMB
adduct and pure reagent thiourea.
The instrument employed was a Carlo
Erba Strumentazione Elemental Analyzer.
Crystals were prepared for both analyses by vacuum filtering
crystals, then placing them on filter paper to air dry for one hour.
If crystals are exposed to air for any extended length of time the
guest hydrocarbon will evaporate and the adduct will decompose.
___
Crystals to be analyzed with the gas chromatograph were then placed in
a minimum amount of boiling, distilled water.
The thiourea dissolved
in the water layer and the 1,2,4 TMB or 1,2,4 TCB formed a separate,
immiscible layer.
The organic layer and the aqueous layer were
separated with a separatory funnel.
The organic cut was analyzed with
the Varion Gas Chromatograph using a 5% diisodecyphthalate and 5%
bentone 34 on Chromosorb W column at 150° C.
helium.
The carrier gas used was
Pure reagent 1,2,4 TMB and 1,2,4 TCB were analyzed with the
gas chromatograph to compare as standards.'
The dried crystals to be analyzed with the elemental analyzer
were placed in small silver capsules and sealed with pliers.
Each
capsule was placed in a electrobalance which measured to the nearest
IO-^mg.
To ensure that the capsule was sealed and not losing weight,
due to evaporation of the 1,2,4 TMB or 1,2,4 TCB, the weight was
monitored for 5 minutes.
If in that time no change in weight was
recorded, the capsule was removed from the balance and placed in the
analyzer.
Cicloesanone and Sulfanamide were used as the standards.
Weight percentages of carbon, nitrogen and hydrogen were measured for
each sample.
21
Adduct Density
The density of an adduct was determined by suspending the adduct
in a mixture of miscible liquids, one more dense than the adduct and
one less dense.
The density of the solution which is in gravity
equilibrium with the adduct is also the density of the adduct (21).
In the case of 1,2,4 TCB a medium of carbon tetrachloride and methanol
was used to suspend the adducts and for the 1,2,4 TMB system, the
medium used composed of heptane and 1,2,4 trichlorobenzene.
Once the
crystals would neither sink nor float in the medium, a known volume
was weighed and the density calculated.
The densities were 1.49 g/ml
and 1.19 g/ml for the 1,2,4, TCB adduct and 1,2,4 TMB adduct
respectively.
Crystal Mounting
Selecting an appropriate crystal for x-ray analysis required
Vi ■
placing crystals on a microscope slide and positioning the slide under
a dissecting microscope.
Ample room was allowed for the crystals to
be cut or fragmented along their length.
Crystals were cut or
fragmented to the appropriate size using a sharp razor blade or
dissecting scalpel.
Once a crystal fragment of suitable size and
shape was selected, a glass fibfer dipped in adhesive Paratone-N was
used to transport the crystal from the microscope slide to a low lead
glass capillary tube of approximately 0.8 mm in diameter.
Care was
taken not to choose pure thiourea crystals which might have
crystalized out of the mother liquor.
22
The capillaries were sealed by heat or glue to prevent air expo­
sure from decomposing the crystal.
To check for twinning (multiple
crystal growth), the crystals were examined under polarized light.
Crystals which extinguished upon rotation between crossed nickle
prisms were used for x-ray analysis.
The 1,2,4 TMB adduct crystal
used for data collection was cylindrical in shape measuring 0.6 mm in
diameter and 0.8 mm in length.
The 1,2,4 TCB adduct crystal was also
cylindrical in shape and had dimensions 0.7 mm in diameter and length
of 0.9 mm.
Photographic Film Studies
A Weissenburg camera was employed to check crystal quality and
estimate unit cell dimensions.
with a nickel filter.
The radiation source used was copper
Weissenburg photographs taken for a dete­
riorated adduct would show few, if any, layer lines and those lines
which Were present would contain indefinite spots.
Once a suitable
crystal was obtained, oscillation, zero level, first level, and second
level photographs were collected to determine approximate unit cell
dimensions.
Numerous Buerger Precession photographs were taken for the 1,2,4
TCB complex.
These photographs were expected to provide support for,
as well as clarification of, the unit cell dimensions.
Problems were
encountered which involved the alignment of the crystal for precession
photographs and this method was abandoned since the photographs were
not necessary to proceed with the diffractometer data collection.
23
Diffractometer Data Collection
Intensity data for both adduct systems were collected on a
Nicolet R3mE automatic four circle diffractometer using the omega scan
technique with the 1,2,4 TCB complex and the theta—two—theta scanning
technique with the 1,2,4 TMB complex.
The x—ray source used was MoKg
radiation of A. = 0.71069 A, and monochromated with a graphite crystal
monochromator.
Both data sets were collected at room temperature.
Throughout the course of the data collection three standard reflec­
tions were measured every one hundred reflections.
There was no
decrease in the intensity of these standards over the course of the
data collection.
For instance, the decrease in the average value of
these standards was about 7% by the end of the data collection for the
1,2,4 TMB complex.
the standards.
Al intensities were corrected for the changes in
Lattice parameters for the 1,2,4 TCB complex were
obtained from the least squares fit of 20 centered reflections for
'i
which 25O<20<35°. For the 1,2,4 trimethy!benzene thiourea complex the
same procedure was followed using 25 centered reflections with
28O<20<31°. The data collected on each complex ranged from 3° to 50°
on 20.
Asmuitlial adsorption correction data was taken for both com­
plexes.
For the 1,2,4 TMB complex the linear absorption coefficient,
y (MoKg) was 4.01 cm-^ and no correction was made for absorption.
For
the 1,2,4 TCB complex, y (MoKg) = 8.89 Cm-^and an empirical absorption
correction was made to the intensity data.
The two data sets were
reduced in the usual manner with appropriate Lorentz and polarization
corrections.
Scattering factors for C1,S,0,N,C and H and anomolous
24
scattering terms for all types except H were taken from the
International Tables for X-ray Crystallography (18); all atoms were
assumed to be in the zero ionization state.
For the 1,2,4 TCB-Thiourea complex, 3397 intensities collected
yielded 1610 observed reflections.
The data set for the 1,2,4 TMB-
Thiourea complex had 3161 intensities collected of which 1536 were
observed reflections.
Criterion for observed reflections was I > 3a.-
The data sets for both complexes reveal the monoclinic primitive
lattice.
In addition, both sets showed the following extinctions in
Table 7.
Table 7.
Extinctions and associated symmetries of the 1,2,4 TMBthiourea complex and the 1,2,4 TCB-thiourea complex.
Reflections Absent
UOO
UOG
UOU
OUO
Symmetry Indicated
n glide perpendicular
*to b 2 fold screw axis on b
From these extinctions the space group P21/c was determined for
both structures.
A least squares fit of 25 centered reflections produced the unit
cell dimension of a = 10.037 A, b = 15.155 A, c = 12.255
A, g = 112.77°, and a = 9.779 A, b = 15,355 A, c = 12.293 A, g =
111.85° for the 1,2,4 TMB-thiourea complex and the 1,2,4 TCB-thiourea
complex respectively.
25
Solution of Structure and Refinement
The 1,2,4 TCB complex was solved initially by direct methods.
Since the two complexes are isostructural with respect to the thiourea
honeycomb lattice, sulfur positions from the 1,2,4 TCB complex were
used for the initial phasing of the 1,2,4 TMB-thiourea complex.
Once
the sulfur positions were found, the thiourea nitrogens and carbon
appeared on the difference maps.
These atoms, along with any other
strong peaks, were added to a model and the model's structure factors
were compared to the observed structure factors.
A resultant R value
was obtained and if the R value decreased, the peaks were left in the
model.
At this point the thiourea positions were well-defined, yet
the channel atoms were disordered.
Refinement for both complexes was done using a block cascade
least-squares refinement program where the minimization function;
M =
'weight (IFobs|- |Fcalc|)^
used to refine 101 parameters in each full matrix block.
Fobs was the
observed structure factor and Fcalc was the calculated structure
factor (22).
The thiourea molecules were well-behaved and thus a model was
easily fit to the thiourea lattice.
Once the carbon, sulfur and
nitrogen atoms of the thiourea were well defined, hydrogen atoms of
the thiourea began to appear on the difference maps and the thiourea
molecules were refined anistropically.
26
The 1,2,4 TMB or 1,2,4 TCB remained disordered in the channel and
were refined isotropically.
In the final refinement the weighting
factor used was
Weight I/ [sigma**2(F) + (.0004F*E)].
The 1,2,4 TMB-thiourea structure refined to R = .1053,
Rw = .0911, Rg = .0990, Rm = .0990, and goodness of fit = 2.399.
The
1,2,4 TCB-thiourea structure with the two ring disordered model
refined to R = .0951, Rw = .0927, Rg = .1061, Rm = .1061, and goodness
of fit = 2.650.
R = 0.15.
Without the model's, both structures refined to about
27
RESULTS AND DISCUSSION
Discussion of X-ray Crystallography
An ideal crystalline substance is a homogeneous solid in which
the atomic or molecular arrangement repeats by translation in three
dimensions; the repeat distance and direction can be described by a
three dimensional coordinate system.
A crystal is composed of atoms
oscillating about regular positioning of a lattice, repeating in
accordance with the crystal system and symmetry (26).
If x-rays are
passed through a crystal the incident beam is diffracted by the
electrons of the atoms according to Bragg's law of diffraction;
nX = SdsinS
i
n
X
d
0
=
=
=
=
(I,2,3,4, . . .)
wavelength of incident radiation
distance between reflecting planes
angle between the incident or reflecting surface
The intensity and coordinates of the reflecting or diffracted
radiation are collected by the diffractometer using a radiation
counter.
The intensity of a diffracted wave is dependent upon the
atomic position and the atomic scattering factor, which is a function
of the number of electrons in the atom.
Furthermore, since changes in
temperature of crystals affects the thermal vibrations of the atoms,
the intensities must be corrected for this temperature effect.
In
28
general the greater the vibrations the more the intensities will be
lowered.
The intensities of the reflections- from the diffracted x—rays are
^i^sctly obtainable from a radiation counters however, the phases of
the reflections are not directly obtainable, yet they are essential
for crystal structure determination.
Crystollographers have shown
that the wave scattered by a crystal can be characterized by a
quantity, Fhkl, referred to as the structure factor (23).
More
generally, the structure factor for any given configuration of matter
is the ratio of the amplitude of the wave scattered by all the matter
in that configuration in any direction to that scattered by a single
electron under corresponding conditions.
Thus* following this
definition, the structure factor of an electron is always unity (24).
The amplitude of a scattered wave is proportional to the intensity,
only after scaling, Lorentz-Polarization corrections, absobbtiori and
other comperical corrections are applied to the intensity.
Mathematically:
1Iikl cal = (Fhkl cal )2
Fhkl = E fje^ frxj+ k yj-H Z j)
or.
29
where
= intensity of nkl reflection
fractional coordinators
fj
=
scattering power of an atom at angle 0
The scattering power of an atom is tabulated in the literature for all
elements.
wave.
The term 0, is referred to as the phase of the reflected
Each
is complex; that is, it is characterized by both a
magnitude, IFy^l, and a phase
The magnitude can be
experimentally observed but, as mentioned previously, the phase cannot
(25).
If, in studying the arrangement of atoms in a given crystal a
particular model is proposed, the set of
computed.
of the model can be
The test for correctness of a crystal-structure model to be
correct is that the set of structure factors computed,
match the observed structure factors, F^ -, 0^g.
calc*
It is, however,
possible to obtain a good agreement with an incorrect structure.
This
calculation is greatly simplified by fast computers.
The ultimate goal in the determination of a crystal's structure
is finding the positions of all the atoms in the unit cell.
These
atomic positions are not found directly but are deduced from the
electron density.
Atomic positions are found where the electron
density is at a maximum.
using the equation:
The electron density, p (x,y,z), is computed
30
p(x>y;z) = i/v*x;£EFhkie~ 2TTi(hx+ ky + lz)
where
V = volume
Fhkl = structure factor of hkl reflection
x
y
= fractional coordinates
z
Thus, once structure factors are determined, the electron density can
be computed using Fourier synthesis.
The Fhfcl calc and Ffcfcl ofcs
determined are refined using least squares calculations.
The measure
used to quantify the agreement between the model and the actual data
is the R value.
The R value equation used for the 1,2,4 TMB complex
and the 1,2,4 TCB complex was:
R=
m F Q l-[FcU _ ,
! 2
I
p
0
I
1/2
R yv=ZCI IF I-IF I IM w e i q h t )±/ *3
ZCFq* (weight
1/2
7
1/7
' Rj= C Z (weiqht*C I I F J - I F J 1 1 ) 1
ZCweight^Fq2I
(calculated for the scale
factor which minimizes R^) (22).
31
Conventionally, R values less than about 0.07 reveal that the
model has "solved" the crystal structure, although technically it only
means that the model fits the data within reasonable agreement.
To
claim the model represents the true crystal structure, the agreement
(R value) between
F q ^ s and
Fca-^c must be acceptable and the model
must adhere to chemical and physical laws.
Aromatic—Thiourea Complexes
The Molecular Structure Corporation's x-ray analysis of 1,2,4
TMB-thiourea complex was unable to resolve the disorder of the 1,2,4
TMB in the channel.
This motivated a new structure determination
using a different model solution.
Furthermore, it was hypothesized
that if the methyl groups in 1,2,4 trimethylbenzene were replaced
with chlorines, forming 1,2,4 trichlorobenzene, that these heavier
chlorine atoms would appear more defined in an x-ray analysis.
If the
chlorine atoms were more defined in an x-ray data set, a correct model
would be assembled easier.
From floatability the densities of 1,2,4 TMB-thiourea and 1,2,4
TCB-thiourea were 1.19 S/ml and 1.49 S/ml respectively.
The elemental
analysis listed in Appendix B proved the thiourea to be of pure
reagent grade and a balance on nitrogen showed the mole ratio of
thiourea to aromatic to be 4.38 and 3.55 for 1,2,4 TMB-Thiourea and
1,2,4 TCB-Thiourea respectively.
These mole ratios were confirmed by
the density measurements which yielded mole ratios of 4.40 and 3.55
for the 1,2,4 TMB-Thiourea and 1,2,4 TCB-Thiourea respectively.
The
distillation of 1,2,4 TCB and the gas chromotography analysis proved
32
the adducts to contain only the pure reagents (i.e. no isomeric
impurities).
Additional structures studied for comparison in this work are
listed in Table 8.
As can be seen, the non-aromatics crystallize in
the same space group R3bar and have similar cell dimensions.
The
adduct containing a 50 mole percent of both 1,2,4 TCB and 1,2,4 TMB
crystallizes in the same space group as the 1,2,4 TMB-thiourea' and
1,2,4 TCB-thiourea complexes and has approximately the Same cell
dimensions.
This change in space group between aromatic and non­
aromatic adducts suggests that there is a fundamental change in the
thiourea channel shape.
This change indicates a possible different
kind of interaction between the aromatic and the thiourea lattice than
that between non—aromatics and thiourea.
The two adduct systems were proved to be isostructural when the
thiourea positions from the 1,2,4 TCB-thiourea were successfully used
for the initial phasing for the thiourea positions in the 1,2,4
trimethylbenzene-thiourea adduct.
Figures 4 and 5 exhibit the
similarities between both complexes' thiourea lattice.
The structures
show a pseudo hexagonal lattice with distorted channel walls.
view is down the a—c diagonal.
The
Both structures have very similar
atomic positions for the thiourea molecules.
The graphics software in
the SHELXTL package allowed for interatomic distances between bonded
and non-bonded atoms to be found (22).
The graphics program showed each sulfur atom to be hydrogen
bonded to NH 2 groups on four adjacent thiourea molecules.
This is
illustrated in Figures 6,.7, and 8 where the hydrogen bonding scheme in
Table 8.
Structural data for related thiourea complexes.
Hydrocarbon
Adducted with
Cyclohexane
CCl4
cis para-menthane
1.2.3
1.2.4
1,2,4
1,2,3
1,2,4
TCB and
TMB
TCB and
TMB
TCB
1,2,4 TMB
1/2/4 TCB and
1,2.4 TMB
I
I
I
All distances and angstroms.
a,
90.0
I
I
B
90.0
I
I
y
120.0
I Space
I Group
I R3bar
I DENSITY
I (a/cm3 )
I 1.138
90.0
I
90.0
I
120.0
I R3bar
I .1.415
90.0
I
90.0
I
120.0
I R3bar
90.0
I
113.8
I
90.0
I P2,/c
I
I
A
I
B
I
C
I
115.708(1)(15.708(1)|12.431(2)I
I
l
l
l
115.539(1)|15.539(1)|12.529(2)|
I
l
l
l
115.935(2)115.935(2)112.489(2)|
I
l
l
l
I 12.64
I 15.3
I 9.8
|
I
I
I
I
I
I
I
I
I
l
l
l
I .9.779(1)|15.355(1) |12.293(2) I
I
l
l
l
|12.3 (I)|15.1 (1)110.0 (2)|
I
I
I
I
I 9.886(7)|15.245(8)|12.313(6)I
I
l
l
l
I
1.16
I
1.27
I P2,/c
90.0
I
111.85 I
90.0
I P2,/c
I
I
1.3
.1.49
90.0
I
112.7
I
90.0
I P2 I/c
I
1.19
90.0
1112.48(4)I
90.0
I P2,/c
I
1.28
34
the thiourea network of the 1,2,4 TMB-thiourea adduct is shown.
The
four hydrogen bonds, denoted as dotted or dashed lines, are of lengths
3.314 A, 3.402 A, 3.454 A, and 3.452 A.
The corresponding lengths for
the 1,2,4 TCB-thiourea adduct are 3.433 A, 3.348 A, 3.446 A, and 3.408
A.
At room temperature pure crystalline thiourea has three sulfur-
nitrogen hydrogen bonds of 3.526 A, 3.394 A, and 3.696 A in length
(15).
The shortening of these hydrogen bonds in the complexes indi­
cates a lower energy state and correspondingly a greater stability.
Although Smith contends that compacting of the adduct structures is
solely responsible for holding the adduct together, a review of Table
2 suggests other factors seem at work.
For example, evidence of this
is the fact that cyclohexane adducts, but benzene does not.
Schlenk suggests a zone of maximum attraction in each unit
cell, corresponding to three coplaner sulfur atoms (see Figure 2).
These zones are evident in both the 1,2,4 TCB-thiourea adduct and the
1.2.4 TMB-thiourea adduct.
Figure 9 sflows three coplaner sulfur in
the 1,2,4 TMB-thiourea adduct, pointing directly into the channel
exhibiting a zone of maximum attraction.
The three thioureas do not
form an equilateral triangle, but instead are slightly distorted about
the a-c diagonal.
The thiourea lattice in each complex is by and large responsible
for the space group symmetry and therefore the positions and '
intermolecular distances and angles are nearly identical for both
structures.
Figure 10 shows the three coplaner sulfur atoms for the
1.2.4 TCB-thiourea adduct with open lines forming a triangle.
The
35
vw
N '' \
Figure 4.
^
''
1,2,4 TMB-thiourea complex viewed down the a c diagonal.
36
Figure 5.
,2,4 TCB-thiourea complex viewed down the a c diagonal.
37
center-to-center intermolecular distances and angles represented by
this triangle are given in Table 9 for both complexes.
In order to obtain an idea of how the aromatic in the channel was
situated a series of electron density difference maps were generated
for the 1,2,4 TCB-thiourea adduct.
The electron density difference
map shown in Figure 11 was generated using only the refined thiourea.
The view is looking down on the plane of the 1,2,4 trichlorobenzene.
The contours range from -0.1 to 2.3 electrons per cubic angstrom.
Table 9.
Center-to—center intermolecular bond distances and angles
for the three coplaner sulfur atoms in the 1,2,4 TMB and
1,2,4 TCB adducts.
1,2,4 TMB--Thiourea
1,2,4 TCB-Thiourea
Distances A
S1-S2
S2-S3
S3-S1
9.043
7.053
8.165
9.067
7.073
7.944
Angles in Degrees "
<S1
<S2
<S3
48.1
59.4
72.5
48.6
57.4
74.0
The dotted lines are levels 0 and -0.1, the dashed lines are levels
0.1 to 1.1 and the solid lines are levels 1.1 to 2.3 electrons per
cubic angstroms.
The plot clearly shows the repeat down the channel
of four peaks.
Upon superimposing an idealized 1,2,4 trichlorobenzene molecule
in the channel it was evident that there are at least four different
arrangements for which the molecule can satisfy the electron density
38
Figure 6.
Hydrogen bonding scheme in the thiourea Lattice of the
1,2,4, TMB-thiourea adduct. The open lines are hydrogen
bonds. The view is down the carbon=sulfur double bond.
39
=Ci
*
Figure 7.
Steroview, down the carbon=sulfur double bond, of the
hydrogen bonding network in within the thiourea lattice.
Open lines are hydrogen bonds.
40
Figure 8
Fr.-: xusrirrurs = t =z
41
scheme.
The combination of these arrangements yielded aromatic ring
carbons overlapping chlorines and adjacent ring carbons.
This gave an
indication of the disorder which arose when constructing a model to
describe the aromatic positioning in the channel.
Figure 12 exhibits
the electron density difference map with an idealized 1,2,4
trichlorobenze molecule superimposed in one of at least four possible
arrangements.
Models for the aromatics in both complexes were constructed by
constraining atoms in the channel which resembled a benzene ring and
refining them using least squares.
For the 1,2,4 TMB-thiourea complex
this resulted in four benzene rings seen in Figure 13.
rings are in pairs which are planer.
are nearly in the same plane.
The two planer pairs of rings
The 1,2,4 TCB-thiourea complex yielded
two benzene rings in the same plane.
Figure 14.
The benzene
This model is shown in
The open lines indicate that it is not known to which
aromatic carbon the substituent is bond;
In both models, atoms were
added where peaks on the difference maps indicated a possible chlorine
or methyl group.
Explanation of the disorder of the aromatics requires examination
of the size and orientation of the guest and thiourea lattice.
Within
the thiourea lattice, coplaner sulfurs occur every third sulfur on the
c-axis and this interplaner distance for both complexes is 12.54 A
(Figure 2).
The maximum lengths of a 1,2,4 trichlorobenzene molecule
and of a 1,2,4 trimethybenzene molecule are 9.77 A and 9.25 A,
respectively, including their van der Waal radii.
Since the aromatics
are found only within the region of the three coplaner sulfurs and
42
Figure 9.
Space filling plot of the three coplaner suffer atoms of
the 1,2,4, TCB-thiourea adduct pointing directly into the
channel.
43
Figure 10.
Three coplaner sulfur atoms of the 1,2,4 TCB-thiourea
adduct with open lines defining the triangle formed by the
sulfur atoms.
44
W
m
W
1'
,X
mmmmhM
r
w
n
m
§
m
m
?
-
m
m
^
€
$
m
^
v
^
^#6
5
:- J
rc ^
, . 's '
'%>
;c%
^ -/s
PQ^S*,.
^
^
^.S '
WBr
Figure 11.
l'z= <>xv
—
<
/
m
:
3
:
:
:
:
&
^
s'x'lw\V
r\>'. r i ^ ' l r ’. / %
-
/
' ''"'
r
v
.
/
.
y
^
''''
Ts-
" t o
Ir^Y
Electron density difference map of the 1,2,4 TCB-thiourea
adduct. X = 24.107 A, Y = 24.107 A
45
-gSOEIiS
Pfiili
r -Z i
ZizZZ'"
z
a
s
i
Cx
-ZC'
-
'■ „ a
##% #
meam#
3
I■~J"~
:%-
^ ar,X^i{ai4v^
Figure 12.
—
_y.
>> ^
Z-
Electron density difference map of the 1.2,4 TCB-thiourea
adduct with an idealized 1.2.4 TCB molecule superimposed
X = 24.107 A. Y = 24.107 A
46
their lengths are shorter than 12.54 A, disorder translationalIy seems
to arise from site disorder and or orientation disorder and not
adjacent aromatics overlapping into the next unit cell.
When the adducts are formed, the aromatics are equivalently
positioned in the same channel unless there is a zone of maximum
attraction unoccupied, then the preceeding aromatics may initiate
another positioning along the channel which is different than that
before the empty zone.
Site disorder arises when the aromatics in a
channel are positioned differently than aromatics in another channel.
The disorder arises because the crystollographic data is an average of
all the positions.
If diffraction data could be obtained for each
unit cell, the disorder could be resolved.
The empty or unoccupied
zones of maximum attraction are responsible for the non­
stoichiometry of these complexes.
In the 1,2,4 TCB-thiourea complex and the 1,2,4 TMB-thiourea
complex the aromatic ring might be positioned equally in any of two or
more unit cells, however, the chlorines or methyl groups on the rings
might be oriented differently.
disorder.
This is referred to as orientation
This occurs since the aromatic ring can remain constant
while the chlorines or methly groups are moved by rotating the
aromatic 180°.
It is site and or orientation disorder which are
responsible for the 1,2,4 TCB and 1,2,4 TMB models having overlap of
atoms.
The disordered aromatics prevent the precise location of the
thiourea and aromatic interactions.
Generally it can be said that the
aromatic interacts with one or all of the three coplaner sulfurs.
The
47
Figure 13.
Model of the 1,2,4 TMB molecule in the 1,2,4, TMB-thiourea
adduct.
48
Figure 14.
Model of the 1.2,4 TCB adduct in the 1.2,4 TCB-thiourea
adduct. The open lines indicate that it is not known to
which ring carbon the substituent is bonded.
49
nature of the strength of this interaction can be understood by
studying the sulfur-carbon double bond length in the three coplaner
sulfurs.
The sulfur-carbon double bond lengths in the three coplaner
thiourea are 1.698(9) A, 1.706(10) A, 1.707(8) A 5 and 1.707(8) A 5
1.698(9) A 5 1.706(10) A for the 1,2,4, TCB adduct and the 1,2,4 TMB
adduct respectively.
These bond distances are about the same as the
sulfur-carbon double bond distance found in pure thiourea.
It can be
concluded that the interaction between thiourea and the aromatic in an
adduct is of the same magnitude as that of the hydrogen bonding in
pure thiourea.
Table 9 shows non-aromatic adducts having a stronger
interaction due to the increased sulfur-carbon double band distances.
This could account for the greater stability of non-aromatic adducts
versus aromatic adducts.
A view of the 1,2,4, TCB model in the plane of the three coplaner
sulfurs can be seen in Figure 15.
The two non-solid bonds in the
aromatic model indicate that it is not known which of the two aromatic
carbons are bonded to the chlorine.
Figure 15 and 16 show the
relationship between the sulfur atoms and the aromatic.
The three
planer sulfur atoms can be seen pointing in at the 1,2,4 TCB model.
Figure 16 is a view looking down the third thiourea’s carbon-sulfur
double bond.
The angle of this figure shows that one sulfur is
pointing directly into the middle of the planer rings while the other
two are pointing into the sides of the rings.
The non-bonded
distances from each of these sulfur atoms to the rings are in
Table 10.
50
The relationship between the coplaner sulfurs and the 1,2,4 TMB
can be seen in Figures 17 through 20.
Each of these figures exhibits
only one of the four rings used in the model.
If Figures 17 through
20 were superimposed, the result would be the four ring model
positioned in the zone of the coplaner sulfurs.
As in the 1,2,4, TCB-
thiourea adduct, there is one sulfur pointing in at the plane of the
1,2,4 TMB model and the remaining two are pointing in at the sides.
The non-bonded distances from each sulfur atom to the rings are listed
in Table 11.
In both adducts, the distances from the sulfur pointing directly
into the plane of the rings, and the aromatic carbons are all too long
for a strong interaction to occur.
The remaining two sulfurs oriented
to the sides of the aromatic, are closer to some of the ring carbons.
For a hydrogen bond to be possible, the atoms must be closer than the
sum of their van der Waal radii and the carbon, hydrogen and sulfur
must be linear.
The van der Waal radius of sulfur is 1.76 and that
for hyrogen is 1.20 A.
is 1.08 A.
The radius for a carbon-hydrogen covalent bond
Thus, the shortest non-bonded distance between a linear
carbon, hydrogen and sulfur is the sum of these radii, or 4.04 A.
From Tables 10 and 11 only one sulfur-carbon nonbonded distance, SlA
to B14 for the 1,2,4 TCB adduct and SlA to F4 for the 1,2,4 TMB
adduct, are of the appropriate distance and angles necessary to be
considered a hydrogen bond.
Both these bonds are linear with a
hydrogen in the middle and their distances are 4.001 A and 3.761 A for
the 1,2,4 TCB adduct and 1,2,4 TMB adduct respectively.
cates that a hydrogen bond is a possibility.
This indi­
51
Table 10.
Atom I
SlA
SlA
SlA
S2A
S2A
S2A
S2A
S2A
S2A
S2A
S3A
S3A
S3A
S3A
Interatomic distances between sulfur and carbon in the
1,2,4 TCB-thiourea adduct structure, Only distances less
than about 4.5 A are tabulated.
Atom 2
Distance in A
BI
B2 ’
B14
BH
B12
B13
BI
B4
B5
B6
BH
B12
B4
B5
3.991
4.485
4.001
4.111
3.709
4.026
4.439
4.108
3.713
3.899
4.355
4.243
4.550
4.078
/
The other most likely form of interaction is a dipole-dipole
attraction between the sulfurs and the aromatic carbons.
This would
require the two unshaired pairs of electrons on the sulfurs inducing
an added dipole in the aromatic C-H gVoup.
Whether the interaction
between the thiourea and the aromatic is of a hydrogen bonding type
and, or a dipole-dipole type the interaction does contribute to
lowering the energy state of the complex.
The possibility of hydrogen bonding and the evidence of dipoledipole interations might contribute to the predicting of which hydro­
carbon will or will not adduct.
52
Table 11.
Interatomic distances between sulfur and carbon in the
1,2,4 TMB-thiourea adduct structure. Only distances less
than about 4.5A are tabulated.
Atom I
SlA
SlA
SlA
SlA
SlA
S2A
S2A
S2A
S2A
S2A
S2A
S2A
S2A
S2A
S2A
S3A
S3A
S3A
S3A
S3A
S3A
S3A
S3A
S3A
S3A
Atom 2
B4
F3
F4
B 25
B26
BI
B6
T3
Tl
T2
Fl
F2
F6
B21
B22
BI
B6
T3
Tl
T2
Fl
F2
F6
B21
B22
Distance in A
•'
4.234
4.539
3.761
4.424
4.483
3.925
3.784
3.724
3.965
3.744
3.569
4.066
3.825
3.763
3.735
3.875
4.116
4.127
3.894
3.410
3.950
4.440
4.584
4.396
3.823
53
Figure 15.
View of the 1,2,4 TCB model in the region of the three
coplaner sulfurs.
54
Figure 16.
Two thiourea molecules with planer sulfur atoms pointing
into the sides of the 1,2,4 TCB model view in looking down
the sulfur=carbon double bond of the third coplaner
sulfur.
55
Figure 17.
One of the four model rings of the 1.2,4, TMB shown in the
region of the three coplaner sulfurs.
56
Figure 18.
One of the four model rings of the 1,2,4 TMB shown in the
region of the three coplaner sulfurs.
57
Figure 19.
One of the four model rings of the 1,2,4 TMB shown in the
region of the three coplaner sulfurs.
58
Figure 20.
One of the four model rings of the 1,2,4 TMB shown in the
region of the three coplaner sulfurs.
59
CONCLUSIONS
Extractive crystallization with thiourea is a novel separations
technique which separates hydrocarbons and notably aromatic systems.
the extractive crystallization process, a unique crystalline
,
complex is formed when thiourea spirals around a selected hydrocarbon
and forms a cage-like entrapment.
Thiourea is selective for classes
of hydrocarbons and is even selective between isomers of the same
emperical formula.
The entrapped hydrocarbon can he recovered from
the complex by steam stripping, followed by phase separation of the
products.
Knowledge of the atomic positions, intermolecular distances and
the intermolecular forces of interaction in these thiourea complexes
might allow an understanding of their selectivity and stability.
From
x-ray crystallographic data the thiourea lattice is well defined in
these complexes.
Schlenk discovered the zones of maximum attraction
occurring in each unit cell where three coplaner sulfur atoms are
pointing directly into the channel.
to one another via hydrogen bonds.
The thiourea molecules are bonded
This accounts for a part of the
stability, but not the selectivity of these thiourea adducts.
The key
to the selectivity of these complexes is thought to lie in the
thiourea/hydrocarbon interaction.
Supporting evidence for an interaction lies in the fact that
thiourea will form adducts with some compounds yet not with other
60
compounds of similar size and shape.
In addition, the carbon-sulfur
double bond distance in thiourea varies between aromatic and non­
aromatic complexes.
This is an indication that there is an
interaction and that it is flexible in nature.
Finally, the nonbended
distances between the coplaner sulfurs and the aromatic are almost at
the distance equal to the sum of the van der Waal radii and, in each
adduct one nonbonded distance is within the appropriate length and
geometry to indicate a possible hydrogen bond.
The nonbonded
distances close to the van der Waal radii of the aromatic indicate a
dipole-dipole interaction.
If in fact a hydrogen bond does exist some credibility might be
added to Fetterly's notion of a "supported hydrogen bond".
However,
the probability of dipole-dipole attractions occurring should not be
ruled out.
Fetterly’s idea does not explain explain adducts which
have no possibilities of hydrogen bonding, i.e. carbon tetrachloride
adduct.
No evidence was found to support Welling's suggestion of a
chlorine/NHg group hydrogen bond in the 1,2,4 TCB thiourea adduct.
Furthermore, no hydrogen bonding was seen between a methyl group and a
sulfur in the 1,2,4 TMB-thiourea adduct.
Diffractometer data sets collected on both the 1,2,4 TMB-thiourea
and 1,2,4 TCB-thiourea adducts showed both adducts crystallizing in
the space group P21/c, which is characteristic of aromatic complexes.
The most difficult problem associated with both complexes was the
disorder of the aromatic in the channel.
The disorder arose from site
and or orientation disorder and not adjacent aromatics overlapping
each other.
A model which take into account the disorder was found
61
for each complex.
Refinement of these models resulted in an R value
of .1053 for the 1,2,4 TBM adduct and .0951 for the 1,2,4 TCB adduct.
Both aromatic models where found to lie in the zone of maximum
attraction created by the three coplaner sulfur atoms in the thiourea
lattice.
It is hoped that the information concerning the structures
of these adduct can be used in future research to determine the
overall selectivity mechanism of these thiourea adducts.
Recommendations
Many aromatic and non-aromatic hydrocarbons form adducts with
thiourea.
The wide range of stability and selectivity of these
adducts pose many questions regarding their structures and chemical
interactions.
The knowledge of the exact nature of the thiourea and
hydrocarbon interaction appears to be vital if the selectivity
mechanism and chemical structures are to be known.
The primary
obstacle is resolving the disorder assbciated with the channel
hydrocarbon.
Steps taken to reduce the disorder might entail utilizing a
guest hydrocarbon, such as carbon tetrabromide, which possesses heavy
atoms that could appear less disordered in the difference maps.
Alternatively, a better 1,2,4 TCB model refined using a full matrix
least squares in the XTAL system might enhance locating the chlorine
atoms in the 1,2,4 TCB adduct.
Another approach might be to find a
guest hydrocarbon which is geometrically large enough so that the
number of orientations possible in the channel are minimized, thus
reducing the orientation disorder.
Furthurmore, if a larger guest
62
hydrocarbon could be found that occupied two or more zones of maximum
attraction the site disorder might be reduced.
The quality of the
x-ray diffraction data could be enhanced if data set were obtained using
low temperatures.
Although 1,2,4 trichlorobenzene is considered to be an inductor,
the role of inductors in thiourea complexes was not fully investigated
in the two aromatic adducts studied.
It appears that the role of an
inductor must be studied in adducts which contain the inductor and
selected hydrocarbon.
For instance, CCl^ is selective for
ethylbenzene in the aromatic mixture of ethylbenzene and oxylene.
In
the same mixture, 1,2,4 trichlorobenzene is selective for the o—
xylene.
Since CCl^ adducts in space group R3bar and 1,2,4, TCB
adducts in P21/c it would be interesting to see which space group
forms when CCl^ inducts ethylbenzene and when 1,2,4 TCB inducts oxylene.
The same intermolecular forces which "appear in the crystalline
adduct are also present in solution.
Therefore, nuclear magnetic
resonance (nmr) spectroscopy and infared spectroscopy may shed light
on the intermolecular interaction between the thiourea and the
hydrocarbon.
63
LITERATURE CITED
V !
64
LITERATURE CITED
1.
Kamler, W. D. and Fohlens G. M. "The Dipole Moment and Structure
of Urea and Thiourea." J. Chem. Phys. 7, Aug. 1942.
2.
Mandelcorns L.s Non—Stoichiometric Compounds, (Academic Press,
New York, 1964).
3.
Angla, B., Ann. Chim,, [12] 4, 639 (1949).
4.
Redlich, O., and C. M. Gable. "Addition Compounds of Thiourea."
J. Am. Chem. Soc., 72, Sept. 1950, p. 4161.
5.
Smith, A. E., "The Crystal Structure of the Urea-Hydrocarbon
Complexes." Acta Cryst., 5, 224 (1952).
6.
Schlenk, W., Jr., "Die Thioharnstoff-Addition organischer
Verbinduneng.", Ann. 573, 142 (1951).
7.
Smith, A. E., "The Crystal Structure of Urea-Hydro-Carbon
Complexes." Acta Cryst., 5, 224 (1952).
8.
Schlenk, W., Jr., "Die Harnstoff-Addition der aliphatischen
Verbindungen.", Ann., 555, 204 (1949).
9.
Cramer, F. D., "Inclusion Compounds." Reviews of
Pure and Applied Chemistry, September 1955, Vol. 5 - No. 3, The
Royal Australian Chemical Institute.
10.
McCandless, F. P., Separation of the Cg Alkybenzenes by Induced
Extractive Crystallization." Ind. Eng. Chem. Prod. Res. Dev.,
19, 612-16 (1980).
11.
McCandless, F. P., "Hydrogenated Monoterpenes:
Separation by
Extractive Crystallization." Ind. Eng. Chem. Prod. Res.
Develop., Vol. 10, 4 406-409 (1971).
12.
Welling, B. L. "Separate Aromatic Compounds by Forming Adducts
with Thiourea: How to Select the Inductor." Masters Thesis in
Chemical Engineering, Montana State University, Bozeman, Montana
(1982).
13.
Spinti, M. J., Personal communication.
14.
U.S. Patent 2499820, 1950. "Thiourea—Hydrocarbon Complexes and
Process for Preparing Same." Lloyd C. Fetterly, Shell Develop­
ment Company.
65
15.
Elcombe5 M. M., and Taylor, J. C. "A Neutron Diffraction Determ­
ination of the Crystal Structures of Thiourea and Deuterated
Thiourea Above and Below the Ferroelectric Transition.",
Acta Cryst., A24, 410 (1968k).
16.
Gorton, P. J. "The Separation of Hydrocarbon Isomers by Extrac­
tive Crystallization with thiourea." Masters Thesis in Chemical
Engineering, Montana State University, Bozeman, Montana (1980).
17.
Fait, J., and Fitzgerald, A., Personal communication.
18.
International Table for X-ray Crystallography, Vol.,
Press, Birmingham, England, 1974).
19.
Bondi, A. "Van der Waal Volumes and Radii."
Vol. 68, 3 441-451, March (1964).
20.
Hamilton, W. C. and Iber, J. A. Hydrogen Bonding in Solids, (W.
A. Benjamin, Inc., New York, 1968).
21.
Stout, G., and Jensen, L. X-Ray Structure Determination:
A Practical Guide, (Macmillan Company, London, 1968).
22.
Sheldrick, G. M. SHELXTL Manual, Rev. 4, (Nicolet XRD Corp.,
Madison, WI August, 1983).
23.
Nyburg, S. C., X-Ray Analysis of Organic Structures, (Academic
Press, New York and London, 1961).
24.
McLachlan, D., X-Ray Crystal Structure, (McGraw-Hill Book
Company, Inc., New York, 1957).
25.
Buerger, M. J., Crystal-Structure Analysis, (John Wiley & Sons,
Inc., New York 1960).
26.
Quinn, T., X-Rays, Electrons and Crystalline Materials,
(Butterworth and Co., England, 1970).
(Kynoch
J. of Phy. Chem.,
•66
I
APPENDICES
4.
67
APPENDIX A
CLASSIFICATION OF CRYSTALS
68
APPENDIX A
There are seven three—dimentional coordinate systems which are
used to classify crystals (18).
In general, the unit cell is
characterized by a certain symmetry and six parameters, three axial
lengths and three interaxial angles.
The lengths of the unit cell
edges are designated a, b, c and the interaxial angles a,6,Y where
is the angle between b and c, g is the angle between a and c, and y is
between a and b.
The following table specifies the seven crystal systems along
with the corresponding unit cell parameters:
Table 12.
The seven possible crystal systems.
Crystal System
No. Independent
Parameters
Triclinic
6
Monoclinic
4
Orthorhombic
3
Tetragonal
2
Parameters
I
afbfc; a = Y = 9 0 o ; Bf90°
2/m
afbfc; a =B=Y=90°
mm m
a=bfc; a = B = Y = 9 0 °
a=b=c; a = B = Y t5S O 0
Rhombohedral
2
Hexagonal
2
Cubic
I
Lattice
Symmetry
4/mmm
a=bfc; a=B=90°; Y=120°
3/m
a=b=c; a =B=Y=SO0
6/mmm
m3m
The essential symmetries of a structure can be categorized into
systems referred to as the Laue Space Groups.
There are 230 space
groups, each unique in describing a particular crystal's internal
69
(i.e. molecular) symmetry.
A crystal's space group can be determined
by systematic x-ray reflection absences, and the space group is listed
in the "International Tables for X-Ray Crystallography."
All symmetry
elements are represented by symbols, figures and letters which are
arranged together to indicate a space group.
70
Table 13.
Symbols for symmetry elements and for the corresponding
symmetry operations in one—, two—, and three—dimensions
[reproduced from (8)].
Prinlfdsymbol Symmclryelementanditsorientation Generatingsymms
ec
tr
rey
wo
vp
ee
cr
ta
o'
r-onwithglideor
Reflectionplane,mirrorplane
.Reflectionthroughaplane
R
e
f
l
e
c
t
i
o
n
l
i
n
e
,
m
i
r
r
o
r
l
i
n
e
•
Reflectionthroughaline
m
'twodimensions)
Reflectionpoint,mirrorpoint
Reflectionthroughapoint
a,b,o
re
‘Axial’glideplane
Glidereflectionthroughaplane,withglidevector
a
J
L
f
O
I
O
]
o
r
[
]
[a
b
l[00l]or1[I00]
i
b
IflOO]or±[ ]
I
c
IflTOlorI[110]
c"
I[ ]orIfO ]or [TT]
1c
(0>hexagonalcoordinatesystem
T
,1(1TO]or ( ]or ( ]
n
‘Diagonal’glideplane
G
la
id
eb
r
e
fl
e
c
t+
ion
t
h
r
o
u+
ghc)aplane,withglidevector
1(001]:1(100]:1(010]
]
(
+
)
:
]
(
b
c
)
:
]
(
a
I[ITO]or ( ]or1[T01]
!(afb+c)
1(110]:1(011]:1(101]
]
(—a+b+c):2(a—bfc);](a+b-c)
d'
‘Diamond’glideplane
G
lidereflectionthroughaplane,withglidevector
I
[
0
0
1
]
:
1
(
1
0
0
]
:
1
(
0
1
0
]
!
(
a
±
b
)+
;i(
b:±
c
)
;a
i(
+ba++c)
c
)j(a±b+c)
1(1TO]:1(01T]:1(T01]
i
(
a
+
b
c
)
]
(
+
+
:
1(110]:1(011]:1(101]
|(—a+b+c):](+a b+c);](a±b-c)
Glideline(twodimensions)
9
G
1(01]:1(10]
Jl
ai
td
te
breflectionthroughaline,withglidevector
1
None
Identity
/i-foldrotationaxis,11
C
o
u
n
t
edrc
lo
ci
ks
wiserotationofS6O//1degrees
a
r
o
u
n
a
n
a
x
/i
fo
old
rm
oe
tn
as
ti
io
oint.11
2 3 4,6
Co
oi
cn
kt
wiserotationof /»degrees
(
tw
di
on
nsp
)
a
ru
on
ut
ne
dracl
po
T
Centreofsymmetry,inversioncentre Inversionthroughapoint
2 = nr, 3,4,5
Rotoinversionaxis,/I
C
o
u
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t
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rc
lo
ci
ks
w
if
so
ell
ro
ot
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t
io
n
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f
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»
de
gh
rr
eo
eu
sgha
a
r
o
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a
n
a
x
,
w
e
d
b
y
i
n
v
e
r
s
i
o
n
t
pointontheaxis'
2
Right-handedscrewrotationof /»degrees
Sj1S2
a
roundanaxis,withscrewvector(pitch)(p/n)t:
n
f
o
l
d
s
c
r
e
w
a
x
i
s
,
n
,
i-2,3
h
e
ra
ell
tei
to
he
se
ho
ic
te
rc
at
ni
so
ln
ato
if
on
ve
ec
par
lst
th
ar
xt
ie
sst
inla
tt
ht
e
de
ir
th
st
co
rr
ew
1 001
010
100
10
1 120
1
0
1 210
1 011
360
, ,
360
,
4
360
4
4
>62,63,64,65
s y m b o l
C e n t r i n g
t y p e o f c e ll
Table 14.
N u m b e r o f
la ttic e p o i n t s
P r i n t e d
C o o r d i n a t e s o f la t t ic e p o i n t s
w i t h i n
p e r ce ll
c e ll
/
P r i m i t i v e
I
O
I
0,0
0,0;ii
T w o d im e n s io n s
P
P r i m i t i v e
C
C e n t r e d
2
h
H e x a g o n a l l y c e n t r e d
3
T h r e e d im e n s io n s
P
P r i m i t i v e
C
C - f a c e C e n t r e d
2
0,0,0;1,1,0
A
/1 - f a c e c e n t r e d
2
0,0,0:0,1,1
B
B - f a c e c e n t r e d
2
0 , 0 , 0 ; j , 0 , j
I
B o d y
2
0,0,0;U,i
F
A l l - f a c e c e n t r e d
R
I
c e n t r e d
c e n t r e d
( d e s c r i p t i o n
w i t h
‘h e x a g o n a l a x e s ’)
w i t h
‘r h o m b o h e d r a l
3
H e x a g b n a l l y
I
c e n t r e d
f
0
j
0, 0, 0 ; 3, }
,
1 0 , 0 , 0 ; ! ,
P r i m i t i v e
H'
,0,0:,5,0;0,j,j;|,0,{
4
R h o m b o h e d r a l l y
( d e s c r i p t i o n
0,0,0
0 , 0 , 0
a x e s ’)
3
0,0,0;!,!,0;!,f,0
(‘o b v e r s e s e t t i n g ’)
(‘r e v e r s e s e t t i n g ’)
.
Symbols for one—, two—, and three-dimensional cells
[reproduced from (8)].
O n e d im e n s io n
72
■
APPENDIX B
ELEMENTAL ANALYSIS
73
APPENDIX B
Table 15.
Elemental analysis for the 1,2,4 TCB-thiourea adduct, the
1,2,4 TMB-thiourea adduct, and pure thiourea.
(I)
Sample Weight (mg)
1,2,4 TCB-Thiourea Adduct
Nitrogen %
1.2829
1.1389
1.8014
22.00
22.46
21.61
(II)
Sample Weight (mg)
1.4673
1.5272
1.4972
Carbon %
24.68
24.35
24.66
Hydrogen %
3.83
3.85
3.84
1,2,4 TMB-Thiourea Adduct
Nitrogen %
26.93
27.07
25.77
(III)
Carbon %
35.58
35.40
37.04
Hydrogen %
6.68
6.68
6.81
Pure Thiourea
% C
% H
% N
% S
% 0
15.83
5.29
37.18
41.65
0.06
74
APPENDIX C
TABLES FOR PUBLICATION FOR THE
1,2,4 TCB-THIOUREA ADDUCT STRUCTURE
75
APPENDIX C
Table 16.
Atomic coordinates and isotropic thermal parameters for the
1,2,4 TCB-thiourea adduct structure.
Atomic coordinates
4
(x 10 ) and
thermal
(A""x 10" )
x
B (5)
'B <.6)
B<1)
BC2)
B C3)
8(4)
B(Il)
B (12)
B (13)
B (14)
B (15)
B(16)
S (I)
3(2)
3(3)
C CI)
C (2)
C (3)
N (11)
N (12)
N (21)
N (22)
N (31)
N (32)
Cl (I)
Cl (2)
Cl
Cl
Cl
Cl
Cl
(3)
(5)
(6)
(7)
(4-)
3317(28)
2143
2198
3427
4601
4546
1635(21)
2507
1982 ■
584
-288
237
3975(2)
- 8 8 (2 )
3182(2)
2765(9)
899(8)
2719(7)
1337(6)
3228(7)
2294(9)
268(11)
1774(7)
3271(10)
4042(65)
4819(27)
482(59)
4425(14)
2411(20)
2848(29)
2515(23)
parameters
isotropic
y
10410(13)
9865
9366
9413
9958
10457
I0462(11)
10258
9 687
9318
9 522
10094
6 4 7 2 ( I)
6 3 7 0 ( I)
3 0 3 0 CI)
6881(5)
7081(5) '
4073(5)
6951(5)
7157(4)
7263(6)
7465(6)
4529(4)
4437(6)
I I046(40)
9341(16)
9615(29)
10714(8)
10740(12)
10757(20)
9275(14)
Li
2589(15)
251 I
3475
4518
4596
3632
667(15)
1824
2461
1940
783
146
4397(2)
1410(2)
2024(2)
4970(7)
936(7)
2226(6)
4296(5)
6067(5)
1570(8)
- 88 (8 )
1362(5)
3285(7)
2154(54)
6008(20)
1213(39)
3105(11)
867(15)
1335(25)
3948(19)
2 1 1 (10)
362
374(17)
184(7)
264(19)
1 3 1 (S)
186(8)
513(46)
687(49)
139(4)
356(43)
746
7 3 CI)*
6 7 ( I)*
70 (I)*
69(4)+
66(3)*
66 (3) +82(3) +
89(3)+
91(4)+
88 (4) +
91(3)+
95(4)+
423(34)
122 (8 )
235(20)
55 (3)
85(5)
116(11)
94 (6)
+ Equivalent isotropic U defined as one third of the
trace of the o r t h o g o n a l ised LL j tensor
Table 17.
Anisotropic thermal parameters for the 1,2,4 TCB-thiourea adduct structure
A n isotropic thermaI
S(I)
S (2)
S (3)
C(I)
0(2)
0(3)
N(Il)
N (12)
N(21)
N (22)
N (31)
N (32)
parameters
U 11
U 22
“ 33
61(1)
60 (I)
81(1)
71 (6)
67(5)
65(4)
56(3)
78(4)
63(5)
I 16(7)
98(5)
120(7)
90 (I)
73(1)
69(1)
69(6)
70 (6)
65(5)107(51
120(6)
116(7)
87(7)
72(4)
65(5)
64(1)
62 (I)
54 (I)
65(5)
63(5)
68(4)
83(4)
70(4)
89(6)
70 CS)
77(4)
82(5)
T h e a ni so tr opi c
,o2 ,.37
(A xlU )
U 23
U 13
U 12
-13(1)
9 CI>
-2(1)
3(5)
-4(4)
-6(4)
3(4)
-24(4)
7(5)
17(4)
3(4)
-9(5)
17(1)
18(1)
18(1)
24(5)
26(4)
24(4)
24(3)
30 (3)
23 (5)
43(5)
4(4)
15(5)
3(1)
-2 (I)
.12(1)
-8(5)
7(4)
-4(4)
2(4)
I (4)
-21(5)
-I I CS)
13(4)
7(5)
■'
temperature factor exponent
+ ...
+ 2 h k a * b + U 12>
takes the form:
Table 18.
H-atom coordinates and isotropic thermal parameters for the 1,2,4 TCB-thiourea adduct
structure.
H-A to m coordin at es
thermal
) and
isotropic
parameters
X
H (12a)
H (12b)
H(I)
H (2)
H (21)
H (22)
H (23)
H (24)
H (31)
H (32)
H (33)
H (34)
(x I
2541
4252
635(66)
600(133)
2889(81)
2 8 7 5 ( I04)
615(69)
-530(132)
3753(78)
•3319(65)
1653(92)
1354(75)
Y
7 399
7111
7443(39)
6539(80)
7142(52)
7473(65)
7640(43)
7252(79)
4065(48)
4929(37)
5087(65)
4214 (47)
Z
6375
6557
4594(52)
2 9 6 7 ( I09)
2386(67)
1416(85)
-258(58)
-1218(114)
3801(60)
3279(51)
1248(81)
629(62)
U
I05
105
83(19)
255(50)
144(29)
I 15(40)
6(19)
269(53)
84(26)
36(19)
181(38)
106(24)
Table 19.
Bond lengths for the 1,2,4 TCB-thiourea adduct structure.
Bond
S(I)-C(I)
S (2)- H (2)
C d ) - N (11)
C (2) -N (21)
C (3)-N (31)
N(Il)-H(I)
N (21)-H(22)
N (22)- H (24)
N (31)- H (34)
N (32)- H (32)
Cl (I)- B (4)
Cl ( I ) - C l (5)
Cl (I)-Cl (7)
C l (2)- B (3)
C l (2)- B (4a)
C l (3)- B (6)
C l (3)- B (13)
C l (3)- B (15)
C l (3)- B (16a)
C l (5)- B (4)
Cl (6)-Bill)
C l (6)- C l (7)
Cl (7)— B (11)
C l ( 4 ) - B (6)
C l (4)- B (2)
lengths
(S)
.706(10)
1.796(124)
1.337(9)
1.325(10)
I.320(8)
I. 168(69)
I). 736(113)
I. 3 5 6 C125)
I). 969(72)
I). 757 (58)
I. 922(66)
1.200(64)
1.303(57)
1.918(32)
I). 687(31)
1.844(47).
I.685(45)
0.756(47)
I.617(47)
0. 730(24)
0.825(27)
0.576(29)
I.250(30)
I.896(30)
0.931(28)
..
S (2)-C (2)
S (3) -C (3)
C (I)-N (12)
C (2)- N (22)
C (3)-N (32)
N (21)-H (21)
N (22)-H (23)
N (31)- H (33)
N (32)- H (31)
Cl (I)-B(S)
Cl (I)-B (12)
Cl (I)-Cl (6)
C l (2)- B (2)
C l (2)- B (3a)
C l (2)- C l (5a)
C l (3)-B(Il)
C l (3)- B (14)
Cl (3) — B.C 16)
C l (5)- B (5)
Cl (S)-ClC2a)
C l (6)- B (12)
C l (7)- B (5)
C l (7)- B (12)
C l (4)— B CI)
Cl (4)- B (13)
1.698(9)
1.707(8)
I.322(10)
1.318(11)
1. 3 3 2 ( I0)
0.973(69)
0.532(77)
'0 . 8 6 9 ( 1 0 1)
0.853(66)
I.423(73)
1.851(64)
1.841 (53)
I.834(26)
I.530(36)
I. 069(24)
1.993 (60)
0.975(52)
I.443(52)
I. 133(26)
I. 069(24)
I.363(26)
1.531 (35)
I.099(38)
0.566(26)
I. 818(29)
79
Table 20.
Bond angles for the 1,2,4 TMB-thiourea adduct structure
Bond angles
B ( 6 > - B ( 5 > - C l (I)
B (12)- B (5)- C I (I)
B ( O ) - B ( S ) - C l (5)
8 ( 1 2 ) - B (5)- C l (5)
Cl ( U - B t S ) - C l (5)
B (4)— B(S)-Cl(Z)
B ( I S ) - B (5)- C l (7)
Cl ( S ) - B ( S ) - C l (7)
B ( I ) - B (6)- C l (3)
B ( 1 3 ) - B ( o ) - C l (3)
B(S) — B 16 )—C l (4)
B (12)- B (6)—C l (4)
B (14) — B (6) -Cl (4)
B (6)- B ( I ) - C I (4)
B ( I S ) - B ( I ) - C l (4)
B ( I ) - B (2)— C l (2)
B ( I ) - B ( Z ) - C l (4)
Cl (2)- B (2)- C l (4)
B ( 4 ) — B ( S ) - C l (2)
Cl ( Z ) - B ( S ) - C l (2a)
B ( 3 ) - B ( 4 ) - C l (I)
B (3) — B (4) — Cl (5)
Cl (I)- B (4)— C l (2a)
B (12)— B (11)— C l (3)
B ( 12)— B ( I l ) - C l (6)
Cl (3)- B (I U - C l (6)
B ( I B ) - B d D - C l (7)
Cl ( B ) - B d D - C l (7)
Cl (6> — B(Il)-B(ISa)
Cl (3)- B (I U — B( Io a )
Cl,(7)- B(Il)-B(IBa)
B (6)- B (12)- C l ( I )
B(IS) -B <1 2 ) - C l (I)
B (6 )- B ( I Z ) - C l (6)
B ( I S ) - B ( I Z ) - C l (6)
B ( S ) - B ( I Z ) - C l (7)
B ( I l ) - B ( I Z ) - C l (7)
Cl ( I ) - B ( I Z ) - C l (7)
B( S ) - B ( 13)- C l (3)
B ( U - B d S ) - C l (3)
B(14; -B (13) -Cl (3)
B (B) — B (13) —C I (4)
B ( I Z ) - B ( I S ) - C l (4)
C l (3)— B (13)— C l (4)
B ( I ) - B (14)- C l (3)
B ( I S ) - B (14)- C l (3)
B(IB)-B(I S ) - C l ( S )
Cl (S)-B(IS)-B(IBa)
B ( I S ) - B ( I B ) - C l (3)
C l (3)- B ( I B )-B(ISa)
Cl ( S ) - B ( I B ) - C l (3a)
S ( U - C d ) - N d I)
NdU-C(D-NdZ)
S (2) - C (2)- N (22)
S (3)- C (3)— M (3I)
N (31)- C (3)- M (32)
C ( 2 ) -M(Zl)-H(Zl)
H(Zl) - N ( Z l ) - H ( Z Z )
C (2)— N (22)- H (24)
C (3)-N (31)-H (33)
H (33) - N (31) -H (34)
C (3)- N (32)- H (32)
B(S)-Cl(I ) - C l ( S )
B ( I Z ) - C l ( I ) - C l (5)
B ( 4 ) - C l ( I ) - C l (6)
Cl ( S ) - C l ( I ) - C l (6)
B ( 4 ) - C l ( I ) - C l (7)
Cl ( S ) - C K U - C l (7)
B(S) - C l ( S ) - C l (I)
Cl ( I ) - C l ( S ) - C l (2a)
B ( I Z ) - C l ( B ) - C l (I)
B ( I Z ) - C l ( B ) - C l (7)
B ( S ) - C l (7)-Cl(I)
B ( IZ)-Cl (7)- C K U
B d U - C l (7)- C I (B)
C K U - C l (7)-Cl (6)
(°)
154.0(23)
97.9(29)
151.3(12)
1 5 1 . I (30)
54.6(25)
137.7(14)
101.8<lo)
106.6(22)
111.4(18)
5 5 . O (44)
110.8(9)
153.5(21)
88.9(14;
147.5(35)
157.5(47)
168.5(12)
16.3(21)
152.2(28)
174.8(9)
148.1(14)
167.5(20)
173.4(23)
104.5(35)
73.6(13)
70.5(17)
1 4 4 . I (23)
167.6(19)
22.0(20)
123.2(27)
4 8 „ 7(15)
170.8(25)
127.3(25)
136.5(20)
160.2(21)
154.7(11)
93.2(24)
58.8(15)
43.8(24)
120.8(22)
129.2(27)
35.3(20)
100.0(45)
1 3 9 . I (9)
136.0(24)
129.5(34)
31.3(32)
7 8 . I (44)
100.0(50)
30.8(21)
168.4(34)
160.3(1+)
119.9(7)
119.2(9)
119.5(7)
121.6(5)
118.2(7)
131.0(54)
97.3(83)
139.3(51)
131.6(48)
110.9(71)
1 14. 4(45).
50.3(28)
82.5(37)
121.9(36)
125.9(46)
114.3(45)
118.3(55)
7 5 . I (31)
151.0(34)
68.7(24)
51.3(37)
59.6(34)
100.5(38)
32.5(30)
t54.9(ol)
B ( 4 ) - B ( 5 ) - C l (I)
B (13) - B (5) -Cl (I)
B ( 4 ) - B ( 5 ) - C l (5)
B (13)— 8 ( 5 ) - C I (5)
B ( B ) - B ( S ) - C l (7)
B ( I Z ) - B ( S ) - C l (7)
Cl ( I ) - B ( S ) - C l (7)
B ( S ) - B ( B ) - C l (3)
B ( I Z ) - B ( B ) - C l (3)
B (14)— B ( O ) - C l (3)
B(I) - B ( B ) - C l (4)
B (I3 ) - B ( B ) - C l (4)
Cl ( S ) - B ( B ) - C l (4)
B ( Z ) - B ( I ) - C l (4)
B ( 1 4 ) — B (I)- C l (4)
B ( S ) - B ( Z)-Cl(Z)
B ( S ) - B ( Z ) - C l (4)
B (2)- B (3)- C l (2)
Cl (Z) -?B <3) -B (3a)
B (5) — B (4) — C I d )
B ( 5 ) - B ( 4 ) - C l (5)
C L ( D - B d ) - C l (5)
C l (5)- B (4)-Cl (Za)
B ( I B ) - B d U - C l (3)
B ( I o ) - B ( I l ) - C l (6)
B ( I Z ) - B d U - C l (7)
Cl ( S ) - B d D - C l (7)
Cl ( S ) - B d U - B ( I S a )
Cl (7) — B ( I I.)— B (15a)
Cl ( B ) - B d U - B ( I B a )
B ( S ) - B ( I Z ) - C l (I)
B(1 U - B ( I Z ) - C l (I)
B ( S ) - B ( I Z ) - C l (6)
B ( I D - B d Z ) - C l (6)
Cl ( U - B d Z ) - C l (6)
B ( B ) - B ( I Z ) - C l (7)
B (13)— B (12)- C l (7)
Cl ( B ) - B ( I Z ) - C l (7)
B ( B ) - B ( I S ) - C l (3)
B ( I Z ) - B ( I S ) - C l (3)
B (5)— B (13)— C l (4)
B ( U - B d S ) - C l (4)
B (14) — B (13)‘-Cl (4)
B (6) — B C1+) -Cl (3)
B d 3 ) — B (14) —Cl (3)
B (14)— B (15)- C l (3)
C l (3)- B ( I S ) -B(Ila)
B d U - B ( I B ) - C l (3)
Cl (3)- B ( I o ) - B d la)
C l (3)- B (16)- B (16a)
C(Z)-S(Z)-H(Z)
S(U-C(I)-NdZ)
S(Z) - C ( Z ) - N ( Z l )
N (21)- C (2)- N (22)
S (3)- C (3)- N (32)
C(D-Ndl)-Hd)
C ( 2 ) - M ( Z l )-H(ZZ)
C (2)-N (22)-H (23)
H (23)- N (22)- H (24)
C (3)- N (31)- H (3+)
C (3)- N (32)— H ( 3 1 )
H <31)— N (32)— H (32)
B (4)- C I ( I ) - C l (5)
B ( S ) - C l ( I ) - C l (6)
B ( I Z ) - C l ( I ) - C l (6)
B ( S ) - C l ( I ) - C l (7)
B ( IZ)-Cl (I)- C K 7 )
C l ( o ) - C l ( I ) - C l (7)
B (4)- C I (5)- C l (I)
B d D - C l (B)-Cl (I)
B(1 U - C l (B)-Cl (7)
Cl ( I ) - C l ( B ) - C l (7)
B d l V - C l (7) -Cl (I)
B ( S ) - C l < 7 ) - C l (6)
B (IZ)-Cl <7)- C K o )
86 . 0 (2 2 )
154.0(25)
31.4(12)
1 5 1 . I (17)
1 0 2 . I (14)
45.8(17)
52.2(25)
128.4(19)
83.3(21)
31.8(18)
9.2(9)
70.8(45)
1 2 0 . 6 (2 2 )
27.5(35)
15o.o(39)
71.4(12)
136.3(20)
65.0(10)
52.5(23)
47.6(19)
5 4 . I (21)
6 . o(24>
97.9(37)
46.4(13)
169.2(16)
48.7(17)
122.2 (2 2 )
92.6(18)
145.2(26)
1 6 7 . I (27)
49.6(25;
102.4(19)
117.3(22)
34.8(10)
67.9(22)
165.7(26)
174.3(20)
2 4 . I (15)
116.3(48)
84.7(20)
102.4(12)
6.8<14i
100.7(9)
8 5 . I (32)
88.8(32)
42.,0(44)
150.7(53)
89.2(21)
92.9(24)
98.3(46)
103.7(43)
1 2 0 .8 (6 )
121.3(7)
118.7(9)
1 2 0 . I (6 )
U7.3(2o)
131.7<o5)
117.4(02)
85.8(86)
114.4(39)
111.0(49)
130.9(57)
4.0(15)
75.8(27)
43.3(15)
68.2(34)
35.7(23)
7.6(18)
169.4(38)
142.7(32)
125.4(47)
17.4(43'
171.7(48)
145.4(47)
104.o(43»
Table 21.
F(qbs) and sigma (F) for the 1,2,4 TGB-thiourea adduct structure
F(obs) and Sigma(F)
h
k
I
Fo
S
2
4
6
8
10
12
I
2
3
4
5
0
0
0
0
0
0
I
I
I
I
I
I
I
I
I
I
I
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
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
88
41
35
14
24
3
'16
64
115
38
36
25
30
12
3
10
6
30
4
13
92
10
6
3
62
3
8
7
3
3
12
68
150
8
I
I
I
I
I
—6
I
I
' I
I
I
I
I
I
-4
I
-3
I
I
I
I
I
I
-3
I
-4
I
2
—6
—6
I
I
I
I
6
7
8
9
10
II
0
I
2
3
4
5
6
7
8
9
10
11
12
I
2
3
4
(-sigma = unobserved)I
h
Ic
5 3
6 3
7 3
8 3
9 3
10 3
11 3
12 3
0 4
I 4
2 4
3 4
4 4
5 4
6 4
7 4
8 4
9 4
10 4
11 4
12 4
I' 5
2 5
3 5
4 5
5 5
6 5
7 5
8 5
9
5
10 5
II 5
12 5
0 6
I
Fo
5
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
18
6
38
4
9
3
■7
10
59
164
102
28
6
5
3
39
32
4
16
3
3
37
92
25
69
69
7
6
15
9
II
7
3
45
I
2
I
-3
2
—4
3
2
I
I
I
I
I
2
-3
I
I
. -3 .
I
—6
—6
I
I
I
I
I
I
2
I
I
I
3
—6
I
("I
0
0
0
0 ■
Trichlorobenzene Thiourea Adduct
h
k
I
I 6 0
2 6 0
3 6 0
4 6 0
5 6 0
6 6 0
7 6 0
8 6 0
9 6 0
10 6 0
II 6 0
12 6 0
I 7 0
2 7 0
3 ■7 0
4 '7 0
5 7 0
6 ■ 7 ‘0
7 7 0
8 7 0
9 7 0
10 7 0
II 7 0
12 7 0
0 8 0
I a 0
2 8 0
3 8 0
4 8 0
5 a 0
6 8 0
7 8 0
8 8 0
9 8 0
•Fo
28
46
13
44
45
3
9
9
17
15
6
38
19
20
15
100
II
IS
16
3
5
6
3
103
4
I10
16
34
7
6
16
24
9
S
h
k
I
10 8
11 8
I
I
I 9
2 9"
I
I
3 9
-4
4 9
5 9
I .
I
6 9
I
7 9
I
8 9
-3
9 9
-6 . 10 9
I
11 9
I
0 10
I
I 10
I
2 10
3 10
I
4 to
2
5 10
2
6 10
2
7 10
-4
a 10
—3
-3
9 10
10 10
—6
I
11 10
I II
-2
2 II
I
3 11
I
4 11
I
2
5 II
6 II
2
7 II
I
a II
I
10 II
2
I
Fo
S
h
Ic
I
Fo
S
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
8
3
IB
86
7
3
17
7
3
3
7
3
3
33
21
69
5
3
12
3
7
15
3
3
3
25
32
17
13
45
4
3
3
3
2
—6
I
I
I
-4
I
2
-4
-4
2
.-6
—6
I
I
I
-2
-4
I
—42
I
-4
—6
—6
I
I
I
I
I
-3
-4
-4
—6
0
I
2
3
4
5
6
7
a
10
I
12
12
12
12
12
12
12
12
12
12
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
15
15
15
15
15
15
16
16
16
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
42
25
6
9
4
6
16
10
3
8
3
6
U
7
23'
4
6
3
31
19
13
4
3
10
4
9
12
24
7
6
9
7
7
6
I
I
2
I
—3
2
I
2
—4
2
-4
3
4
5
6
7
■ 10
0
I
2
3.
4
5
6
I
2
3
4
5
6
0
I
7
2
2
I
-3
-3
-7
I
-I
I
-3
-4
2
-3
2
I
2
2
2
2
2
2
Table 21.
(Continued)
F<obs) and sigma CF) (-sigma = unobserved):
Tri chlorobenzene Thiourea Adduct
h
h
3
4
5
I
2
3
O
I
-10
-a
—6
-4
-2
O
2
4
6
a
10
12
-i i
-10
-9
-a
-7
—6
-5
-4
—3
-2
-I
0
I
2
k
I
Fo
S
16 0
10
16 0
5
16 0
4
17 0
5
17 0
3
17 0
10
18 0
20
18 0
3
0 I
3
0 I
10
0 I
18
0 I 160
0 I
27
0 I
2
■0 I 134
0 .I
84
0 I
60
0 I
3
■0 I
3
0 I
10
I I
3
I I
a
I I
10
I I
72
I I
2
I I
49
I I
46
I I
27
I I
57
13
I I
I I
22
I I
3
21
I I
I I 229
I
-3
-3
—3
-4
I
I
—6
—6
2
I
I
I
-I
I
I
I
-5
—6
2
-6
2
I
I
-5
I
I
I
I
I
I
I
I
I
h
k
3 I
4 I
5 I
6 I
7 I
a I
9 I
10 I
11 I
12 I
-I I 2
-10 2
-9 2
-a 2
-7 2
—6 2
-5 2
-4 2
-3 2
-2 2
-I 2
0 2
I 2
2 2
3 '2
4 2
5 2
6 2
7 2
a '2
9 2
10 2
11 2
12 2
I'
Fo
S
k
Fo
5
h
I;
I
8
I
-10 3 I
10
I
32
I
-9 3 I
17
I
39
I
-a 3 I
3
17
I
-7 3 I
20
I
I
7
2
—6 3 I
75
I
9
2
-5 3 I
17
I
21
I
-4 3 I
27
I
7
2
-3 3 I
69
9
I
2
-2 3 I 137
I
3
—6
-I 3 I 333
i
14
I
0 3 I
29
i
3
—6
I 3 I
32
I
3
-5
2 3 I
26
i
10
2
3 3 I
41
I
6
2
4 3 I
26
i
2
-5
5 3 I
II
i
73 .
I
6 3 I
5
i , 74
I .
7-3 I
3
i
72
I
8 3 I
6
i
I
9 3 I
35
72 .
i
79
I
10 3 I
6
i
3
I
11 3 I
10
i
20
I
12 3 I
3
i
73
I
-10 4 ■ I
14
i
96
I
-9 4 I
8
i
25
I
-8 4 I . 9
i
82
I
-7 4 I
3
i
13
—6 4 I
39
Ii
30
I
-5 4 I
23
45
i
3
-5
-4 4 I
i
3
-6
—3 4 I
49
i
3
-6
-2 4 I
63
i
7
-3
-I 4 I 341
i
9
2
0 4 I
78
2
I
-5
I
I
I
I
I
I
I
I
I
I
I
I
I
-2
-5
2
I
-3
2
—6
I
2
2
-5
I
I
I
I
I
I
I
I
2
3
4
5
6
7
8
9
10
11
12
-10
-9
-8
-7
-6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
7
8
9
10
II
■4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
I-
I
Fo
S
h
k
I
23
I
54
I
29
I
58
I
60
I
47
10
I
I
3
I
10
I
3
I
3
I
7
I
15
I
6
I
33
I
10
I
60
I
11
I
20
I
2
I
19
I
48
I 147
I 112
I 102
14
I
I
2
I
12
I
3
I
36
I
7
I
6
I
8
I
3
I
I
I
I
I
I
I
-5
2
—6
—6
-3
I
-3
.I
I
I
I
I
—4
I
I
I
I
I
I
-4
I
-5
I
2
-3
2
—6
12
-10
-9
-8
-7
—6
—5
-4
-3
-2
-I
0
I
2
3
4
5
’6
7
8
9
10
II
-10
-9
-8
-7
—6
-5
—4-3
-2
-I
0
5
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
7
7
7
7
7
7
7
I
Fo
S
I
10
I
8
I
12
I
9
I
3
I
31
I ■ 35
I
24
I 157
I
21
I
29
I
72
I
16
I
29
I
66
I
11
I
2
I
28
I
35
I
3
I
9
I
9
I
6
I
3
I
II
I
17
I
5
I
34
I
4
I
7
I
58
I
39
I
33
I
58
2
2
I
2
-5
, I
I
I
I
I
I
I
I
I
I
I
—5
I
I
—6
2
2
-4
—6
2
I
-3
'I
-3
2
I
I
'I
I
(Continued)
FCobs) and sigma(F) C-sigrna = unobserved):
h
k
I
Fo
I
2
3
4
'5
6
7
7
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
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
109
12
a
9
10
11
-9
-8
-7
-6
-5
-4
-3
-2
-I
a
8
8
8
O 8
I 8
2 8
3 8
4 8
5 8
fa 8
7 8
8 8
9
8
10 8
II 8
-9
9
-8
9
S
I
I
a
■I
5
-3
12
I
27
I
32
I
5
-3
15
I
8
2
7
-3
3
-6
14
I
5
—3
28
I
9
2
2
-5
89
I
54
I
7 - I■
38
I
36
I
I
7
26
I
76
I
13
I
6
2
35
I
4
-4
3
-6
3
—6
a
3
3
-6
6
-3
h
k
-7
—6
-5
-4
-3
-2
-I
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
10
10
10
10
O
I
2
3
4
5
6
7
8
9
10
11
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
I
Fo
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
3
49
28
4
3
17
16
91
6
12
22
45
12
7
6
6
8
9
10
3 .
3
9
37
3
4
25
11
32
4
20
3.
25
69
10
S
T r ichlorobenzene Thiourea Adduct
h
k
-5
6 10
I
7 10
I
8 10
—3
10 10
-5
11 10
I
-8 I I
I
-7 11
I
-6 11
2
-5 11
I
-4 11
I
-3 11
-2 11
I
I
-I 11
0 11
2
-3
I 11
-3
2 11
3 11
2
2 ■
4 -U
2
' 5 11
6 11
-6
-6
7 II
2
8 II
I
10 11
-5
-8 12
-4
-7 12
I
-6 12
-5 12
I
I
-4 12
-3
-3 12
I
-2 12
-I 12
-5
I
0 12
I
I 12
2
2 12
I
Fo
S
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
3
3
3
3
3
3
3
17
3
19
3
15
31
17
45
12
3
14
3
8
16
II
5
8
3
3
10
10
54
8
8
11
4
6
-5
-6
—6
-6
-6
—6
-6
I
-5
I
-5
I
I
I'
I
I
—6
I
-5
2
I
2
-4
2
-6 '
—6
I
2
I
2
2
I
-4
2
h
k
I
Fo
5
.h
3
4
5
6
7
10
-7
-6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
7
-7
-6
-5
-4
-3
-2
—I
0
I
2
3
4
5
12
12
12
12
12
12
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
14
14
14
14
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
3
10
7
12
3
11
3
3
12
3
15
3
8
35
27
6
17
15
10
14
9
7
9
12
17
3
24
3
10
10
3
16
7
-3
-6
2
2
2
-6
2
-6
—6
I
—6
I
-5
2
I
I
-3
I
I
2
I
6
—6
-5
-4
-3
-2
-I
0
I
2
.3
4
5
-5
-4
I;
I
Fo
s
14
15
15
15
15
15
15
15
15
15
15
15
15
16
16
-Z
16
-2 16
-I 16
0 16
I 16
2 16
3 16
3
4 16
2
-4 17
I
-3 17
I ' -2 17
—6
-I •17
I
0 17
-5
I 17
2
2 17
2
3 17
-6
-I 18
I
0 18
3
I 18
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
7
10
11
9
3
10
22
14
4
14
10
3
8
9
3
3
3
17
'4
3
13
3
3
II
8
8
13
6
3
9
5
3
6
8
3
2
2
2
—6
2
I
I
-4
1
2
—6
2
2
-6
-6
-6
I
-4
-6
I
-A
U U-
Table 21.
2
2
2
-3
-6
2
-4
—A
—3
bo
IsO
Table 21.
(Continued)
F(Obs) and Sigma(F)
h
k
-10 0
-8 0
-6 0
-4 0
-2 0
O 0
2 0
4 0
6 0
8 0
10 0
12 0
-I I I
-10 I
-9 I
-8 I
-7 I
—6 I
-5 ' I
-4 I
-3 I
-2 I
-I
I
0 I
I I
2 I
3 I
4 I
5 I
6 I
7 I
8 I
9 I
10 I
I
(-sigma = unobserved):
Fo
S
h
k
2
3
2
14
2
73
6
2
2 235
2
19
2
30
2
94
2
16
2
44
2
7
3
2
2
7
2
3
18
2
7
2
2
11
2
39
2
30
2
24
2 112
2 241
2
8
2
30
2
25
20
2
2
17
2 143
2 . 30
2
2
2
12
26
2
6
2
3
2
-5
I
. I
I
I
I
I
I
I
I
2
—6
2
-6
I
2
I
I
I
I
I
I
I
I
I
I
I
I
I
-5
I
I
2
-6
11
12
-I I
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
7
8
9
10
11
12
-I I
-10
-9
-8
-7
—6
-5
-4
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
3
3
3
3
3
3
3
3
I
Fo
2
9
2
5
2
3
2
6
2
37
2
17
2
22
2
41
2
33
2
66
2
79
2 I 14
2
38
2
93
2 270
2 151
2
89
2 , 62
2
2
2
2
2
3
2
25
2
15
2
6
2
13
2
10
10
2
2
5
32
2
2
3
2
24.
2
42
2
24
2
68
5
T r ichlorobenzene Thiourea Adduct
h
2
—3
-4
-2
-I
-6
-3
0
I
I
I
2
I
3
■I
4
5
I
I
6
I
7
■I
a
I
9
I
ii
I ' -i i
I .-io
I
-9
I ■ -a-5
-7
-5
—6
-5
-5
I
-4
I
-3
-3
-2
2
-I
0
2
2
I
-3
2
I
3
-5
4
I
5
I
6
7
I
I
8
k
I
Fo
S
h
k
I
Fo
S
h
k
i
Fo
3 2
3 2
3 2
3 2
3 2
3 2
3 2
3 2
3 2
3 2
3 2
3 2
3 2
3 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
4 2
115
341
4
46
45
78
27
24
31
43
13
5
7
7
8
3
13
13
13
49
42
51
82
83
5
9
154
74
10
40
2
9
3
to
I
I
2
I
I
I
I
I
I
.1
I
-3
3
—3
2
—6
I
I
I
I
I
I
I
I
2
I
I
I
I
I
-5
2
-5
2
9
11
-10
-9
—8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
7
8
9
-10
-9
-8
-7
—6
-5
-4
-3
-2
—1
0
■I
4
4
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
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
5
9
6
19
3
28
28
5
118
49
36
121
14
32
2
18
38
6
51
4
18
3
3
9
5
59
53
5
2
II
3
147
28
28
-3
2
-3
I
-5
I
I
-2
I
I
I
I
I
I
-4
I
I
2
I
-3
I
—6
-6
2
-3
I
I
2
3
4
5
6
7
8
9
10
11
-10
-9
-8
-7
-6
-5
-4
-3
-2
—I
0
I
2
3
4
5
6
7
8
9
10
11
-10
-9
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
7
8
a
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
8
38
32
34
14
6
16
15
3
3
11
3
3
3
7
8
8
9
90
150
56
7
14
55
17
14
22
3
6
12
3
3
3
9
-2
-5
I
-3
I
I
I
S
I.
I
I
I
I
-3
I
I
-6
—6
2
-6
-5
-5
2
2
I
I
I
I
I
I
I
I
I
I
I
-6
-3
2
—6
—6
—6
2
Table 21.
(Continued)
F (obs) and sigma(F) (-sigma = unobserved):
h' k
-8
-7
-6
-5
-4
-3
— 2.
-I
O
I
'2
.3
4
5
6
7
8
10
11
-9
-8
-7
—6
-5
-4
-3
-2
-I
O
I
2
3
4
5
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
a
8
'8
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
I
Fo
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
21
31
3
6
37
11
24
54
52
29
6
54
7
4
18
7
3
3
3
4
3
16
8
7
80
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
6
48
46
20
7
4
11
3
S
I
I
.-5
2
I
I
I
I
I
I
2
I
2
-3
I
2
—6 ■
—6
-6
-4
-6
I
2
'
2
I
-5
2
I
I
I
2
-4
I
-5
h
k
I
6 9 2
7 9 2
8 9 2
10 9 2
-9 10 2
-8 10 2
-7 10 2
—6 10 2
-5 .10 2
-4 10 2
—3 10 2
-2 10 •2
-I 10 2
0 10 2
I 10 2
2 10 2
3 10 2
4 10 .2
5 10 2
6 10 2
7 10 2
8 10 2
10 10 2
-9 11 2
-8 11 2
-7 II 2
—6 II 2
-5 II 2
-4 II 2
-3 II 2
-2 I I 2
-I II 2
0 11 2
I 11 2
T r ichlorobenzene Thiourea Adduct
k
I
Fo
S
h
k
I
Fo
S
h
k
I
I
2 11
60
3 11
3
—6
4 11
16
I
—6
5 11
3
6 11
2
10
7 11
II
2
10 11
10
2
-a 12
7
2
I
-7 12
11
40
I ' —6 12
-5 12
7
2
46
-4 12
I
-3 12
42
I
40
I
-2. 12
— I■12
15
I
56
I
0 12
36
I
I 12
19
I
. 2.'12
-5
3 12
3
4 12
3
—6
-4
5 12
5
3
—6
6 12
7 12
3
“6
2
-a 13
8
-7
13
10 '
2
—6 13
5
-3
-5 13
3 --5
—4 13
4
-4
-3 13
I
29
-2 13
6
2
-I 13
3
-5
0 13
23
I.
I 13
3
-5
2 13
21
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
2
6
26
12
3
28
3
3
3
11
13
3
3
7
3
37
14
7
5
45
6
6
2
I
I
—6
I
3
4
5
6
-7
13
13
13
13
14
14
14
14
14
14
14
14
14
14
14
14
14
14
15
15
15
15
15
15
15
15
15
15
15
15
16
16
16
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
20
18
8
5
5
15
18
5
14
3
8
3
23
12
8
18
.3
3
6
3
12
12
5
7
5
4
5
10
8
9
8
7
5
8
I
I
2
—4
-4
I
I
-3
I
—6
2
-5
I
I
2
I
-6
—6
-3
-I
0
I
2
3
4
-4
-3
-2
-I
0
I
2
3
-I
0
-10
-8
—6
-4
-2
0
2
4
6
a
-I I
- 10
-9
16
16
16
16
16
16
17
17
17
17
17
17
17
17
18
18
0
0
0
0
0
0
0
0
0
0
I
I
I
I
I
I
I
I
2
2
2
2
2
Fo
S
h
2
2
2
2
2
2
2
6
10
5
3
9
3
18
11
32
35
22
3
II
-6
—6
—6
-5
-4
—3
-2
-I
0
I
2
3
4
5
6
—6
-5
-4
—6
2
I
-5
—6
2
-5
I
I
2
-3
I
-3
-3
-3
2
-4
-6
2
-6
I
I
I
I
I
-5
I
-3
-2
-I
0
I
2
3
4
5
-5
-4
-3
-2 16
2
2
2
2
2
—6
2
I
—3
2
-3
—4
-3
2
2
2
2
2
-4
2
-8
-7
—6
-5
-4
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
Fo
S
8'
2
3 ■ -6
27
I
3
—6
3
-6
-4
4
3
-6
7
-3
16
I
3
-6
7
3
3
-6
3
—6
3
—6
6
-3
3
-6
30
I
7
2
13
I
170
I
151
I
21 I
4
17
I
42
I
37
I
22
I
3
—6
3
3
3
-6
8
3
13
3
3
3
3-
56
2
I
I
I
I
I
12
69
131
Table 21.
(Continued)
F(obs) and sigma(F) (-sigma = unobserved):
T r ichlorobenzene Thiourea Adduct
h
k
I
Fo
h
-3
-2
-I
0
I
2
3
4
5
6
7
8
9
11
-I I
-10
-9
I
I
I
I
I
I
I
I
I
I
I
I
I
I
2
2
2
2
•2
2
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
3
3
3
3
3
3
3
3
142
28
63
183
24
7
59
25
21
12
5
9
5
3
10
14
8
-8
—7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
7
8
2
2
2
2
2
2
2
2
6
22
2
25
43
15
163
7
95
4
25
50
22
25
9
47
5
S
I
I
I
I
I
I
I
I
I
I
•-3
2
—3
—6
. 2
I
2
2
I
—5
I
I
I
I
I
I
2
I
I'
I
I
2
I
—3
h
k
I
9 2 3
11 2 3
-I I 3 3
-10 . 3 3
-9 3 3
—8 3 3
-7 3 3
—6 3 3
-5 3 3
-4 3 3
-3 3 3
-2 3 3
-I 3 3
0 3 3
I 3 3
2 3 3
3 3 3
4 3 .3
5 3 3
6 3 3
7 3 3
8 3 3
9 3 3
11 3 3
-I I 4 3
-10 4 3
-9 4 3
-8 4 3
4 3
-7
—6 4 3
-5 4 3
-4 4 3
-3 4 ■ 3
-2 4 3
Fo
S
k
3
—6
-I 4
9
2
0 4
3
—6
I 4
7
2
2 4
13
I
3 4
I
4 4
11
85
5 4
I
9
■I
6 4
7 4
10
I
82
I
8 4
29
I
9 4
81
I
II 4
2
-4
-I I 5
10
I
-IQ 5
18
I
-9' 5
-8 5
89
I
-7 5
185
I
21
I ■ —6 j 5
-5 5
12
I
3
-5
-4 5
17
I
-3 5
12
-2 5
I
—3
-I 5
6
3
—6
0 5
I 5
8
2
12 ' I
2 5
9
2
3 5
13
I
4 5
I
5 5
23
15
I
6 5
7 5
59
I
39
8 5
I.
9 5
84
I
234
I
II 5
I
Fo
3
3
3
3
3"
3
3
3
3
3
3
3
3
.3
3
3
3
3
3
2
95
17
13
2
15
20
25
30
22
4
5
9
3
-4
I
I
I
-5
I
I
I
I
I
-4
-4
2
6
S
—6
3
48
3
3
3
3
3
3
52
54
24
122
6
24
18
-3
I
I
I
I
I
I
I
I
I
2
I
I
3
4
-3
3
14
3
3
22
3
7
5
I
-5
I
-6
29
20
9
68
3
3
3
3
3
•
-
2
4-
h
-10
-9
-8
-7
—6
-5
-4
-3
. -2
-I
0
I
2
3
4
5
6
7
8
. 9
10
II
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
k
I
Fo
11
6 3
26
6 3
13
6 3
6 3
29
6 3
17
36
6 3
6 3
29
6 . 3 111
6 3
676 3
5
89
6 3
6 3
33
6 3
11
6 3
4
6 3
9
6 3
68
6 3
19
3
6 3'
6 3
14
6 3
7
6 3
3
3
9 3
7 3
3
15
7 3
7 3
7
7 3
18
7 3
3
7 3
61
7 3
19
7 3 I 13
7 3
4
28
7 3
30
7 3
7 3
93
h
k
I
Fo
5
2
2
I
3
4
I.
I
5
I
6
I
7
I
8
I
10
I
-10
2
-9
I
—8
I
-7
- —6
I
-3
-5
I
-4
I
-3
I
-2
—6
-I
’I
0
2
I
-6
2
-7
3
4
-6
I
5
2
6
I
7
-5
8
10
I
I
-10
I
-9
-3
-8
I
-7
I ' —6
I
-5
7
7
7
7
7
7
7
7
8
8
8
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
6
31
33
33
2
I
I
I
-5
2
2
-6
2
2
I
-5
-5
I
I
I
I
I
I
I
I
I
I
I
-6
-6
S
8
8
8
8
8
8
3
a
8
3
3
3
8
3
8
3
8
8
8
3
S
S
8
8
9
9
9
9
9
9
3
3
3
.3
to
9
3
10
11
19
3
3
29
9
a
112
26
11
43
10
II
18
41
3
3
3
3
3
3
11
2
3
3
3
7
3
-6
.3
—6
3
3
3
3
7
18
10
2
-5
I
I
Table 21.
(Continued)
FCobs) and sigma(F) (-sigma = unobserved):
Tri chlorobenzene Thiourea Adduct
h
k
I
Fo
S
h
k
-4 9 3
—3 9 3
-2 9 3
—1 9 3
0 9 3
I 9 3
2 9 3
3 9 3
4 9 3
5 9 3
6 9 3
7 9 3
8 9 3
10 9 3
-9 10 3
-8 10 3
-7 10 3
-6 10 3
-5 10 3
-4 10 3
“3 10 3
-2 10 3
-I 10 3
0 10 3
I 10 3
2 10 3
3 10 3
4 10 3
5 10 3
6 10 3
7 10 3
10 10 3
-9 11 3
-a II 3
12
35
2
26
4
7
80
11
3
8
5
5
16
3
3
I
- I
-5
I
-3
2
I
I
-5
2
-3
-3
I
-7
-7
-6
-5
-4
—3
-2
-I
0
I
2
3
4
5
6
7
8
2
-5
2
I
2
—3
I
I
I
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
13
13
13
13
3
9
13
9
5
86
14
17
9
12
3
3
15
3
8
3
7
3
-6
2
I
-5
-5
I
-8
-7
-6
-5
-4
-3
-2
-I
0
I
2
3
4
5
—6
6
2
-7
-3
-8
-7
—
—6
-5
6'
Fo
S
h
3
13
3
16
3
39
3
3
3
3
3
17
3
3
3
15
3
46
3
37
3
a
3
15
3
28
3
7
3
3
3
3
3
3
3 v, II
3
13
3
23
3
3
3
14
3
16
31
3
3
17
3
26
3
3
3
5
3
30
3
9
3
3
3
3
6
3.
3
20
I
I
I
-5
-5
I
-5
I
I
I
2
I
I
3
-4
-3
-2
-I
0
I
2
3
4
5
-7
-6
I
—6
-6
—6
I •
I
I
-5
I
I
I
I
I
-6
-3
I
2
-6
—6
-3
I
k
I
Fo
5
13 3
13 3
13 3
13 3
13 3
13 3
13 3
13 3
13 3
13 3
14 3
14 3
14 3
-4 14 3
-3 14 3
-2 14 3
-1 1 14 3
0 14 3
I 14 3
2 14 3
3 14 3
4 14 3
5 14 3
—6 15 3
-5 15 3
-4 15 3
-3 15 3
-2 15 3
-I 15 3
0 15 3
I 15 3
2 15 3
3 15 3
4 15 3
6
24
6
6
16
11
19
4
3
10
8
3
3
13
II
24
3
17
15
10
-3
I
2
2
I
I
I
-4
—6
2 .
2
“6
—6
I
I
I
—6
3
10
I
I
2
2
—6
2
6
-3
5
-3
9
2
11
2
-3
9
6
5
II
3
3
23
8
-4
2
-6
—6
I
2
h
k
I
Fo
S
h
k
I
Fo
S
-5
-4
-3
-2
-I
0
I
2
3
-4
-3
-2
-I
0
I
2
-10
16
16
16
16
16
16
16
16
16
17
17
17
17
17
17
17
0
0
0
0
0
0
0
0
0
0
I
I
I
I
I
I
' I
I
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
3
3
11
3
6
7
9
3
9
10
3
3
3
5
3
-6
—6
2
-6
-3
3
2
—6
2
2
-6
—6
' -6
-4
-7
—6
-5
-4
-3
4
4
42
109
137
Rl
16
33
6
3
32
39
21
11
10
3
3
15
3
10
25
29
101
I
I
I
I
I
I
2
-3
I
I
I
2
2
-6
2
I
I
I
I
I
2
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
4
4
4
4
4
4
4
8
-3
-2
-I
0
I
2
3
4
5
6
7
8
9
II
-11
-to
4-
44
4
-2
2
4
-I
2
2
2
2
2
2
2
2
4
4
4
5
57
24
42
-8
—6
-4
-2
0
2
4
6
8
-11
-10
-9
-a
-7
—6
-5
-4
4
4
4
4
4
4
4
4
4
4
4
4
4
16
51
49
67
54
124
96
24
16
3
8
3
9
70
10
13
51
23
-6
-9
-8
—6
0
2
I
2
3
4
5
—6
2
I
I
I
I
I
6
7
8
2
2
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
42
2
15
50
3
7
10
—6
I
-5
2
I
I
I
I
I
I
I
I
-2
I
-5
I
I
—5
2
Table 21.
(Continued)
F(obs) and sigma(F) (-sigma = unobserved) :
TrichLorobenzene Thiourea Adduct
h
k
I
h
9
11
-I I
-10
-9
-a
-7
-6
-5
-4
-3
—2
-I
O
I
2
'3
4
5
6
7
8
9
II
-I I
-10
-9
2
2
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
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
4
4
4
4
4
4
4
4
4
4
- a
-7
-6
-5
-4
-3
-2
Fp
S
h
k
8
2
-I 4
3
-6
0 4
9
2
I 4
20
I
2 4
10
I
3 4
27
I
4 4
3
—5 5 4
20
I
6 4
2
-5
7 4
42
I
8 4
63
I
II 4
5
I
-I I 5
201
I
-10 5
98
I
-? 5
42
-8 5
I
15 . I
-7 5
7
I
—6 5
17
I
-5 5
47
I
-4 5
6
-2.
-3 5
15
I
-2 5
3
-6
-I. 5
13
2
0 5
3
-6
I 5
3
-6
2 5
3
—6
3 5
3
4 5
-5
27
I
5 5
5
-2
6 5
53
I
7 5
I10
8 5
I
53 . I '-10 6
84
I
-9 ■6
40
-B 6
I
I
Fo
S
4
27 ■ I
-7
35
I
4
—6
I
4
72
-5
I
4 129
-4
4
37
-3
I.
4
47
I
-2
4
23
I
-I
14
■I
4
0
4
18
I
I
4
7
2
2
4
9
2
3
4
5 ' -4
4
24
4
I
5
4
7
2
6
4
27
I
7
4
7
2
8
4
14
I
10
•4 , 44
I ■ -10
4
10 . I
-9
4
53
I
- a
4
30
I
-7
4
45
I
-6
4
20
I
-5
4
57
I
—4
4
50
I
-3
4
15
I
-2
4
28
I
-I
II
'4
I
0
4
2
I
9
4
23
I
2
4
—6
3
3
4
5
-4
4
4
3
-6
5
4
I
6
17
k
I
Fo
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
7 4
7 4
7 4
7 4
7 4
7 4
7 4
7 4
7 4.
7 4
7 4
7 4
7 4
7 4
7 4
7 4
7 4
16
3
12
21
88
12
8
5
34
102
33
18
3
7
3
3
3
9
3
9
3
25
S
63
107
10
23
7
39
6
3
7
12
6
S
I
-5
I
I
I
I
I
2
I
I
I
I
-5
2
—6
—6
—6
2
—6
2
-5
I
2
I
I
I
I
I
I
2
-5
2
I
-3
h
k
7
8
10
— 10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
7
8
10
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
7
7
7
a
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
9
9
9
9
-9
9
9
9
9
9
9
I
Fo
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■
35
5
3
4
3
14
19
33
6
29
44
5
18
5
69
12
49
48
3
3
7
3
3
22
10
8
3
18
6
II
23
2
II
67
S
I
-3
-6
-4
—6
I
I
I
2
I
I
-3
I
-2
I
I
I
I
-5
—6
-3
—6
-7
I
2
2
-5
I
-2
I
I
-5
I
I
h
I;
L
Fo
I
9
9
9
9
9
9
9
9
10
to
10
10
10
to
10
10
10
to
10
to
10
10
I0
10
10
11
11
11
11
11
11
11
11
11
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
A
4
4
4
A
A4
4
4
4
4
4
4
4
4
3
3
26
16
5
5
5
7
7
12
3
39
,17
7
20
10
7
39
9
16
6
43
7
3
3
7
10
4
8
14
18
42
5
9
3
4
5
6
7
. 10
-9
—8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
7
-9
-8
-7
-6
-5
-4
—3
-2
-U
S
-5
-5
I
I
-3
-3
-4
—3
2
I
-5
I
I
2
I
I
2
I
2
I
-3
I
2
—6
—6
3
2
-4
2
I
I
t
—3
Table 21
(Continued)
F(obs) and sigma(F). (-sigma = unobserved):
Trichlorobenzene Thiourea Adduct
h
h
0
I
2
3
4
5
6
-a
-7
-6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
-8
-7
-Ca
-5
-4
-3
-2
0
I
2
3
k
I
Fo
H
4
54
11 4
31
11 4
5
11 4
11
11 4
17
11 4
3
11 4
6
12 4
3
12 4
7
12 4
3
12 4
10
12 4
21
12 4
44
12 4
12
12 4
12
12 4
23
12 4
19
12 4
19
12 4
21
3
12 4
12 4
10
12 4
a
13 4
10
13 4
ii
13 4
5
13 4
7
13 4
6
13 4
24
13 4
8
13 4
13
13 4
14
13 4 . 3
13 4
10
7
13 4
S
I
I
-3
2
I
—6
-3
—6
2
—6
2
I
I
I
I
I
I
I
I
—6
2
2
2
2
—3
2
-3
I
2
I
I
—6
2
2
h
4
5
-7
—6
-5
-4
—3
-2
-I
0
I
2
3
4
5
-6
-5
-4
-3
-2
-I
0
I
2
3
4
-5
-4
-3
' -2
-I
0
I
k
I
Fo
13 4
3
13 4
9
5
14 4
14 4
7
14 4
6
a
14 4
14 4
13
14 4
7
14 4
12
14 4
21
14 4
5
14 4
17
14 4
a
14 4
14
14 4
6
15 4
3
15 4
3
15 4 .. 6
15 4 • 9
15 4
5
15 4
23
15 4
9
15 4
6
15 4
4
15 4
7
15 4
3
16 4
17
16 4
11
16 4
5
16 4
5
16 4
3
16 4
■ 3
16 4
9
2 16 4
3
S
Fo
S
h
I;
16 4
3
17 4
10
17 4
7
17 4
10
17 4
3
17 4
3
0 5
5
0 5
26
35
0 5
0 5
2
0 5
94
0 5
88
0 5
10
0 5
16
4
0 5
0 5
28
I 5
7
9
I 5
I 5
3
I 5
24
I 5
11
I '5
75
I 5
38
I 5 . 71
I 5
51
I 5
49
I 5
50
I 5
5
I 5
32
I 5
2
24
I 5
4
I 5 I03
5
I 5
18
6
I 5
3
—6
2
-3
2
—6
—6
-3
I
I
—4
I
I
I
I
-4
I
2
2
-5
I
I
I
I
I
I
I
I
2
I
7
8
-I I
-10
-9
—8
-7
—6
-5
—4
—3
—2
-I
0
I
2
3
4
5
I
I
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
-6
2
-3-4
-2
3
—1
-3
0
2
I
I
-10
2
-8
I
—6
-4
I
-2
-3
I
.o
2
2
4
I
-3
6
—6
a
—6
— lit
—3 • -10
2
-9
-3
—8
I
-7
2
—6
-3
-5
-4
-4
-3
3
-6
-2
I
-I
2 • 0
-4
I
2
-3
—6
3
—6
2
—6
k
I
-5
I
I
I
-5
6
7
8
-I I
-10
-9
-8
-7
-6
-5
-4
-3
-2
-I
0
3
3
3
3
3
3
3
3
3
3
3
S
h
k
I
5
12
I
5
3
—6
21
I
5
3
—6
5
5
38
I
5
10
I
5
12
I
5
45
I
5
38
I
5
24 ■ I
5
96
I
5
48
I
5
41
I
5 107
I
5 HS
I
5
21
I
5
5
-2
5
11
I
5
2
7
5
25
I
5
18
I
5
15
I
5
3. —6
5
6
-3
5
3
-6
5.
4
—4
5
13
I
5
2
-5
5
52
I
5
46
I
I
5 107
I
5
15
5
23
I
5
23
I
I
2
3
4
5
6
7
8
-11
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
I
Fo
4
4
4
4
4
4
5
5
6
7
4
4
4
5
5
5
a
4
5
-i i
— 10
-9
-8
-7
5
5
—6
Fo
5
5
5
5
5
5
5
5
5
5
'
S
126
I
43
I
15
I
JI
I
3
-5
13
I
4
-4
10
2
7 . 2
6
-3
25
I
26
I
33
I
6
2
48
I
47
I
25
I
54
I
18
I
29
I
70
I
14
I
4
-3
2
9
15
I
37
I
13
I
10
2
17
I
-4
5
13
I
to
2
9
2
58
I
Table 21.
(Continued)
F <obs) and sigma(F) (-sigma = unobserved):
Tri chlorobenzene Thiourea Adduct
h
h
-5
-4
-3
k
5
5
5
— '2
5
■ -I
5
0 5
I 5
2 5
3 5
4 5
5 5
6 5
7 5
8 5
-10 6
-9
6
-8 6
-7 6
-6 6
-5 6
-4 6
-3 6
-2 6
-I 6
0'6
I 6
2 6
3 6
4.6
5 6
6 6
7 6
8 6
10 6
I
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
Fo
S
h
k
35
I
33
I
74
I
29
I
26
I
9
I
9
I
22
I
28
I
53
I
3
-5
32
I
5
-4
3
-6
11
2
3
—6
7
2
27
I
■25
I
2
-5
61
I
25
I
33
I
I
109
-5
2
41
I
10
I
14
I
16
I
7
2
10
2
9.
2
9
2
3
—6
-10
-9
—8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
7
10
-10
-9
-8
-7
-6
-5
-4
-3
-2
-I
0
I
2
3
4
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
8
a
8.
8
8
8
8
8
I
Fo
5
a
5
ii
5 ■ 3
5
25
5
3
5
II
5
49
5
12
5
23
5
33
5
53
5
13
9’
5
5
48
5
21
5
9
5
5
6
5
5
3
5
6
5
9
5
14
5
3
5 ■ 12
5
II
5
3
13
5
5
8
5
79
5
12
5
8
20
5
5
6
5
7
S
k
2
5 8
2
6 8
-5
.7 a
I
-10 9
-5
-9 9
I
-a 9
I
-7 9
I
-6 9
I
-5 9
I
-4 9
I
. -3 9
I
-2 9
2
-I 9
I
0 9
I
I 9
2
2 9
-4
3 9
-3 ■
4 9
-7
.5 9
-3
6 9
2
•7 9
I
-9 10
-5
-8 10
I
-7 ■10
I
—6 10
-5
—5 10
I
-4 10
2
-3 10
I
-2 10
I
— I 10
2
0 10
I
I 10
2
2 10
2
3 10
I
Fo
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
II
24
9
3
3
13
7
33
38
74
3
7
3
11
7
48
14
3
10
22
9
14
21
16
10
33
10
3
10
50
23
a
44
18
S
2
I
2
—6
-6
I
2
I
I
I
-5
2
-5
I
2
I
I
-5
2
I
2
I
I
I
2
I
I
, -5
I
1 I
I
2
I
I
h
k
I
Fo
4
5
6
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
-8
10
10
10
11
11
11
1.1.
11
II
II
II
11
II
11
11
11
11
11
11
12
12
12
12
12
12
12
12
12
12
12
12
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
12. 5
12 5
13 5
4
9
26
5
3
S
3
16
27
14
II
13
10
3
14
31
7
3
7
3
13
3
13
3
3
18
52
II
5
15
5
a
7
3
S
-4
2
I
-4
—6
2
-6
I
I
I
I
I
2
-5
I
I
2
—6
3
—6
I
—6
I
—6
—6
I
I
I
-3
I
-4
2
3
—6
h
k
-7
—6
-5
—4
-3
-2
-I
.0
I
2
3
4
5
-7
—6
-5
-4
—3
-2
-T
0
I
2
3
4
-6
-5
13
13
13
13
13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
14
14
14
15
15
15
15
15
15
15
15
15
-4
-3
—2
-I
0
I
2
I
Fo
S
5
3
5 ■ 11
5
9
5
13
5
3
11
5
5
8
5
3
5
3
5
16
5
12
5
16
5
3
5
3
5
4
5
7
5
7
5
6
5
13
5 ' 12
5
6
5
14
5
3
5
6
5
9
5
7
5
8
5
II
5
11
5
14
5
8
5
3
5
12
5
.6
-6
2
I
-6
2
2
—A
—6
I
2
I
—6
—iS
-4
3
2
-3
I
I
-3
I
r-6
-3
2
3
2
2
2
I
2
2
2
*■3
Table 21.
(Continued)
F(obs) and sigma(F)
k
I
3 15
-5 16
-4. 16
-3 16
5
5
5
5
5
5
5
5
5
5
5
h
-2 16
-I 16
O 16
I 16
2 16
-2 17
-I 17
-10 o
-S o
6
0 6
-4 0 6
-2 o 6
o o 6
2 0 6
-6
4
o
(3
0 6
S 0 6
-11 I 6
-10 I 6
I 6
-9
-8 I 6
I 6
-7
—6 I 6
-5 I 6
-4 I 6
-3 I 6
I 6
-2
6
-I
o
I
I
I
I
T r !chlorobenzene Thiourea Adduct
S
h
t;
I
Fo
S
h
k
I
Fo
S
h
I;
I
Fo
S
h
I-:
I
Fo
Ti
4
5
3
9
cb
-4
-4
2
I
I
-5
—3
3
I
i
I
I
I
I
I
-.5
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
13
26
16
3
I
I
I
I
-4
I
I
I
I
I
-9
—3
—7
-2
2
-I
7
2
2
2
I
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
2
-5
-4-3
7
7
7
7
7
7
7
28
9
8
16
73
48
32
16
27
47
3
5
2
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
-7
38
3
2
-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
22
a
I
I
I
I
I
I
I
6
6
11
21
6
3
Fo
3
18
—6
2
3
4
5
-3
6
6
1+
I
-3
I
3
3
—6
—6
10
I
I
I
I
I
I
—3
I
16
166
20
28
.14
4
41
3
3
16
—6
—6
28
I
I
-3
I
I
I
I
-4
I
6
6
2
6
169
30
I
I
6
(-sigma = unobserved):
20
4
20
44
8
8
2
8
-11 2
-10 2
-9 2
-B 2
-7 2
-6 2
-5 2
-4 2
-3 2
-2 2
-I 2
0 2
I 2
2 2
3 2
4 2
5 2
6 2
7 2
-I I
-10
-9
-8
-7
—6
-5
-4
3
3
3
3
3
6
3
3 ‘ 6
3
6
15
7
7
9'
5
11
3
37
5
60
89
47
46
36
■5
31
10
101
24
8
4
17
5
5
14
23
60
29
2
27
-2 3
-I
3
0 3
3
I
I
2
2 3
3
3
3
-3
6 3
I
7 3
-5
-11 4
I
-10 4
-2
-9 ::4
I
-a 4
I
-7 • 4
I
—6 4
I
. -5 .4
I
-4 4
-2
-3 4
I
-2 4
I
-I 4
I
0 4
I
I 4
2
2 4
-4
3 4
I
4 4
-3
5 4
-3 ■
6 4
I
7 4
I
-I I 5
I
-10 5
I
-9 5
-5
-8 5
I
—3
2
3
4
5
8
2
4
17
-4
I
11
2
4
14
3
-4
I
-5
I
I
12
39
5
33
5
64
-2
I
—6 5
-5
-4
-3
5
5
5
-2 5
-I 5
0 5
I 5
2 5
3 5
4 5
5 5
6 5
7 5
— 10 6
-9 6
' -8 6
-7 6
2
-6
17
I
I
I
-5
—4
-3
8
.1
-2
I
I'
-I
21
15
65
3
8
15
3
3
0
—6
I
2
I
2
-6
—6
2
3
4
5
I
6
7
-5
-10
6
6
6
6
6
6
6
'6
6
6
6
6
6
6
7
6
6
6
6
6
6
6
6
6
6
&
6
6
6
6
2
26
19
69
30
19
7
8
10
20
.9
3
15
11
•28
7
40
51
I
2
—6
I
I
I
2
14
42
15
I
I
-5
I
I
I
8
2
17
I
-3
2
6
—6
3
54 • I
I
12
—6
0 7
7
2 7
3 7
4- 7
5 7
6 7
7 7
— 10
8
-9 8
-8 8
-7 8
—6 8
-5 8
-4-3
-2
-I
8
8
8
8
0 8
I 8
2 8
3 8
4- 8
3
—6
5
7
2
6
8
a
22
6
4
20
4
13
26
2
69
13
4
14
8
3
7
6
9
15
12
6
29
3
3
68
13
5
15
7
8
22
6
6
28
6
4-
I
I
2
-3
I
—3
I
I
-5
I
I
—3
I
2
—6
3
-3
2
I
I
2
I
-5
—5
I
I
—3
I
2
2
I
I
-4
Table 21.
(Continued)
F(obs) and Sigma(F)
h
k
I
Fo
-10 9
-9 9
-B 9
-7 9
-6 9
-5 9
-4 9
—3 9
-2 9
-I 9
O 9
I 9
2 9
3 9
4 9
5 9
6 9
-9 10
—8 10
-7 10
-6
10
-5 10
-4 10
-3 10
-2 10
-I 10
O 10
I 10
2 10
3 10
4 10
5 10
6 10
-9 II
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
14
7
8
3
26
17
'26
10
76
5
3
18
32
7
3
9
3
8
5
3
13
13
7
12
54
15
II
17
16
14
14
9
8
16
6
6
6
6
6
6
6
6
6
6
6
6
6
6
S
(“Sigma = unobserved)!
h
k
I
I
-8 11 6
2
-7 11 6
2
—6 II 6
-5
-5 11 6
I
-4 I I 6
I
-3 11 6
I
-2 11 6
I
-I 11 6
I
0 II 6
-3
I 11 6
-5
2 11 6
I
3 II 6
I
4 II 6
5 11 6
2
—6
-8 12 6
2
-7 12 6
-6
—6 12 6
2
-5 12 6
-3
-4 12 6
-6
-3 12 6
I
-2 12 6
I
-I 12 6
2
0 12 6
I
I 12 6
I
2 12 6
I
3 12 6
I
4 12 6
I
5 12 6
I . -7 13 6
—6 13 6
I
I
-5 13 6
2
-4 13 6
2
-3 13 • 6
I
-2 13 6
Fo
S
6
-3
8
2
5
-3
23
I
10
2
3
-5
41
I
10
2
22
I
42
I
3
-6
5
-3
10
2
3
—6
5
-4
9
2
5
-3
25
I
17 ' I
7
2
14
I
7
2
6
-3
14 ' I
8
2
3
—6
7
3
20
I
5
-4
12
2
5
—3
5
-4
II
2
16
I
TrichLorobenzene Thiourea Adduct
h
k
I
Fo
S
-I 13
‘ 0 13
I 13
2 13
3 13
4 13
-7 14
—6 14
-5 14
-4 14
-3 14
-2 14
-I ,14
0 ■14
I 14
2 14
—6 15
■ -5 15
-4 15
-3 15
' -2 15
-I 15
0 15
I 15
2 15
—4 16
-3 16
-2 16
-I 16
0 16
-10 0
-8 0
-6 0
—4 0
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
5
19
22
7
5
II
3
12
3
16
20
13
9
3
7
3
10
3
3
5
3
10
7
8
3
5
10
4
3
10
26
46
II
23
-3
I
I
2
-3
2
—6
2
—6
I
I
I
2
—6
2
-6
2
—6
—6
-3
-6
2
3
2
—6
-4
2
-4
—6
2
I
I
I
I
h
I:
I
Fo
S
-2 0
0 0
2 0
4 0
6 0
-I I I
-10 I
-9 I
-8 I
-7 I
—6 I
-5 I
-4 ' I
-3 I
-2 I
-I I
0 I
I I
2 I
3 I
4 I
5 I
6 I
7 I
-I I 2
-10 2
-9 2
-S 2
-7 2
-6 2
-5 2
-4 2
-3 2
-2 2
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
7
7
7
26
53
122
10
3
4
7
3
5
11
11
57
14
21
37
64
2
4
45
9
8
38
10
6
8
5
7
21
26
16
51
15
39
17
I
I
I
I
-5
-4
2
-5
-3
I
I
I
I
I
I
I
-5
-3
I
2
2
I'
2
-3
2
-3
2
I
I
I
I
I
I
I
h
I;
I
Fo
5
-I
0
I
2
3
4
5
6
7
-11
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
7
-11
-10
-9
-8
-7
—6
2
2
2
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
4
4
4
4
4
4
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
7
7
7
66
2
23
48
6
4
5
7
6
3
21
6
6
24
3
71
2
21
39
52
12
6
6
3
14
46
I
-5
I
I
-2
-3
-4
2
-3
-6
I
-2
2
I
-5
I
-5
I
I
I
I
2
2
—6
I
I
2
2
—6
2
—6
I
I
I
-
a
10
3
13
3
25
II
vo
H
Table 21.
F(obs) and
h
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
7
-I I
— TO
-9
-8
-7
-6
-5
-4
—3
-2
-I
0
I
2
3
4
5
cb
-10
-9
-8
(Continued)
b
igm'a CF) <-sigma = unobserved):
k
I
Fo
S
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
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
7
7
7
46
22
2
■ 53
55
42
31
37
12
3
9
3
3
7
13
11
4
19
14
4
20
79
43
31
14
21
13
24
30
12
3
7
6
27
I
I
-5
I
I
I
I
I
I
—6
2
—6
—6
3
I
2
-4
I
I
-3
I
I
I
I
I
I
I
I
I
I
—6
3
3
I
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
h
k
I
-7
—6
-5
—4
-3
-2
-I
0
I
2
3
4
5
6
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
-10
-9
-8
6
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
8
8
8
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
7
7
7
Fo
S
I
27
I
12
I
21
2
7
I
13
2
9
I
11
I
17
I
19
I
28
I
25
2
8
—6
3
2
8
2
9
3 . —6
2
10
I
,12
-5
. 3
26 . I
9
2
I
I 09
39
I
18
I
I
13
8
2
—3
5
25
i
2
II
8
2
-6
3
3
—6
—6
3
-3
5
Tri chlorobenzene Thiourea Adduct
I
FO
S
h
k
I
Fo
5
h
k
I
Fo
S
B 7
-7
8
7
—6
a 7
-5
7
-4
8
8 7
-3
8
7
-2
-I
8 '7
7
0 8
I 8 7
2
8 7
3
8 7
7
4
8
5
8 7
7
6 VS
9
7
-9
-a 9 7
-7 ,9 7
7
—6 9
9
7
-5
9
7
-4
7
-3
9
-2
9
7
9
7
-I
7
0 9
7
I 9
7
2 9
7
3 9
9
7
4
5
9
7
' -9 10 7
-8 10 7
7
-7 10
-6 10 7
7
-5 10
25
32
II
3
•38
23
21
62
12
6
21
26
3
6
4
13
3
19
3
9
3
3
3
19
10
5
3
25
3
3
3
3
13
6
I
I
I
-5
I
I
I
I
I
-2
I
I
-6
-3
-4
I
-5
I
-5
2
-5
-5
-5
I
2
-3
-6
I
—6
—6
—6
—6
I
-3
—4
-3
-2
-I
0
I
2
3
4
5
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
-8
-7
-6
’ -5
-4
■ -3
-2
-I
0
I
2
10
10
10
10
10
10
10
10
10
10
II
II
11
11
11
11
11
11
11
11
11
11
II
12
12
12
12
12
12
12
12
12
12
12
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
7
7
7
4
II
7
-4
I
2
2
I
I
-3
-3
—3
3
3
—6
I
I
2
I
-5
2
2
2
—6
I
2
I
I
—6
2
I
—6
-4
-3
—6
—3
I
3
4
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
-6
-5
-4
-3
-2
-I
0
I
2
-5
-4
-3
-2
-I
0
I
—2
-10
-8
—6
-4
12
12
13
13
13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
15
15
15
15
15
15
15
16
0
0
0
0
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
9
8
3
6
7
6
19
15
13
3
5
7
12
5
14
6
10
3
3
14
6
9
11
8
3
3
15
5
5
3
7
4
38
19
2
2
-6
-3
2
-3
I
I
I
—6
-3
2
2
—4
I
-3
2
—6
—6
I
-3
'2
2
2
—6
-6
I
-4
-4
-6
2
-4
I
I
h
k
to
63
13
5
5
6
7
6
3
14
15
7
34
3
10
11
6
3
17
10
14
17
3
6
19
3
4
5
3
6
16
a
8
8
Table 21.
(Continued)
F(obs) and sigma (F) (-sigma = unobserved):
n
K
-2
O
O
O
O
O
O
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
2
2
2
2
4
6
-11
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
O
I
2
3
4
5
6
-I I
-10
-9
I
8
a
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
-5
2
-4
-3
-2
-I
2
8
8
8
8
8
8
2
8
-8
2
-7
-6
2
2
2
8
2
a
S
h
I
22
I
11
I
77
I
3
-6
4 . -4
6
-3
6
2
27
I
7
2
49
I
8
I
21
I
2
-5
8
I
23
I
34
I
54
I
18
I
3
-5
46
I
10
2
6
3
7
3
9
2
18
I
8
2
7
2
7
2
15
I
12
I
93
I
26
I'
18
I
0
I
2
3
4
5
6
-11
-10
-9
-8
-7
—6
ho
6 2
-5
-4
-3
-2
-I
0
I
2
3
4
5
-11
-10
-9
-8
-7
-6
-5
-4
-3
-2
I
Fo
B
2
8
2
8.
2
8
2
a
2
8
2. 8
2
8
3
8
8
3
3
8
3
8
3
8
8
3
3 8
3
a
3 8
3
8
3 8
3 8
3 8
3
8
3
8
3
8
3 8
4
8
4 8
4
8
4 8
4
8
4
8
4
8
4 8
4 ■B
4
a
14
12
13
6
31
3
4
11
8
18
24
10
10
2
46
3
2
■13
15
62
25
8
3
5
3
7
17
I
I
I
-3
I
-6
-4
2
2
k
8
18
15
9
53
49
4
I
I
I
I
-5
I
-5
-5
I
I
I
I
2
—6
-3
-6
3
I
■ 2
I
I
I
I
I.
-3
T r ichlorobenzene Thiourea Adduct
h
I:
i
-I
4
0 4
I 4
2 4
3
4
4 4
5 4
6
4
-10
5
-9
5
-8
5
-7
5
— 6 lt5
-5 '- 5
-4
5
-3
5
-2 ■5
■ -I
5
0 5
I 5
2
5
3 5
4 5
5 5
6 5
-10
6
-9
6
-a 6
-7
6
—6 6
-5
6
6
-4
-3
6
Cd
-2
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
a
a
a
a
8
8
a
8
8
8
S
8
8
8
Fo
S
h
k
I
Fo
S
22
I
-I
9
I
0
18
I
I
10
2
2
14
I
3
15
I
4
3 ' —6
5
18
I
-10
9
2
-9
3
—6
-a
26
I
-7
28
I
—6
46
I
-5
2.1
I
-4
7
2
-3
25
I
-2
5
-3
. -I
24
I
0
16
I
I
7
2
2
48
I
3
13
- I
4
9
2
5
3
-6
-10
8
2
-9
12
2
-8
6
—3
-7
3
-5 ’• -6
13
I
-5
6
6
6
6
6
6
6
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
a
8
8
8
8
8
8
8
8
8
8
8
8
3
8
8
8
8
8
a
a
8
8
8
8
8
8
8
8
a
74
25
5
5
5
13
7
3
8
3
16
19
28
31
12
20
52
13
13
17
16
3
6
3
3
13
'3
17
4
I
I
-3
—4
-3
I
2 ■
—6
2
—6
I
I
I
I
I
I
I
I
I
I
I
2
-3
—6
—6
I
-5
I
a
28
8
8
8
8
26
a
8
a
8
25
6
8
3
3
-5
14
I
I
' -4
-3
-2
2
-5
-I
0
S
8
8
8
8
3
37
23
-4
I
I
-5
I
I
h
k
I
Fo
S
I
2
3
4
5
-9
—8
-7
—6
-5
-4
-3
-2
—1
0
I
2
3
4
-9
-8
-7
-6
-5
-4
-3
-2
—I
0
I
8
8
8
8
8
9
9
8
8
8
8
B
8
8
3
8
8
8
8
8
a
.8
8
8
8
8
8
8
8
8
3
18
9
3
5
•9
16
6
6
10
21
4
8
14
7
3
47
10
3
3
3
6
16
II
29
7
6
19
—6
I
2
—6
-4
2
I
2
2
I
I
-4
2
I
2
—6
I
2
—6
—6
-6
-3
I
I
I
2
3
4
-8
9
9
9
9
9
9
9
9
9
9
9
9
10
10
10
10
10
10
10
10
10
10
10
10
10
10
11
a
8
8
8
3
8
5
3
2
-2
I
-3
a
8
8
2
8
3
—6
8
a
3
3
—6
—6
-6
vo
Co
Table 21.
(Continued)
F(Gbs) and Sigwa(F)
h
k
L
Fo
S
—
6
3
8
2
—
6 11 8 ’ 7
-6
3
-5 I I 8
-6
-4- 11 a
3
2
a
- 3 11 8
I
n
- 2 11 8
24
I
- I 11 8
3
-6
0 11 a
10
2
I 11 8
19
2 11 8
I
2
10
3 11 8
-3
5
-7 12 8
-6
3
—
6 12 8
I
12
-5 12 8
—
6
3
- 4 12 8
7
3
- 3 12 a
I
15
- 2 12 8
I
26
- I 12 8
2
a
0 12 , 8
3
—
6
I 12 8
3
-6
2 12 8
.10
2
3 12 8
—
6
3
-7 13 8
I
21
- 6 13 8
16
I
-5 13 8
—
6
3
-4 13 8
—6
3
-3 13 8
2
II
- 2 13 8
3 ' -6
- I 13 8
—6
3
0 13 8
—6
3
I 13 a
-C d
3
2 13 8
-6
3
-5 14 ' 8
—6
3
-4 14 8
-7 11
(-sigma = unobserved):
h
-3
-2
-I
0
I
-4
-3
—2
-I
-10
-8
—6
-4
-2
0
2
4
-11
-10
-9
-8
-7
-6
-5
-4
-3
-2
-I
0
I
2
3
4
5
I
Fo
S
14 B
14 8
14 8
14 8
14 8
15 8
15 8
15 8
15 8
0 9
0 9
0 9
0 9
0 9
0 9
0 9
0 9
I 9
I 9
I 9
I 9
I 9
I 9
I 9
I 9
I 9
I 9
I 9
I 9
I 9
I 9
I 9
I 9
I 9
15
3
8
6
5
11
7
11
3
6
10
4
81
30
51
12
4
■, 8
5
10
19
5
13
7
60
2
24
26
33
9
3
12
3
3
I
—6
2
-3
-4
2
-3
2
—6
-3
2
-3
I
I
I
I
-4
2
—3
2
I
-3
I
■2
I
-5
I
I
I
2
-5
2
—6
—6
k
T r ichlorobenzene Thiourea Adduct
h
k
I
-^l I 2 9
-10 2 9
-9 2 9
-8 2 9
-7 2 9
—6 2 9
-5 2 9
—4 2 9
-3 2 9
-2 ’ 2 9
-I 2 9
0 2 9
I 2 9
2 '.:‘2 9
3 2 9
4 2 9
5 ,2 9
-10 3 9
-9 3 9
-8 3 9
-7 3 9
—6 3 9
-5 3 9
-4 3 9
-3 3 9
-2 3 9
-I 3 9
0 3 9
I 3 9
2 3 9
3 3 9
4 3 9
5 3 9
-10 4 9
Fo
S
-6
3
—6
3
I
19
2
8
I
41
-3
5
5 - -3
.I
32
-2
6
I
25
I
27
-3
5
I
16
I
11
I
61
3
6
-6
3
-6
3
2
10
I
16
2
7
-3
5
20
I
I
19
I
13
62
I
I
50
-5
3
10
2
'Cl
12
6
3
3
2
-3
—6
—6
h
-9
-8
-7
-6
-5
-4
-3
-2
-I
0
I
2
3
4
5
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
-10
-9
-8
k
I
Fo
S
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
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
13
3
20
31
3
9
3
12
3
17
8
6
34
13
9
7
18
3
10
15
12
42
13
56
21
24
28
3
3
7
Ii
3
11
5
I
-5
I
I
-5
2
-5
I
-5
I
2
2
I
I
2
2
I
—6
2
I
I
I
I
I
I
I
I
-6
—6
3
2
—6
2
-3
h
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
-10
-9
-8
-7
-6
-5
-4
—3
-2
-I
0
I
2
3
4
-9
-8
-7
-6
-5
-4
I
k
I
6 9
6 9
6 9
6 .O
6 9
6 9
6 9
6 9
6 9
6 9
6 9
6 9
6 9
7 9
7 9
7 9
7 9
7 9
7 9
7 9
7 9
7 9
7 9
7 9
7 9
7 9
7 9
7 9
8 9
8 9
8 9
a
9
8 9
8 9
Fo
S
11
I
12
I
44
I
32 . I
10
I
16
I
14
I
6
-3
I
54
3
2
6
-3
12
2
12
2
3
—6
17
I
11
2
3
-f.
7
2
II
I
13
I
3
-5
21
I
12
I
8
2
23
I
3
-6
3
—6
8
2
12
I
3
—6
9
2
I
23
3
—5
20
I
Table 21.
(Continued)
F(obs) and sigma(F) (-sigma = unobserved):
Tri chlorobenzene Thiourea Adduct
h
h
k
I
—3 8
-2 8
-I 8
0 8
I 8
-2 8
3 8
-9 9
-8 9
-7 9
—6 9
—5 9
-4 9
-3 9
-2 9
-I 9
0 9
I 9
2 9
3 9
-8 10
-7 10
—6 10
-5 10
-4 10
—3 10
-2 10
-I 10
0 10
I 10
2 10
3 10
-8 11
-7 II
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
Fo
6
4
3
3
34
18
3
5
8
3
3
9
3
3
54
6
3
8
3
5
7
11
22
12
3
8
7
7
8 '
10
3
8
3
3
5
-3
-4
-5
—6
I
I
-6
-4
2
-6
-6
2
-6
-5
I
-3
-6
2
-6
-4
3
2
I
I
—6
2
2
2
2
2
-6
2
—6
—6
h
k
I
Fo
S
-6 11 9
-5 11 9
-4 11 9
-3 11 9
-2 11 9
-I 11 9
0 11 9
I 11 9
2 11 9
-7 12 9
—6 12 9
-5 12 9
-4 12 9
-3 12 9
-2 12 9
-I 12 9
0 12 9
I 12 9.
2 12 9
-5 13 9
—4 13 9
"3 13 9
-2 13 9
-I 13 9
0 13 9
-4 14 9
-3 14 9
-2 14 9
-I 14 9
-10 0 10
—8 0 10
—6 0 10
-4 0 TO
-2 0 10
5
3
5
7
18
3
10
13
3
9
8
3
18
5
3
a
5
■20
3
3
15
7
7
3
9
10
17
3
3
13
22
9
11
66
-4
—6
-3
2
I
-6
2
I
—6
■2
2
—6
I
-3
-6
2
-4
I
-6
—6
I
3
2
-6
2
2
I
-6
-6
' I
I
2
I
I
k
I
0 0 10
2 0 10
4 0 10
-10 I 10
-9 I 10
-8 I 10
-7 I 10
-6 I 10
-5 I 10
-4 I 10
-3 ■ I 10
-2 I 10
-I .J 10
0 - I 10
I ■ I 10
2" I 10
3 'I 10
4 • I 10
-10 2 10
. -9 2 10
-8 2 10
-7 2 10
—6 2 10
-5 2 10
-4 2 10
—3 2 10
-2 2 10
-I 2 10
0 2 10
I 2 10
2 2 10
3 2 10
4 2 10
-10 3 10
Fo
h
k
I
3
-5
-9
11
2
-8
5
-4
-7
2
—6
. 11
3
—6
-5
7
2
-4
16 ■ I
-3
8
■2
-2
42
I
-I
19
I
0
3
-5
I
20
I
2
10
I
3
4
-4
4
22
I ' -10
38
I
-9
3
—6
-8
3
-6
-7
9
2
—6
7
2
-5
16
I
-4
4
-3
-3
19
I
-2
15
I
—1
10
I
0
19
I
I
23
I
2
24
I
3
23
I
4
II
I
-10
II
2
-9
3
-6
-8
3
—6
-7
3
-6
—6
3
3
3
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
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
S
Fe
h
k
I
Fo
S
' 5
-3
—5
9
2
-4
23
I
-3
II
I
-2
63
I
-I
3
-5
0
14
I
I
18
I
2
3
-5
3
7
2
4
17
I
-9
15
I
-8
7
-3
-7
7
3
-6
18
I
-5
12
I
-4
3
—6
-3
14
I ' -2
3
-5
-I
0
12
I
8
2
I
3
-5
2
33
I
3
17
I
A
38
I
-9
23
I
-R
12
I
-7
3
-6
-6
3
—6
-5
3
-6
-T6
-3
-3
10
2
-2
13 ■ I
-I
8
2
0
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
6
6
6
6
6
6
7
7
7
7
7
10
10
10
10
10
10
I0
10
10
10
I0
10
10
10
10
I0.
10
I0
10
10
10
10
10
10
10
10
10
id
10
10
10
10
10
10
32
3
45
6
3
35
5
20
16
3
6
a
19
14
16
.13
33
30
3
10
8
10
3
3
7
6
26
9
3
a
27
IT
3
3
I
-5
I
S
7
7
7
7
-5
I
-3
I
I
—6
-3
I
I
I
I
I
I
-5
2
2
2,
—6
—6
-3
-.3
I
2
-5
I
I
~6
-6
Table 21.
(Continued)
F<obs) and sigma(F) (^sigma = unobserved):
I
Fo
I 7 10
2 7 10
3 7 10
-9 a 10
-a a 10
-7 a 10
-6 a 10
-5 a 10
—4 a 10
-3 a 10
-2 a 10
-I a 10
O a 10
I a 10
2 a 10
3 a 10
-8 9 10
-7 9 10
—6 9 10
—5 9 10
-4 9 10
-3 9 10
-2 9 10
-I 9 10
O 9 10
I 9 10
2 9 10
-a 10 10
-7 10 10
-6 10 10
-5 10 10
-4 10 10
-3 10 10
-2 10 to
7
12
28
a
3
3
3
a
10
26
8
a
33
3
7
5
3
3
3
3
15
7
5
7
12
3
9
3
3
6
3
7
4
5
h
k
h
k
I
2
-I
0
I
I
I
2
2
-6
-.7
-6
-6
-5
-6
2
-4
2
-3
I
-2
2
-I
0
2
I
I
—6
-6
-5
3
-4
-4
-3
-6
—6
-2
—6
-I
0
-6
-4
I
2*
-3
-4
-2
-10
3
-a
2
-6
—6
-4
2
-6
-2
-6
0
—3
2
—6 ' -10
-9
-3
-4
-a
—7
-4
10
10
10
10
11
11
11
11
11
11
11
11
11
12
12
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
11
11
S
VZ
12
12
12
12
13
13
13
0
0
0
0
0
0
0
I
I
I
I
Fo
S
2
a
I
32
—6
3
2
9
2
7
3
—6
I
18
I
17
12
2
-4
4
3 ■ -6
3
—6
3
—6
3
—6
I
13
3
—6
12 ■ 2
.8
2
11
2
6
—3
-6
3
9
2
3
-6
3
-6
I
19
41
I
-3
5
3
-5
13
I
-6
3
2
12
7
2
—3
5
5
-3
T v ichlorobenzene Thiourea Adduct'
h
k
I
Fo
28
-6 I 11
3
-5 I 11
7
-4 I II
-3 I II
24
-2 I 11
7
I II
-I
19
46
0 I II
I I II
10
9
2 I II
3 I II
3
3
-10 2 II
3
-9 '2 I I
10
—8 2 11
3
-7 :2 11
14
—6 ■ 2 11
13
-5- 2 I I
11
-4 2 11
39
-3 2 II
10
-2 2 II
4
-I 2 II
6
' 0 2 II
17
I ■ 2 II
2 2 II
7
3
3 2 .11
3
-10 3 I I
9
-9 3 II
13
-8 3 11
3
-7 3 II
—6 3 11 . 16
5
-5 3 I I
4
-4 3 II
32
-3 3 II
5
-2 3 11
14
-I 3 11
I:
L
I
. 0 3
I 3
-5
2 3
2
I
3 3
-9 4
2
-a 4
I
I
-7 4
—6 .4
2
2
-5 4
—6
-4 •4
-6
—3 4
—6
-2 4
2
-I 4
-5
0 4
I 4
I
I
2 4
I
3 4
-9 5
I
I . -8 5
-7 5
-4
-3
-6 5
I
-5 5
-4 5
2
—6
-3 5
—6
-2 5
2
-I 5
I
0 5
-5
I 5
I
2 5
3 5
-3
-3
-9 .6
I
-a
6
—3
-7 6
I
—6 Cd
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
II
11
11
11
11
11
II
11
11
11
11
11
11
11
11
11
II
11
11
S
'h
h
k
-5
15
I
20
I
-4
-3
I
15
—2
2
8
-I
5
-4
0
I
'14
—6
I
3
I
2
14
-9
-5
3
I
22
-a
I
-7
44
—3
—6
6
-5
24 • • I
—4
10
2
-3
3 ■ -6
I
-2
23
-I
3
—6
6
-3 • 0
I
2
12
-8
I
12
-7
3
-6
—6
a
2
18
I
-5
-5
3
—4
3
-5
■ -3
24
I
-2
I
-I
15
3
—6
0
I
8
2
6
-3
2
—6
3
-7
2
—6
12
—6 • -5
3
10
—4
2
6
6
6
6
6
6
6
6
7
7
7
7
7
7
7
7
7
7
7
8
8
B
S
8
8
a
Fo
s’
a
a
8
H
9
9
9
9
I
Fo
II
28
11
a
11
a
11
6
11
11
11
3
11
3
II
7
11
3
11
7
II '
3
II
4
11
3
11
16
II
13
11
3
II
31
11
12
8
11
11
S
11
11
11
15
II
17
11
18
11
6
II
3
11
3
II
3
II
3
II
16
8
II
II
9
II
9
II
3
S
I
2
2
3
2
—6
—6
Z
—6
3
-6
-4
—6
I
I
—6
I
I
2
2
2
I
I
I
-3
—6
-6
—6
—6
I
2
2
2
-6
Table 21.
(Continued)
F(Obs) and sigma (F) (-sigma = unobserved):
Trichlorobensene Thiourea Adduct
h
k
I
h
-3
-2
-I
O
I
-7
-6
-5
-4
-3
-2
—I
O
-6
-5
-4
—3
-2
-I
—3
-8
—6
-4
-2
.O
2
-9
9
9
9
9
9
10
10
10
10
10
10
10
10
11
11
11
11
11
11
12
0
0
0
0
0
0
I
I
I
I
I
I
I
I
II
11
II
II
11
11
11
11
II
11
II
11
II
II
II
11
11
11
11
II
12
12
12
12
12
12
12
12
12
12
12
12
12
12
- a
-7
—6
-5
-4
—3
-2
Fo
S
h
k
8
2
11
2
5
-4
—6
3
3
—6
3
—6
'8
2
5
-4
II
2
6
-3
13
I
3
—6
3
—6
9
2
3
-6
3
—6
9
2
11
2
20
I
3
—6
10
'2
13
I
3 ■ -6
10
2
14
I
14
I
3
—6
6
-3
10
2
14
I
6
—3
48
I
9
2
3
— 6
-I
0
I
2
. -9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
-9
—8
—7
—6
-5
-4
-3
-2
-I
0
I
2
-9
-8
-7
I
I
I
I
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
—6
-5
-4
I
Fo
s
12
3
-6
12
3
—6
12
7
2
12
12
2
12
18
I
12
14
I
12
13
I
12
22
I
12
6
-3
12
14
.I
12
10
2
12
3
-6
12
32
I
12
3
—6
12
10
2
12
12
2
12
9
2
12. "10
2
1.2 ■ 3
-6
12
8
2
12
4
-4
12 . 9
2
12
3
-5
12
16
I
12
25
I
12
8
2
12
9
2
12
3
—6
12
3
—6
12
5
-3
12
7
2
12
16
I
12
8 ■ 2
12
II
2
k
I
“3 4
-2 4
-I 4
0 4
I 4
2 4
-8 5
—7 5
-6 5
-5 5
-4 5
-3 5
-2 5
-I '-‘5
0 5
I 5
-8 6
. -7 6
-6 6
-5 6
-4 6
—3 6
-2 6
-I 6
0 6
I 6
-8 7
-7 7
—6
7
-5 7
—4 7
-3 7
-2 7
-I 7
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
Fo
4
17
22
7
8
•3
5
8
18
3
22 '
13
3
18
3
6 ■
12
6
3
6
5
3
5
8
7
30
6
j 8
8
3
3
13
14
6
S
h
I;
I
-3
I
I
2
2
—6
-4
.2
I
—6
I
I
—6
I
—6
-3
2
-3
-6
-3
-3
0
■I
-7
-6
-5
-4
—3
-2
-I
0
—6
-5
-4
-3
-2
-I
-5
-4
-3
-2
—8
-6
-4
-2
0
-8
-7
—6
-5
—4
-3
-2
-I
0
7
7
8
8
8
8
8
8
8
8
9
9
9
9
9
9
10
10
10
10
0
0
0
0
0
I
I
I
I
I
I
I
I
I
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
13
13
13
13
13
13
13
13
13
13
13
13
13
13
-Cb
-4
'2
3
I
-3
2
— 6i
-6
I
I■
-3
Fo
S
h
7
-3
I
3
—6
-8
8■ 2
-7
12
2
—6
8
2
-5
9
2
-4
5
-4 • —3
9
2
-2
3
—6
-I
3
-6
0
20
I
-8
3
—6
-7
6
-3
—6
13
2
-5
23
I
-4
2
8
-3
5
-4 ' -2
2
8
-I
10
2
0
12
2
-8
3
-6
-7
4
-4
—6
14
I
-5
32
I
-4
5
—3
-3
3
-6
-2
8
2
-I
5
-3
0
5
—4
-7
II
2
-6
7
2
-5
15
I
-4
3
—6
-3
3
—6
’ -2
k
I
I 13
2 13
2 13
2 13
2 13
2 13
2 13
2 13
2 13
2 13
3 13
3 13 •
3 13
3 13
3 13
3 13
3 13
3 13
3 13
4 13
4 13
4 13
4 13
4 13
4 13
4 13
4 13
4 13
5 13
5 13
5 13
5 13
5' 13
5 13
Fo
S
.12
6
15
3
19
3
11
22
3
10
6
9
7
19
8
7
8
9
14
3
11
7
12
14
12
7
10
3
19
10
12
3
9
10
2
-3
I
-6
I
—6
I
I
-6
2
—3
2
2
I
2
2
2
2
I
—6
2
3
I
I
I
2
.2
-6
I
2
2
-6
2
2
Table 21.
(Continued)
F(obs) and Sigma(F)
h
k
I
-I
5
5
6
6
6
6
6
6
6
13
13
13
13
13
13
13
13
13
O
-7
-6
-5
-4
-3
-2
-I
Fo
(-sigma = unobserved):
S
h
k
I
Fo
3
-6
14 .
I
3
-6
3
—6
7
2
10
2
17
I
17
I
8
2
—6
-5
-4
-3
-2
-5
-4
-3
—6
7
7
7
7
7
8
8
8
O
13
13
13
13
13
13
13
13
14
10
6
7
8
3
3
9
10
14
s'
2
-3
2
2
—6
—6
2
2
I
T r ichlorobenzene Thiourea Adduct
h
-4
-2
-7
-6
-5
-4
-3
-2
-7
k
I
O 14
O 14
I
I
I
I
I
I
2
14
14
14
14
14
14
14
Fo
S
h
k
I
Fo
S
h
k
I
Fo
S
3 ■ -6
8
2
3
"6
3
-6
12
2
3
—6
14 ■ I
7
3
II
2
-6
-5
-4
-3
-2
-6
-5
-4
2
2
2
2
2
3
3
3
14
H
14
14
14
14
14
14
8
8
11
3
8
3
12
7
2
2
2
—6
2
-6
I
-3
-3
-2
-6
-5
-4
-3
-5
—4
3
3
4
4
4
4
5
5
14
14
14
14
14
14
14
14
23
13
3
9
4
7
9
3
I
I
-6
2
-4
3
2
-6
OO
Table 22.
Observed and calculated structure factors for the 1,2,4 TCB-thiourea adduct structure.
Observed and calculated structure factors:
T r ichlorobenzene Thiourea Adduct
h
k
I
h
2
4
6
8
10
I
2
3
4
5
6
7
8
10
0
I
2
3
4
5
7
9
10
I
2
3
4
5
6
7
9
II
12
0
0
0
0
0
0
I
I
I
I
I
I
I
I
I
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
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
Fo
Fe
h
45 ■ 54
21
23
18
17
7
8
12
11
8
8
33
33
59
56
19
20
19
20
13
14
15
15
6
4
5
4
15
17
2
2
7
4
47
48
5
5
3
2
32
31
4'
5
3
5
6
8
35
30
77
76
4
3
9
10
3
4
19
20
■5
4
4
2
5
3
•30
29
I
2
3
4
5
7
8
10
I
2
3
4
5
6
7
8
9
10
11
0
I
2
3
4
5
7
8
9
10
I
2
3
4
5
k
I
Fo
4 0
84
4 0
52
4 0
14
4 0
3
4 0
3
4 0
20
4 0
17
4 0
8
5 0
19
5 0
47
5 0
13
5 0
35
5 0
35
5 0
4
5 '0
3
5 0
7
.5 0
4
5 0. M 6
5 0 ■ 4
6 0
23
6 0
14
6 0
24
6 0
6
6 0
22
6 0
23
6 0
5
6 0
5
6 0
9
6 0
8
7 0
4
7 0
10
10
7 0
7 .0
8
7 0
51
Fe
k
85
6 7
54
7 7
15
8 7
4
0 8
3
2 8
21
3 8
17
4 8
8
5 8
17
6 8
46
7 8
13
8 8
37
9 8
36
10 8
6
I :;9
3
2 9
9
3 9
5
5 ,9
5
6 9
5
'9 9
20
0 10
14
I 10
21
2 10
6
5 10
26
7 10
22
8 10
4
I II
5
2 II
9
3 II
6
4 II
6
5 II
8
0 12
II
I 12
7 ' 2 12
50
3 12
I
Fo
Fe
h
k
0
5
6
0
9
9
0
8
8
0
53
42
0
56
56
0
8
8
0
17 . 17
0
3
3
0
3
I
0
8
8
0
12
12
0
5
5
0
4
5
0
9
8
0
44
41
0
4
4
0
9
10
0
4
I
0
4
4
0
17
17
0 . 11
13
0
35
35
0
6
5
0 . 3
2
0
8
7
0
13
13
0
16
17
0
9
8
y
0
5
0
23
24
0
21
19
0
13
12
0
3
I
0
4
3
5
6
7
10
2
3
4
5
0
I
2
5
I
2
3
4
5
6
0
I
2
3
3
0
-8
—6
' -4
-2
2
4
6
12
-10
—9
12
12
12
12
13
13
13
13
14
14
14
14
15
15
15
15
15
15
16
16
16
16
17
18
0
0
0
0
0
0
0
0
I
I
I
Fo
0
3
0
8
0
5
4
0
0
3
0
6
0
3
0
12
0
16
0
10
0
7
0
5
0
5
0
6
0
12
0
4
0
3
0
4
0
3
0
3
0 ‘ 3
0
5
0
5
0
10
I
5
I
9
I
82
I
14
I
69
I
43
I
30
I
5
I
4
I -5
Fe
h
k
3
-8 I
10
—6 I
-5 I
3
2
-4 I
2
-3 I
2
-2 I
4
-I I
12
0 I
17
I I
10
2 I
8
•3 I
5
4 I
4
5 I
6
6 I
13
7 I
2
8 I
I
9 I
2
10 I
6 - 11 I
0
-11 2
0
-8 2
5
-7 2
4
-5 2
9
-4 2
5
-3 2
10
-2 2
85
-I ' 2
15
0 2
74
I 2
41
2 2
32
3 2
5
4 2
5 2
6
4
6 2
I
Fo
I
37
I
25
I . 23
I
14
I
29
I
7
I
11
I
2
I
11
I 117
I
4
I
16
I
20
I
9
I
4
I
5
11
.I
I
4
I
4
I
7
I
.5
I
3
I
37
I
38
I
37
I
37
I
40
I
2
I0
I
I
37
I
49
I ' 13
I
42
I
7
Fe
37'
24
25
13
26
6
16
4
9
119
4
16
20
9
4
4
II
I
4
8
7
7
38
38
38
35
49
3
9
35
48
12
42
6
Table 22.
(Continued)
Observed and calculated structure factors:
T r iCh IorObenzene Thiourea Adduct
h
h
7
12
-10
-9
-7
—6
-5
—*4-3
-2
-I
0
I
2
3
4
5
8
9
11
-10
-9
-8
-6
-5
-4
-3
-2
—I
0
I
2
3
4
k
I
2 I
2 I
3 I
3 I
3 I
3 I
3 I
3 I
3 I
3 I
3 I
3 I
3 I
3 I
3 I
3 I
3 I
3 I
3 I
3 I
4 I
4 I
4 I•
4 I
4 'I
4 I
4 I
4 I
4 I
4 I
4 I
4 I
4 I
4 I
Fo
Fe
h
15
4
5
9
10
38
9
14
35
70
170
15
16
13
21
13
6
3
18
' 5
7
4
4
20
12
23
25
32
174
40
12
28
15
29
15
3
4
7
9
36
11
14
31
67
171
16
13
15
21
15
3
4
16
4
7
4
6
21
11
21
27
26
158
39
11
28
12
31
5
6
7
9
-10
-B
-7
—6
-5
-4
-2
-I
0
I
2
3
5
7
8
10
12
-10
-9
-8
-6
-5
-4
-3
-2
-I
0
I
2
3
k
I
4 I
4' I
4 I
4 I
5 I
5 I
5 I
5 I
5 I
5 I
5 I
5 I
5 I
5 I
5 I
5 I
5 I
5 I
■5 I
5 I
5 I
6 I
6 I
6 I
6 I
6 I
6 I
6 I
6 I
6 .1
6 I
6 I
6 I
6 I
Fo
Fe
31
32
24
24
5
4
5
5
■8
7
17
17
. 5
4
■30
30
6
4
10
9
10
8
25
28
75
71
57
51
52
51
4
7
6
3
18
.19
3
4
4
2
5
2
4
I
6
5
4
5
16
16
18
18
12
10
80
79
II
14
15
9
37
36
8
6
15.
14
34 ■ 35
k
I
4 6 I
6 6 I
7 6 I
9 6 I
10 6 I
-9 7 I
-8 7 I
—6 7 I
—4 7 I
-3 7 I
-2 7 I
-I 7 I
0 7 I
I .7 I
2 -7 I
3‘ 7 I
5 7 I
6 7 'I
7 7 I
9 7. I
10 7 I
-B
8 I
I
-6 a
-5 8 I
-3 8 I
-2 8 I
-I a I
0 B I
I 8 I
2 8 I
I
3 a
4 8 I
5 8 I
6 8 I
Fo
Fe
h
k
6
9
14
14
18
18
5
4
5
2
6
6
9 • 9
17
17
4
I
30
30
20
18
17
16
29
30
56
59
6
7
4
4
6
8
14
15
16
15
7
8
4
2
7
6
14
16
5
9
46
48
28
23
3
4
19
21
19
18
4
5
13
13
40
39
7
6
2
3
7
11
—6
-5
-2
. -I
0
I
2
3
4
5
6
9
10
11
-7
—6
-3
-2
—l
I
3
4
5
—6
-4
-2
-I
0
I
2
4
6
8
8
9
9
.9
"9
9
9
9
9
9
9
9
9
9
9
10
10
10
10
10
10
10
10
10
11
11
II
11
II
II
II
II
H
I
Fo
18
I
I
4
I
25
I
14
9
I
8
I
I
46
I
3
I
6
I
II
I . 23
I
6
I
4
I - 4.
I
5
I
5
I
5
I
19
I
13
I
6
I
16
I
10
I
13
I
35
I
5
I
9
I
10
I
7
I
16
I. 9
I
23
I
6
I
7
I
4
Fe
h
k
I
Fo
Fe
18
7 -11
2
8 11
25
-8 12
15
-5 12
9
-4 12
7
-3 12
46
-2 12
I
-I 12
7
0 1.2
12
2 12
24
5 12
7
6 12
0
7 12
I
-7 13
4
-4 1.3
0
-2 13
3
0 13
19 •
I 13
14
2 13.
7
4 13
15
5 13
11
6 13
7 1,3
13
35
-7 14
5
-6 14
9
-5 14
9
—4- 14
11
-3 14
18
-I 14
12
I 14
23 ' 2 14
5
4 14
6
5 14
0
6 14
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
1
I
I
I
I
I
8
5
4
5
5
27
4
4
6
3
5
4
6
6
6
8
4
18
14
9
9
4
2
5
6
28
2
7
6
3
4
4
5
5
5
8
-I
17
13
8
6
4
7
4
O
4
6
9
12
4
3
8
4
4
S
5
7
5
3
4
6
9
12
5
5
8
3
4
(Continued)
Observed and calculated structure factors:
T r ichlorobenzene Thiourea Adduct
h
h
-6
-5
-4-2
-I
0
2
3
5
-5
—I
2
—4
—3
-2
-I
2
I
-8
-6
—4
-2
0
2
4
6
8
10
-I I
-9
-8
—7
“6
-5
k
i
Fo
Fe
h
15 i
5
6
15 i
6
5
15 i
5
3
15 i
5
4
15 i
II
9
15 i ' 7
8
15 i
7
7
15 i
5
5
15 i
4
5
16 i
4
6
16 i
9
a
Iti i
7
7
17 i
6
5
17 i
4
I
17 i
4
3
17 i
6
7
17 i
5
4
18 i
4
I
0 2
7
6
0 2
37
37
0 2
3
2
0 2 120 133
0 2
10
10
0 2
15
16
o ■2
48
46
0 2
8
9
0 2
22
24
0 2
4
4
I 2
4
6
I 2
9
a
I 2
4
6
I 2
5
6
I 2
20
20
I 2
15
14
-4
-3
-2
-I
0
I
2
3
4
5
7
8
9
11
-9
-8
-7
—6
-5
-4
—3
—2
-I
0
I
2
3
4
8
.9
11
12
-11
-9
k
I
Fo
I 2
I 2
I 2
I 2
I 2
I 2
I 2
I 2
I 2
I 2
I 2
I 2
I 2
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 2
2 2
2 2
2 2
2 2
2 2
3 •2
3 2
12
57
123
4
15
13
10
9
73
15
6
■ 13
3
4
19
9
11
21
17
34
41
58
19
47
138
77
46
32
13
7
7
5
5
17
Fe
10
53
I 11
4
12
15
11
9
71
14 '
5
13
I
2
18
10
13
21
14
35
42
55
19
52
140
74
45
31 '
14
8
7
0
6
17
k
I
-7 3 2
-6 3 2
-5 3 2
■ -4 3 2
-3 3 2
-2 3 2
-I 3 2
0 3 2
I 3 2
2 3 2
3 3 2
.4 3 2
5 3 2
6 .3 2
7 ■3 2
9' 3 2
-11 4 2
-9 4 ’ 2
—8 4 2
-7 4 2
—6 4 2
-5 4 2
-4' 4 2
-3 4 2
-2 4 2
-I 4 2
0 4 2
I 4 2
2 4 2
3 4 2
4 4 2
6 4 2
8 4 2
II 4 2
Fo
Fe
h
k
12
14
-9
22
23
-7
12
12
—6
35
35
-4
59
61
-3
174 159
-2
2 ■ 4
-I
23
26
0
23
26
I
40
37
3
14
13
4
13
13
5
16
17
6
22
22
8
7
6
-9
3
4
-7
4
4
-6
7
8
-3
7
7
-I
7
8
0
25 . 25
I
22
23
2
26
25
3
42
42
4
42
28
5
3
5
6
5
4 8
79
79
9
33
33
-10
5
7
-6
20
23
-5
5
5
—4
5
5
—3
5
5
-2
5
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
7
7
7
7
7
7
I
Fo
2
to
2
14
2 . 14
2
60
2
25
2
19
2
62
2
7
2
16
2
9
2
19
2
3
2
26
2
9
2
5
2
30
2
27
2
6
2
75
2
14
2
14
2
4
2
20
2
16
2
17
2
7
2
a
2
8
2
6
2
3
2
4
2
4
2
4
2
46
Fe
10
15
16
60
21
8
65
9
15
II
18 ’
0
27
10
5
31
27
7 ■
72
13
14
7
19
15
18
8
9
7
5
3
3
3
7
37
h
k
I
Fo
Fe
—I
0
I
2
3
4
5
6
9
-9
-8
-7
-5
-4
-3
-2
-I
0
I
2
3
4
6
7
-7
-6
-5
—4
-2
-I
0
I
2
4
7
7
7
7
7
7
7
7
7
8
8
B
3
8
8
8
8
8
8
8
8
8
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
77
28
4
7
28
9
7
11
6
4
II
16
3
19
6
12
28
27
15
3
27
4
9
4
78
29
3
8
27
9
6
13
.5
4
II
16
4
20
4
8
27
25
1-1
2
77
2
9
2
R
I
I
41
5
24
23
10
3
7
2
8
8
9
9
9
9
9
9
9
9
9
9
2
2
2
2
2
2
2
2
2
2
R
4
4
41
3
24
23
I0
4
6
I TOT
Table 22.
Table 22
(Continued)
Observed and calculated structure factors:
T r ichI orobenzene Thiourea Adduct
h
h
I
9 2
9 2
10 2
10 2
10 2
10 2
10 2
10 2
10 2
10 2
10 2
10 2
10 2
10 2
10 2
10 2
11 2
1.1 2
11 2
11 2
11 2
11 2
11 2
11 2
11 2
11 2
12 2
12 2
12 2
12 2
12 2
12 2
12 2
12 2
Fo
Fe
h
k
I
30
30
8
7
5
7
6
6
5
4
4
2
6
5
20
21
4
I
24
23
22
20
20
22
8
6
29
29
18
17
9
9
4
2
5
6
15
14
I
3
12
12
II
11
3
4
13
13
6
7
13
14
6
8
7 ' 7
4
3
19
20
7
9
3
4
23
23
5
I
-6
-4
-3
-2
-I
0
2
3
4
5
—6
-5
-3
-I
I
2
3
4
-4
-3
-I
3
4
5
-5
-4
-2
-I
I
—2
0
-10
-8
-6
13
13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
15
15
15
15
15
15
16
16
16
16
16
17
17
0
0
0
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
3
3
3
Fo
Fe
k
I
5
-4 0 3
4
10
-2 0 3
9
0 0 3
5
4
17
18
2 0 3
18
4 0 3
17
II
12
6 0 3
6
5
8 0 3
10 . 10
-9 I 3
9
8
—8 I 3
4
I
-7 I 3
8
—6 I 3
7
9
9
-5 I 3
7
7
—4 I' 3
4
5
-3' „1 3
12
11
-2 I 3
6
5
-r I 3
4
2 ■
0 I 3
9
9
I -:1 ! 3
6
6
2 I 3
6
6
.3 I 3
4
I
4 I, 3
5
5 I 3
6
4
2
6 I 3
4
3
8 I 3
4
4
-11 2 3
4
4
-10 2 3
4
4
-9 2 3
4
4
-8 2 .3
14
■14
-7 2 3
8
9
-5 2 3
4
I■
—4 ■2 3
15
15
-3 2 3 '
3
3
-2 2 3
6
6
-I 2 3
Fo
Fe
87
77
103
9
22
19
11
4
7
29
6
35
67
73
14
32
93
12
4
30
13
II
6
4
5
7
4
3
II
13
22
8
83
4
90
78
117
10
25
20
12
7
7
28
5
38
66
63
15
28
95
II
3
30
13
12
6
6
2
5
6
3
11
13
19
10
80
7
h
k
I
Fo
0 2 3
I. 2 3
2 2 3
3 2 3
4 2 3
5 2 3
6 2 3
7 2 3
II 2 3
-10 3 3
-9 3. 3
-8 3 3
-7 3 3
—6 3 3
-5 3 3
-4 3 3
-3 3 3
-2 3 3
0 3 3
■ I 3 3
2 3 3
3 3 3
4 3 3
5 3 3
7 3 3
8 3 3
-11 4 3
-lb 4 3
-9 4 3
-8 4 '3
■ -7 4 3
—6 4 3
—5 4 3
-4 4 3
48
2
13
25
11
13
5
24
5
4
7
6
44
5
5
42
15
41
5
9
45
94
II
6
9
6
4
6
5
7
12
8
30
20
Fe
h
k
I
Fo
Fe
47
-3
5
-2
1.2
0
26
I
10
2
14
4
3
5
25
6
I
7
3
8
6
-11
4
-8
44
-7
4
—6
3
-5
44
-4
21
-3
39 • -2
7
-I
10
0
44
I
91
2
II
3
6
5
10
7
5
9
4
-10
7
-9
5
-8
7
-7
12
-6
6
-5
26
-4
19
—3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
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
43
120
49
9
7
8
to
13
15
II
4
15
10
5
35
24
27
28
12
63
3
12
9
7
11
4
5
13
7
15
8
18
15
57
32
112
46
8
7
8
II
14
15
II
4
15
1.2
3
37
23
1.2
27
13
61
5
13
8
8
12
4
5
12
7
13
9
17
16
43
102
6
8
-9
-8
-7
-6
-5
-4
-3
-2
-I
0
I
2
3
4
-9
—8
-4
-3
-I
I
2
3
4
6
-7
-6
-3
-I
0
I
3
7
k
Table 22.
(Continued)
Observed and calculated structure factors:
h
Fo
Fe
h
6 3
6 3
6'3
6 3
6 3
6 3
6 3
6 3
6 3
6 3
7 3
7 3
7 3
7 3
7 3
7 3
7 3
7 3
7 3
7 3
7 3
7 3
7 3
7. 3
7 3
8 3
8 3
8 3
8 3
8 3
8 3
8 3
8 3
8 3
34
3
45
17
6
5
35
10
7
4
8
4
9
31
10
58
14
1.6
47
3
16
17
17
5
4
5
6
10
15
4
4
57
14
6
35
I
2
3
4
5
8
-10
-8
-6
-5
-4
-3
-I
I
2
3
5
8
-8
—6
-5
-4
-2
-I
0
I
2
5
7
-7
-6
-5
-2
0
+
44
20
7
6
36
8
6
3
6
4
13
31
9
43
14
15
49
4
17
17
16
1
5
3
7
10
17
2
14
55
II
4
k
I
Fo
Fe
a 3
8 3
8 3
8 3
8 3
.a 3
9 3
9 3
9 3.
9 .3
9 3
9 3
9 3
9 3
9 3
9 3
9 3
9 3
10 3
10 3
10 3
10 3
10 3
10 3
10 3
10 3
10 3
10 3
10 3
II 3
11 3
11 3
II ■ 3
11 3
22
5
6
9
21
6
4
4
9
5
6
18
13
3
41
5
4
8
4
4
7
5
44
7
9
5
6
8
4
7
8
20
9
8
21
3
5
11
21
5
4
3
8
6
5
14
14
4
42
6
2
7
2
2
7
0
46
8
a
6
7
6
4
9
9
21
II
8
h
k
I
Fo
Fe
h
k
I
I 11 ' 3
2 11 3
3 11 3
4 11 3
5 11 3
6 11 3
—6 12 3
-5 12 3
-4 12 3
-2 12 3
-I 12 3
0 12 3
I .12 3
2 12 3
5 12 3
6' 12 3
-5 13 3
-3 13 3
-2 13 3
-I 13 3
0 13 3
I 13 3
• 2 13 3
5 13 3
-7 14 3
-4 14 3
-3 14 3
-2 14 3
0 14 3
I 14 3
2 14 3
3 14 3
5 14 ' 3
-4 15 3
24
19
4
8
14
3
6
7
12
7
8
16
9
13
15
4
10
12
3
3
8
6
10
5
4
7
6
13
9
7
5
5
5
5
25
-3
18
0
I
3
7
4
15
-3
2
0
6
I
7
3
11
. -4
6
2
a
-10
17
-8
10 - -6
14
-4
15
-2
4
0
II
2
11
4
4
6
3
-I I
9
-9
6
-8
9
-7
5
—6
3
-5
6
-4
6
-3
13
-2
8
-I
7
0
5
I
5
2
5
3
4
5
15
15
15
15
In
16
16
16
17
17
0
0
0
0
0
0
0
0
0
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
44
4
4
Fo
5
5
12
4
6
3
5
5
5
4
8
26
25
34
28
63
49
12
8‘
4
5
36
5 .
7
26
12
22
56
70
41
3
17
3
16
Fe
h
k
5
6 I
5
7 I
10
8 I
I
9 I
6
-10 . 2
I
-8 2
4-7
2
—6 2
3
-5 2
I
-4 2
7
-3 2
26
-2 2
24
-I 2
27
0 2
29
2 2
63
4 2
50
5 2
12 ' 7 2
9
8' 2
3
9 2
5
— 11 3
36
-10 3
7
-9 3
7
-8 3
25
-6 3
11
-4 3
20
-3 3
56
-2 3
63
-I 3
38
0 3
a
I 3
17
2 3
3
3 3
16
4 3
I
Fo
Fe
4
20 . 20
4
II
9
4- ■. 6
4
4
5
6
48
8
4
5
5
4
13
15
4
15
14
4
52
49
4
22
15
4
3
8
4
29
30
412
1.2
4
21
22
4
22
21
4
8
8
4
26
25
4
4
2
4
5
3
4
4
6
4
5
5
4
10
10
4
5
5
4
14
13
4
10
9
4
22
22
4
32
32
4
3
4
4 103
99
50
4
51
22
21
'4
4
8
8'
442
4
9
10
1 0 3
-2
-I
0
I
2
4
5
6
8
9
-9
-8
-7
-5
—4
-3
-I
0
I
2
3
4
5
7
8
-10
-9
-8
-5
-4
.-3
-2
-I
0
I
k
T r ichlorobenzene Thiourea Adduct
Table 22.
(Continued)
Observed and ca Iculat-ed structure factors:
T r ichlorobenzene Thiourea Adduct
h
h
k
5 3
7 3
9 3
-a 4
—6 4
-5 4
-4 4
-3 4
-2 4
-I 4
0 4
I 4
2 4
3 4
4 4
5 4
6 4
7 4
8 4
II 4
■10 5
-9 5
-a 5
-7 5
—6 5'
-5 5
-4 5
-3 5
-2 5
-I 5
0 5
I 5
2 5
3 5
Fo
Fe
4 ■ 24
4
8
4
7
4
14
4
27
4
56
4
27
4
43
4
21
4
14
4
18
4
37
4
66
4
19
4
24
4
12
4
7
4
9
4
4
4
5
4
12
4
4
4
14
4
4
4
7
4
23
4
5
4
27
4
15
4
23
4
10
4
29
4
26
4
a
25
9
a
17
26
58
21
44
20
14
18
37
65
21
25
13
8
10
I
I
13
2
12
3
6
23
5
28
16
23
9
31
25
9
I
h
k
4 5
5 5
6 5
7 5
-8 6
-7 6
-5 6
-4 6
-3 6
-2 6
-I 6
0 6
I 6
2 6
3 6
4 6
6 6
-10 7
-8 7
—6 7
-5 7
-4 7
-3 7
-2 7
-I 7
0 7
I 7
2 7
4 7
5 7
7 7
-B
8■
-7
8
—6 8
I
Fo
4
14
4
5
4
4
4
12
4
9
4
8
4
6
4
II
4 • 45
4
6
4
4
4
3
4
18
4
52
4
17
4
9
4
4
4 .. 5
4
5
4
13
4
4
4
32
4
55
4
5
4
12
4
4
4
20
4
3
4
3
4
6
4
18
4
7
4
10
4
17
Fe
k
I
Fo
Fe
h
k
I
14
-5 8 4
6
-4 8 4
5
-3 8 4
12
-I 8 4
7
I a 4
8
2 8 4
7
3 8 4
4
4 8 ’4
47
-10 9 4
-9 9 4
5
4
-S 9 4
3
-6 9 4
IS .
.9 4
52
—3 ■- 9 4
16
-I 9 4
10
0' 9 4
3
3 19 4
4
4 ■9 4
7'
-9 10 4
13
-8 10 4
6
—6 10 4
21
—5 10 4
51
-4 10 4
3
-3 10 4
9
-2 10 4
3
-I 10 4
18
0 10 4
I
I 10 4
3
2 10 4
9
4 10 4
18
5 10 4
5
-9 11 4
9
-8 11 4
19
-6 11 4
3
15
22
9
35
6
25
24
11
5
4
9
6
12
6
34
13
8
4
6
20
9
3
10
5
4
20
5
8
22
3
4
5
4
5
7
21
10
35
5
25
24
10
5
2
9
6
12
3
37
13
9
4
5
22
8
6
12
5
4
18
2
7
23
5
2
■5
2
-5
-4
-3
-I
0
I
3
4
-7
-5
-4
-3
-2
-I
O
I
2
3
'5
6
-a
-7
-5
-3
—2
-I
0
2
3
5
—6
-4
-3
—2
11
11
11
11
II
11
11
11
12
12
12
12
12
12
12
12
12
12
12
12
13
13
13
13
13
13
13
13
13
13
14
14
14
14
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
Fo
Fe
h
I;
I
Fo
Fe
7
8 • -I
9
7
0
21
21
2
5
7
3
27
29
4
16
17
-3
6
6
-I
9
10
0
4
5
3
5
4
-5
11
8
—4
23
21
I
6 ■ 6
-3
6
6
■ -I
12
12
-8
10
10
-6
10
-2
11
II
11 ■
0
5
5
2
4
5
4
5
7
8
6
7
-11
4
5
- 10
12
12
-8
4
3
-7
7
7
—6
7
7
-5
5
3
-4
4
0
-3
5
6
-2
3
5
-I
4
5
0
7
8
I
4
0
3
14
14
14
14
14
15
15
15
15
16
16
16
17
17
0
0
0
0
0
0
0
I
I
I
I
I
I
I
I
I
I
I
I
I
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
6
11
9
4
■ 7
4
12
4
4
9
6
5
5
5
13
18
43
45
5
8
14
4
4
13
5
38
20
36
26
25
25
3
16
12
?
II
8
2
7
4
12
5
3
8
5
4
6
7
13
19
46
45
9
13
2
3
II
6
38
18
36
2°
25
24
4
16
13
Table 22.
(Continued)
Observed and calculated structure factors:
T r ichlorobenzene
rea Adduct
h
h
I
Fo
Fe
h
I S
I 5
I 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
2 5
3 5
3 5
3 5
3 '5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
3 5
52
9
6
11
19
5
6
23
20
12
49
24
21
55
60
11
6
4
13
9
7
7
26
24
55
8
12
12
64
22
8
5
7
5
54
10
6
11
18
4
8
21
16
11
50
25
18
54
62
12
5
5
14
9
7
5
24
21
52
10
11
10
63
22
8
7
8
5
-11
-9
-8
-7
—6
. -5
—4
-3
-2
-I
0
I
2
4
5
6
7
8
-I I
-9
-a
-7
-6
-5
-4
—3
-2
-I
•0
I
2
3
4
6
k
I
Fo
Fe
h
k
I
Fo
Fe
4 5
4 5
4 5
4 5
4 5
4 5
4 5
4 5
4 5
4 5
4 5
4 5
4 5
4 5
4 5
4 5
4 5
4 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
4
13
13
17
3
24
24
13
28
9
15
36
7
5
8
19
7
5
9
6
5
4
30
18
17
38
15
14
4
5
II
14
27
17
2
15
13
18
3
22
26
15
25
11
14
35
7
5
6
19
6
5
7
6
5
4
32
21
15
38
16
13
6
4
14
14
26
16
-10 6
-8 6
-7 6
—6 6
-4 6
-3 6
-2 6
-I 6
I 6
2 6
3 6
4 6
5 .6
6 -6
7 6
8' 6
-10 '7
-9 7
-7 7
-5 7
-4 7
-3 7
-2 7
-I 7
0 7
I 7
2 7
3 7
4 7
5 7
-9 8
-8 8
—6 8
-5 8
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
6
3
14
13
31
13
17
55
21
5
7
a
3
5
5
4
4
6
13
5
25
6
12
17
27
7
5
25
II
5
4
7
6
5
4
3
14
12
30
12
19
59
21
5
6
9
2
4
4
5
4
614
10
24
7
9
18
28
9
5
25
II
3
4
7
a
0
I;
I
-3 8
-2 8
-I 8
0 8
I 8
2 8
3 8
4 8
5 8
6 8
7 8
-8 9
-7 9
—6 9
-5 9
-4 9
-2 9
0 9
I 9
2 9
3 9
5 9
6 9
7 9
-9 10
—8 10
-7 10
—6 10
-5 to
-4 10
-2 10
-I 10
0 to
I 10
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
Fo
Fe
h
k
I
Fo
Fe
7
7
4
6
40
39
6
7
4
3
10
10
3
2
4
3
5
6
12
12
5
3
7
6
4- ' 6
17
17
19
16
38
39
3
I
6
6
4.
6
24
24
7
7
5
2
II
II
5
2
7
7
II
II
a
8
5
4
17
12
5
3
5
7
26
24
12
II
4
2
2
3
5
6
-7
-5
—4
-3
-2
-I
0
2
3
4
to
10
10
10
11
11
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
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
22
9
5
13
4a
14
7
6
6
5
7
16
3
4
7
7
9
27
5
8
4
3
5
5
7
6
4
23
10
2
13
3
4
14
7
7
7
6
9
14
3
4
6
3
10
28
3
6
-7
-5
-2
-I
0
2
4
5
-6
-5
-4
-2
-I
2
3
4
-5
-4
I
I
8
6
8
3
4
6
8
4
46
7
8
6
3
9
8
9
5
2
8
1 0 5
4
5
7
-I I
-9
-S
-7
-6
-S
-4
-3
-2
-I
O
I
2
4
5
6
7
8
-7
-5
-4
-3
-2
-I
O
I
2
3
4
6
8
k
Table 22.
(Continued)
h
k
I
Fo
Fe
h
Fe
h
k
I
-I
I
4
-6
-5
-4
—3
-2
-I
0
I
-3
-I
I
-2
-8
-6
-4
—2
0
2
6
-10
-9
-7
—6
-5
-4
-2
-I
0
I
2
3
14
14
14
15
15
15
15
15
15
15
15
16
16
16
17
0
0
0
0
0
0
0
I
I
I
I
I
I
I
I
I
I
I
I
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
6
6
6
6
6
6
6
6
6
6
7
5
4
4
5
6
7
4
4
6
5
4
9
7
5
8
85
10
15
7
21
a
10
10
23
4
4
14
3
86
15
11
19
6
6
I
3
3
5
4
7
3
I
6
4
0
11
7
6
10
84
9
14
6
19
6
10
11
22
6
4
16
7
85
15
11
18
5
6
7
-11
-9
-7
-5
-4
—3
-2
-I
I
2
3
4
5
7
-9
-8
-7
-6
-4
-3
-2
-I
0
I
2
3
5
7
-I I
-9
-7
4
7
4
4
5
20
28
46
25
22
18
17
7
53
12
3
7
8
11
30
15
14'
10
40
24
16
8
13
24
I
9
7
7
5
-6 4
-4 4
—3 4
-2 4
-I 4
0 4
I 4
2 4
3 4
5 4
6 4
-10 5
-9 ,5
-7 ■- 5
—6 5
-5' 5
-4 ■5
-2 5
-I 5
0 5
I 5
2 5
3 5
4 5
5 5
6 5
7 5
-9 6
-8 6
-7 6
—6 6
-5 6
-4 6
-2 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
6
k
I
I 6
I 6
I 6
2 6
2 6
2 6
2 6
2 6
2 •6
2 6
2 6
2 6
2 6
2 6
2 6 '
2 6
2 6
3 6
3 6
3 6
3 6
3 6
3 6
3 6
3 6
3 6
3 6
3 6
3 6
3 G
3 6
4 6
4'6
4 6
Fo
4
7
'4
.5
6
19
30
45
24
24
18
16
5
51
12
4
9
■7 ,
12
30
15
14
3
37
25
17
a
14
24
4
8
5
7
6
Fo
Fe
h
k
I
20
17
17
18
3
3
32
35
11
12
9
12
4 • 6
8
9
33
33
4
3
8
8
6
4
II
10
6
8
13
16
8
11
4
5
13
13
to
10
35
34
15
16
10
11
4
5
4
5
5
5
10
II
5
3
8
7
6
5
14
14
3
5
21
21
26
26
7
10
-I
.o
I
2
5
6
-10
-9
-8
-7
—6
-4
-2
-I
I
2
4
5
7
-9
-8
-7
-6
-5
-2
-I
I
2
3
4
5
-10
-9
-8
6
6
6
6
6
6
7
7
7
7
7
7
7
7
7
7
7
7
7
a
a
8
a
a
3
8
a
8
a
8
8
9
9
9
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
Fo
22
8
4
9
27
6
4
14
5
II
3
10
7
13
35
7
7
4
4 .
5 '
8
6
3
15
35
7
8
3
4
11
15
7
4
4
Fe
h
k
23
—6 9
8
-5 9
3
-4 9
9
-3 9
29 ■ -2 9
6
I 9
2 9
3
15
3 9
6
5 9
12
-9 10
I
-6 10
13
-5 10
a
-4 10
12
'-3 10
35
-2 10
6
-I 10
7
0 10
4 '
I 10
■0
2 10
4
3 10
S
4 10
6
5 10
4
6 to
16
-9 11
34
-7 11
7
-5 11
9
—4 11
3
-2 II
4
-I 11
12
0 11
14
I 11
6
4 11
2
-7 12
4
-5 12
I
Fo
Fe
6
13
6
8
6
13
6
5
6 . 39
6
9
6
16
6
3
6
4
6
4
6
6
6
6
6
4
6
6
6
29
6
8
6
5
6
8
6
8
6
7
6
7
6
5
6
4
6
8
6
46
12
6
5
6
21
6
5
6
11
ib
22
6
5
6
5
6
13
II
11
13
4
40
9
17
2
5
2
8
8
46
27
7
7
8
8
7
7
7
3
6
4
10
5
20
4'
II
22
4
5
13
J
Tri chlorobenzene Thiourea Adduct
1 0 6
Observed and calculated structure factors:
Table 22.
(Continued)
Observed and calculated structure factors:
Tri chlorobenzene Thiourea Adduct
h
h
I
12
12
12
12
12
12
12
12
13
13
13
13
13
13
13
14
14
14
14
14
14
“Cb 15
-I 15
0 15
I 15
-3 16
0 16
•10 0
-8 0
— C3 0
-4 0
-2 0
0 0
2'0
6
6
6
6
6
6
6
6
'6
6
6
6
6
6
6
6
6
6
-4
-3
-2
-I
I
2
4
5
-6
-3
-2
0
I
2
4
-6
-4
-3
-2
-I
I
Fo
Fe
8
4
7
3
7
4
3
10
6
6
8
10
11
4
5
6
8
10
6
7
6
4
6
4
6
5
6
5
6
3
6
4
6
5
6
5
7 ' 13
7
24
7
6
7
12
7
13
7
27
62
7
8
0
8
I
a
2
2
9
4
4
7
10
12
4
4
3
7
10
8
2
4
3
4
4
3
4
6
14
23
5
12
14
27
65
h
k
I
4 0 7
-10 I 7
-7 I 7
—6 I 7
-5 I 7
-4 I 7
-3 I 7
-2 I 7
-I
I 7
2 I 7
3 I 7
4 I 7
5 I 7
6 I 7
-I I 2 7
- -9 2 7
-8 2 7
—7 2 7
-6 2 7
-5 2 7
—4 2 7
-3 2 7
-2 2 7
-I 2 7
I 2 7
2 2 7
6 2 7
-10 3 7
-a
3 7
-7 3 7
-5 3 7
-3 3 7
-2 3 ■ 7
• -I 3 7
Fo
Fe
5
3
4
4
6
4.
6
6
29 ' 30
7
6
II
11
19
20
32
34
23
24
5
I
4
0
19
20
5
4
4
I
3
2
11
13
.13
16
8
9
26
27
8
9
20
19
9
10
34
34
12
12
24
23
4
4
11
11
3
0
14
12
35
36
11
10
20
19
26
28
k
I
Fo
Fe
h
k
I
Fo
0 3 7
6
I 3 7
3
2 3 7
3
4 3 7
7
5 3 7
23
6 3 7
4
7 3 7
5
-10 4 7
6
-8 4 7
13
-7 4 7
5
—6 4 7
12
-5 4 7
23
-4 ,4 7
II
-2 4 7
27
—1 4 7
23
22
Oi 4 7
I 4 7
16
2 4 7
19
3 4 7
6
5 4 7
5
-I I 5 7
3
-10 5 7 . 7
-9 5 7
6
-7 5 7
10
—6 5 7
7
-4 5 7
10
-3 5 7
40
-2 5 7
22
-I 5 7
16
0 5 7
7
I 5 7
11
2 5 7
6
3 5 7
12
4 5 7
15
8
3
3
7
24
2
4
8
14
5
13
25
5
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
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
7
7
7
7
7
7
7
7
7
7
7
7
7
6
4
3
14
14
6
11
4
7
5
5
9
10
14
13
4
4
4
5
6
13
4
56
20
9
7
4
13
6'
4
13
16
9
26
28
23
15
19
6
6
2
6
6
9
8
9
39
21
13
6
to
7
13
15
6
6
6
6
6 6
-10 7
-3 7
-7 7
-5 7
-4 7
-3 7
-2 7
-I 7
0 7
I 7
3 7
. 4 7
5 7
-7 8
-6 8
-5 8
' -3 8
O
19
Fe
h
k
I
Fo
Fe
-•2 8
5
4
-I 8
I
0 8
14
I 8
13
3 8
6
4 8
10
-8 9
3
—6 9
3
—4 9
5
0 9
5
I 9
8
4 9
II
-6 10
13
-3 10
13
-2 JO
3
-I 10
4
0 10
4 •
I 10
5
5 10
6
-8 I I
15
-6 11
3
-5 11
57
-4 1.1
21
-3 11
II
-I 11
7
0 11
I II
3
12
3 11
5 • 4 II
,3
-8 12
13
-7. 12
16
-5 12
Cn
-4 12
16
2 12
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
12
11
32
6
11
13
6
10
4
10
5
13
7
6
4
5
32
7
4
3
7
8
3
17
5
5
3
9
5
7
9
3
,10
8
12
II
33
5
12
13
5
9
3
10
3
12
7
7
7
7
7
7
7.
8
8
I
4
33
6
0
2
10
5
18
5
5
0
8
5
7
I
9
7
107 1
k
(Continued)
Observed and calculated structure factors:
T r ichlorobenzene Thiourea Adduct
h
h
3
4
-5
-3
-2
-I
2
3
-5
-3
0
2
-5
-4
-I
-10
—6
-4
-2
0
2
4
-9
-a
-7
-6
-5
-4
-2
-I
0
I
2
4
k
I
Fo
Fe
12 7
12 7
13 7
13 7
13 7
13 7
13 7
13 7
14 7
14 7
14 7
14 7
15 7
15 7
15 7
0 8
0 .a
0 8
6 8
0 8
0 8’
0 8
I 8
I 8
I 8
I 8
I 8
I a
I 8
I 8
I 8
I 8
I 8
I 8
5
4
4
10
a
7
4
6
7
5
7
5
6
4
8
4
19
10
31
II
5
39
3
14
4
25
4
11
4
12
17
27
9
23
4
I
2
11
a
6
' 4
7
8
4
6
7
5
3
10
3
18
11
32
12
5
39
6
15
2
24
5
11
4
13
19
28
10
22
h
k
I
Fo
Fe
5 I 8
6 I a
-11 2 8
-10 2 8
-9 2 8
-8 2 a
-7 2 8
—6 2 S
-5 '2 8
-4 2 8
-3 2 8
-2 2 8
-I 2 3
0 2 8
I 2 8
2 2 B
4 2 8
-I I 3 8
-10 3 8
-9 3 8
-8 3 8
-7 3 8
—6 3 8
-4 3 8
-I 3 8
0 3 8
I 3 8
2 3 8
3 3 8
-10 4 8
-9 4 8
-8 4 8
-7 4 ' 8
-6 4 8
5
3
4
5
9
4
3
4
8
6
48
13
9
7
6
7
16
•' 6
4
9
12
5
■5
23
6
8
32
13
4
3
8
4
9
8
3
I
6
3
9
I
3
2
6
6
49
13
9
6
5
4
15
5
I
9
11
6
6
25
7
7
31
13
4
I
8
2
.8
9
I
Fo
Fe
■h
k
.1
Fo
-5 4 8
-4 4 8
-3 4 8
-I 4 8
0 4 a
I 4 8
2 4 8
3 4 8
4 4 8
6 4 8
-10 5 8
-8 5 a
-7 .5 a
—6 -.5 8
-5 5 3
-4‘ 5 8
—3 •5 8
-I 5 8
0 5 8
I 5 8
2 5 8
3 5 8
4 5 a
6 5 8
-to 6 a
-7 6 8
-5 6 , 8
-4 6 a
-3 6 a
-I 6 8
0 6 a
4 6 8
5 6 8
-9 7 8
5
27
25
II
5
9
5
7
7
9
5
13
15
24
II
4
13
12
8
4
25
7
5
4
7
28
24
10
5
11
3
8
7
10
6
13
14
25
10
2
13
II
II
3
25
-7
-6
-5
-4
-3
-2
-I
0
I
2
3
4
-8
—6
—4
-3
-I
0
2
3
-9
-8
-7
7
7
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
8
8
B
8
10
14
16
6
10
27
7
'7
9
k
6
6
6
I
5
8
-6
7
7
13
13
-5
-4
-2
-I
3
3
0
38
13
7
4
4
38
12
8
5
2
2
3
—6
-5
-4
3
a
8
9
9
9
9
9
9
9
9
9
9
9
10
10
10
a
8
8
8
8
8
8
8
8
8
8
S
8
8
8
8
8
8
8
8
a
8
8
8
8
8
8
8
a
4
7
9
14
13
19
12
9
5
5
8
Z
3
5
11
4
7
4
24
5
8
a
6
8-
15
Fe
h
k
L
Fo
Fe
9
-3
11
-I
15
2
20
-6
6
-3
II
-2
26
-I
5
I
7
2
3
7
10
-5
3
-3
7
-2
9
-I
15
0
13
3
20
—6
13 ' -5
10
-2
I
-3
2
-I
7
-4
I
-2
3
-8
5
-4
9
-2
10
10
10
II
II
11
11
11
11
11
12
12
1.2
12
12
12
13
13
13
14
14
15
8
8
8
8
8
8
8
8
3
10
4
4
4
6
12
5
10
5
6
3
7
13
4
5
11
I
9
2
4
3
7
13
6
9
6
6
4
9
14
I
2
10
7
4
6
6
6
4
3
40
14
25
5
3
0
8
5
25
6
7
5
14
2
-I I
-9
-S
-6
-5
—4
a
8
8
8
8
8
8
8
3
8
8
8
8
8
a
6
8
4
6•
15
a
6
0
0
0
9
9
5
41
15
26
6
4
5
0
9
9
0 9
I 9
I 9
I 9
I 9
I 9
I 9
-I
5
10 ■ 10
7
7
-4
5
31
32
I 801
Table 22.
(Continued)
Observed and calculated structure factors:
T r ichlorobenzene Thiourea Adduct
n
K
I
Fo
Fe
h
k
Fe
h
k
I
-2
-I
O
I
3
-9
—8
-7
-4
-2
-I
I
2
3
4
-9
-8
-7
-5
-4
-3
-2
-I
I
2
3
-9
-7
—6
-4
-2
O
I
2
I
I
I
I
I
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
.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
12
13
17
5
6
9
4
21
17
13
14
8
6
31
3
5
8
4
10
10
6
32
26
5
5
6
7
10
16
4
6
9
4
3
II
13
17
5
6
9
I
21
18
15
16
8
5
31
I
3
10
6
12
10
6
32
27
6
7
6
3
4
5
-10
-9
. -7
-6
-5
-4
-3
-2
-I
0
I
4
5
-9
-7
—6
-5
-4
-3
-2
-I
I
2
4
5
-9
4
4
4
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
16
7
2
2
8
6
8
3
21
6
29
12,
11
14
3
5
6
5
4
21
18
5
7
6
30
5
4
6
8
5
3
4
S
10
-I 7
0 7
I 7
4 7
-9 3
-7 8
—6 8
-4 8
I a
2 8
-8 9
-5 9
-2 .9
I -9
-8 10
-7' 10
-6 10
-5 10
-3 10
-2 10
. "I 10
0 10
I 10
3 10
-3 11
-2 11
0 11
I 11
-7 12
—6 12
■-4 12
-I 12
I 12
-4 13
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
11
17
3
6
8
4
3
—6
-5
-4
- —2
7
7
7
7
7
7
I
Fo
9
17
9
7
9
4
9
4
9
9
9
5
9
8
9
6
9
21
9
7
9
29
9
II
9
12
9
14
9
3
9
6
9
6
9
"6
9
6
9
22
9
17
9
5
9 • 8
9
7
9
28
9
,4
9
6
9
6
9
9
9
5
9
4
9 . 6
•9
7
9
II
Fo
Fe
h
6
4
12
4
6
5
12 ■
10
1.8
9
4
4
28
4
3
6
11
6
4
3
3 '
4
5
4
3
9
.5
7
5
4
9
4
10
8
6
0
12
3
5
5
II
9
16
10
2
5
27
5
3
6
11
8
2
2
I
3
4
3
3
10
5
7
4
4
10
3
10
8
-3
-2
0
-4
-3
-10
-8
-6
-4
-2
2
-10
-8
-7
—6
-5
-4
-2
-I
I
2
-10
-9
-8
-6
-5
-4-3
-2
-I
0
I
2
—8
k
I
Fo
Fe
h
13 9
13 9
13 9
14 9
14 9
0 10
• 0 10
0 10
0 10
0 10
0 10
I 10
I 10
I 10
I 10
I 10
I 10
I 10
I 10
I 10
I 10
2 10
2 10
2 10
2 10
2 10
2 10
2 10
2 10
2 -10
2 10
2 10
2 10
3 10
3
4
5
5
9
7
II
5
6
34
6
5
4
8
4
21
10
10
5
11
19
4
4
8
10
8
5
10
12
12
1.2
6
6
5
3
4
6
4
8
6
12
3
3
33
6
5
5
8
I
21
11
II
6
12
19
3
3
a
8
7
6
II
13
11
13
7
4
4
-7
—6
-5
-3
-2
0
I
2
4-10
-9
-7
-5
-4
-2
-I
0
I
2
-8
-7
-6
-5
-3
0
2
3
-a
-7
-6
—5
-4
-3
-2
k
I
Fo
Fe
3 10
3 10
3 I0
3 10
3 10
3 10
3 10
3 10
3 10
4 10
4 J0
4 10
4- I0
4 10
4 10
4 10
4- 10
4 10
4 10
5 10
5 10
5 10
5 10
5 10
5 10
5 10
5 1.0
6 I0
6 10
6 10
6 to
6 10
6 10
6 10
1.2
17:
5
4
7
N hj
Table 22.
9
3
9
9
2
9
8
4
7
4
9
10
6
7
5
7
H
6
6
VO
4
4
17
9
19
12
18
9
20
11
32
6
5
5
5
7
■7
4
4
16
23
18
10
16
23
17
10
8
8
4
4
10
7
5
9
8
9
7
6
17
15
17
15
O
(Continued)
Observed and calculated structure factors:
Trichlorobenzene Thiourea Adduct
h
h
k
I
Fo
Fe
0 6
I 6
2 6
-7 7
-6 7
-4 7
-3 7
-2 7
I 7
2 7
3 7
-9 8
-5 8
-4 8
—3 8
-2 8
-I 8
0 8
2 8
-4 9
—3 9
-I 9
0 9
2 9
-I 10
0 10
2 10
-7 I I
-5 II
-4 II
-3 .11
-5 12
-3 12
-2 12
10
10
10
10
10
10
10
10
IT)
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
5
4
5
13
4
4
14
7
4
6
14
4
4
5
13
4
4
17
4
8
.4
3
6
5
4
16
4
4
9
9
6
7
6
4
6
4
7
12
5
5
14
6
2
4
16
4
3
5
14
I
2
18
I
6
3
4
6
2
3
16
3
4
8
9
7
5
4
4
h
k
I
-I 12 10
-3 13 10
-a, 0 11
-6 0 11
0 0 11
-10 I 11
-9 I 11
—6 I 11
.-4 I 11
-3 I 11
—2 I 11
— I I 11
0 I 11
I I 11
2 I ii
-8 2 ii
-6 2 11
-5 2 11.
-4 2 ii
-3 2 11
-2 2 11
I 2 11
2 2 11
-9 3 ii
-8 3 11
—6 3 11
-3 . 3 11
-I 3 11
0 3 11
I 3 11
2 3 11
3 3 11
-8 4 '11
—6 4 11
Fo
5
4
10
21
7
6
3
14
4
12
4
10
23
5
5
5
7
"6
6
20
5
9
4
4
7
8
16
7
8
10
8
4
7
7
Fe
3
5
9
21
8
4
2
14
4
13
2
11
24
7
3
4
■6
8
.6
19
4
8
4
5
8
8
16
8
7
10
9
2
7
7
k
t
-4 4 ii
-3 4 11
-I 4 11
0 4 11
2 4 11
-8 5 11
-7 5 11
-5 5 11
—4 5 11
-I 5 11
0 5 11
2 5 11
-a. ,i<i> 11
—6 '- 6 11
-5 6 11
-4"- 6 11
-3 !6 11
-2 6 ii
"I 6 11
2 6 ii
-8 7 11
-4 7 11
-3 7 11
-I 7 11
0 7 11
I 7 11
-8 8 11
-7 8 11
■ -6 a 11
-5 a •11
•-4 a 11
2 8 11
-7 9 11
-6 9 11
Fo
Fe
h
k
11
11 , -5
22
24
-3
12
13
—2
5
6
-6
12
12
-4
6
6
-2
• 6
6
—6
4
■3
-3
9
9
-2
12
13
-I
8
8
-8
4
5
—6
6
7
-■2
5 ' 4
0
14
13
2
4
2
-7
4
4
—6
3
3
—4
6
4 . —3
4
5
I
3
5
2
8
a
—9
7
6
-a
16
15
-7
6
5
-6
4
3 . -4
4
I
-3
5
4
-I
a
6
I
a
a
2
9
10
-9
8
8
-8'
4
4
-6
5
I
-4
9
9
9
10
10
10
11
11
II
11
0
0
0
0
0
I
I
I
I
I
I
2
2
2
2
2
2
2
2
2
3
3
3
3
I
Fo
II
5
II
4
II
6
II
4
11
6
II
7
5
11
II
5
11
6
II
10
12
5
12
6
12
5
12
7
12
7
12
5
12
7
12
25
12
4
12
3
12
6
12
9
12
7
12
7
12 ■ II
12
7
12
5
12
16
12
5
12
6
12
5
12
5
12
4
12
5
Fe
h
k
I
Fo
Fe
2
-2
I
-I
6
0
5
I
4
-7
6
—6
4
-5
4'
-4
5
-2
10
-I
7
0
5
I
7
-7
7
-6
7
—4
3
-3
6
-I
25 ' -8
4
-I
3 ■
0
3
I
8
-7
4
-6
6
-3
’ 10
-■2
6
-7
3
-6
17
-5
3
-■4
5 . -2
5
-6
4 ■ '-3
5
-2
4
-I
3
3
3
3
4
4
4
4
4
4
4
4
5
5
5
5
5
6
6
6
6
7
7
7
7
8
8
8
8
B
9
9
9
9
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
1.3
12
12
12
1.2
12
8
13
4
4
3
8
46
9
11
4
4
4
9
11
7
■9
6
4
3
1.5
4
4
7
7
4
6
4
5
5
10
6
12
4
7
12
3
5
5
9
4
6
8
12
5
4
3
9
II
6
10
5
3
15
4
.3
co cr>
Table 22.
2
6
4
5
5
8
5
II
I
H
H
O
Table 22.
(Continued)
Observed and calculated structure factors:
T r ichlorobenzene Thiourea Adduct
h
h
I
Fo
Fe
h
0 0
45
54
0 0
21
23
0 0
18
17
0 0
7
8
0 0
12
11
I 0
a
8
I 0
33
33
I 0
59
56
I 0
19
20
I 0 . 19
20
I 0
13
14
I 0
15
15
I 0
6
4
I 0
5
4
2 0
15
17
2 0
2
2
2 0
7
4
2 0
47
48
2 0 • 5
5
2 ■0
3
2
2 0
32
31
2 0
4'
5
3
2 0
5
3 0
6
8
3 0
35
30
3 0
77
76
3 0
4
3
9
10
? 0
3 0
3
4
3 0
19
20
3 0
5
4
3 0
4
2
3 0
5
3
4 0 . 30,
29
I
2
3
4
5
7
8
10
I
2
3
4
5
6
7
8
9
10
11
k
I
Fo
Fe
4 0 ■ 84
4 0
52
4 0
14
4 0
3
4 0
3
4 0
20
4 0
17
4 0
8
5 0
19
5 0
47
5 0
13
5 0
35
5 0
35
5 0
4
5 0
3
5 0
7
5 0
4
5 0 . m'6
5 0
4
0 6
0
23
I 6 0
14
2 6 0
24
3 6 0
6
4 6 0
22
5 6 0
23
7 6 0
5
8 6 0
5
9 6 0
9
10 6 0
8
I 7 0
4
2 7 0
10
3 7 0
10
4 7 ■0
8
5 7 0
51
85
54
15
4
3
21
17
8
17
46
13
37
36
6
3
9
5
5
5
20
14
21
6
26
22
4
5
9
6
6
8
11
7
50
k
I
Fo
Fe
h
6 7
7 7
a 7
0 a
2 8
3 8
4 a
5 8
6. a
7 8
8 8
9 8
10 .8
I -9
2 9
3 9
5 ■9
6 9
9 9
0 10
I 10
2 10
5 10
7 10
8 10
I 11
2 11
3 11
4 II
5 11
0 12
I 12
2 12
3 12
0
0
0
0
0
0
0
0
0
0
0
0
0
0
5
9
8
53
56
■8
17
3
3
8
12
5
4
9
44
4
9
4
4
17
II
35
6
3
3
13
16
9
7
23
21
13
3
4
6
9
8
42
56
8
17
3
I
8
12
5
5
8
41
4
10
I
4
17
13
35
5
2
7
13
17
8
5
24
19
12
I
3
5
6
7
10
2
3
4
5
0
I
2
5
I
2
3
4
5
6
0
I
2
3
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
(I
0
0
0
0
0
k
I
Fe
Fe
h
12
12
12
12
13
13
13
13
14
14
14
14
15
15
15
15
15
15
16
16
16
16
17
0 18
-8 0
—6 0
-4 0
-2 0
2 0
4 0
6 0
12 0
-10 I
-9 I
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3
8
5
4
3
6
3
12
16
10
7
5
5
6
12
4
3
4
3
3
3
5
5
10
5
9
82
14
69
43
30
5
4
5
3
10
3
2
2
2
4
12
17
10
8
5
,4
6
13
2
I
2
6
-8
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
7
8
9
10
II
-I I
-8
-7
-5
-4
-3
-2
-I
0
0
0
0
0
■0
0
0
0
I
I
I
I
I
I
I
I
I
I
0
0
5
4
9
5
10
85
15
74
41
32
5
6
4
0
I
2
'3
4
5
6
k
I
Fo
Fe
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 I
I I
2 I
2 I
2 I
I
2 I
2 I
2 I
2 I
2 I
I
2 I
2 I
2 I
2 I
2 I
37
25
23
14
29
7
11
2
II
117
4
16
20
9
4
5
11
4
4
7
5
3
37
38
37
37
40
2
I0
37
49
13
42
7
37
24
25
13
26
6
16
4
9
I19
4
16
20
9
4
4
II
I
4
8
7
7
38
38
38
35
49
3
9
35
48
12
42
6
111
2
4
6
a
10
I
2
3
4
5
6
7
8
10
0
I
2
3
4
5
7
9
10
I
2
3
4
5
6
7
9
II
12
0
k
APPENDIX D
TABLES FOR PUBLICATION FOR THE 1,2,4
TMB-THIOUREA ADDUCT STRUCTURE
113
APPENDIX D
Table 23.
Atomic coordinates and isotropic thermal parameters for the
1,2,4 TMB-thiourea adduct structure.
Atomic coorn inates
10*) and isotropic
thermal Darameters I
10")
F(I)
F i2 1
F C.31
Fi+)
F (S)
F (6)
T (3)
Ti+)
T(S)
T (6)
Ti I)
T (2)
B(I)
B (2)
B (3)
Bi + )
B(S)
B<ti)
B (21)
B ('22J
Bf 23)
8(2+)
8(25'
B C2ti)
S CI)
S (2)
S (3)
C CI)
C (2)
C (3)
N(Il)
N (12)
N (21)
N f22)
N (31)
N (32 J
Bi 10)
B ( 12)
B (13)
TO)
Fh(I)
Fh (2)
Fh (.3)
Fm (I)
TmCD
Fm (2)
Tm (3)
Tm (2)
Bm (IJ
3250f77)
1.812
990
1605
30+2
■‘•So5
3855(72)
293+
1650
1287
2208
3+32
+202 (.31J
+Slti
+069
2708
209+
28+1
295+(27)
260+
1279
50+
653
1978
+007(3)
-29(3)
313+ (3.)
2875(10)
93+ C10'
2719(10)
3295(9)
1+30 CS.)
332(9)
2537(8.)
1762(8)
3505(8)
20+8(58)
372(338)
+32ti(70)
2+3(5+)
3390(71)
576(+3)
2203(70)
+758(35)
+750(58)
+597(19+)
523(57)
331+(229)
I132(91)
y
z
+7ti(+9)
2178(til I
272
1+96
— 20+
1981
-+77
3150
-27+
3832
202
33+7
3+0(52)
2991 (37 I
-296
3137
-510
2203
-87 ,
I 12+
5+8
977
762
191 I
627(16)
3056(27)
315
+207
-293
+608
-589
3860
-277
2709
2307
331
255(25)
2+12(26J
til3
1296
399
+ 16
- 1+0
6lS
-+93
173+
-30 I
2631
6507(2),
+393C2)
6+05(2.1 '' •"1+03(2)
3000(2)
2035(2)
6892(5)
+995(8)
7101 (6.)
932(8)
+067(e)
2226(8)
7129(5)
til0 1 ItiJ
697+(5)
+3+2(7)
7506(5)
-1+2(6)
7275(5.)
' 1558(7)
+527(5)
1350(6)
+++9(5)
326+(6) ■
-672(33)
+01+C+8)
-2335 (207 I.
— Sti (
.271J
-583(38)
5573C53)
+57(30)
-iooac++)
-630 ('+! J
+u58 ('51J
157(28)
651+2)
-922(+3)
3357(56)
802(50)
2808(6+I
533(33).
3ti++ C++)
2501 (108.)
7733(1+5)
-8+2(36)
21 9 6 (+to)
79+(139)
221 (1.81 )
510(50)
-178(80)
Li
IC)35 (152)
210(38)
199 (4-1)
95(18)
1+8(30)
Ito+(30)
137(+9;
222 (67)'
1+6(36)
227(+9)
117(13)
253(33)
I07(13)
102(11)
102(12)
122(15)
9+(12)
212(23)'
80
175(25)
62(12)
69 CU)
81(1+)
575 C114)
73(1) *
6? CIJ*
71 Iljt6 9 C+)*
7 0 (+)*
■ 7 0 (+) *
86(+)t
82(+)t
Sti (+) *
88(+)w
92(+)*
87 ('+ )t
50
50
50
50
50
■50
50
50
50
50
50
50
50
* Equivalent isotropic U defined as one third of the
trace of the orthogonaIised U.^ tensor
114
Table 24.
Anisotropic thermal parameters for the 1,2,4 TMB-thiourea
adduct structure.
rtni=otropic thermal parameters
S(I)
S (2)
S (3)
C(I)
C (2)
CCS;
N(H)
N (12)
N (21)
N (22)
N (31)
N (32)
u Il
58(2.)
60 (2)
SI (2)
i)3 i6)
66(7)
68 (7)
79(6) '
60 f5)
119(8.)
6V (6)
105(7.)
103(7)
U22
U33
85(2)
67(2;
0 6 (2 )
57(6)
71 (6)
70 (6)
107(7)
104.(7)
71 (5)
93(6)
62 (5)
60(5)
61 (2)
61 (2)
51 (I;
74(7)
70 (6)
71 (6)
62(5)
83(6)
58(5)
9(1 (6;
74(5)
78(5)
IO 1)
U23
-15(1;
9(1;
-2(1)
'10(5;
-13(5)
-13(5)
-24(5;
-5(5;
19(4;
14(5)
-5(4)
-17(4)
U 13
8(1)
3(1)
11(1)
13(6)
24(5)
26(5)
17(5)
31 (5;
22 (5)
16(5)
-3(5)
14(5)
U 12
' 4(2)
-3 (I;
10(2)
0 (5)
3(5)
-2 (5;
I (5)
4(5)
18(5)
-17(5)
24(5)
11 (5;
Theban isotropic temperature factor exponent takes the form:
-S-^Ch SH-iU 11 + ... + 2hka*b*U12)
Table 25.
H-atom coordinates and isotropic thermal parameters for the
1,2,4 TMB-thiourea adduct structure.
':
H At cm coo r d i nates
(xIO^)
t herma I pa ra meters
(A-^x 10 )
. x
HCl la)
HCll b.)
H C 12a)
H C 12b)
H C2 1a )
H C2 1b )
H C22a)
H C 22b)
H C31a)
H (3 lb)
H C 32a)
H C 32b)
2619
4304
803
1037
862
-71
2763
290 8
Y
7336
7091
7136
6813
6963
7764
7806
6873
1500
51 19
1335
3035
3997
4254
5041
4136
a nd
z
is o t ropic
LI
6421
6592
4708
3527
I 16
1 16
98
98
-20
102
102
107
107
I 10
HO
I03
103
-91 I
1412
2 159
I463
592
3367
3915
115
Table 26.
Bond lengths for the 1,2,4 TMB-thiourea adduct structure.
bond
s <i:>-c <i:>
S (3) -C (3)
C(I)-N(IC)
C (2)- N (22)
C ( 3 ) — N (32)
Table 27.
lengths
(Pu
1.684 (I I)
1.709(10)
I.365(11)
1. 3 4 5 ( I I>
1.319(11)
S
C
C
C
(2) — C (2)
(I >-N (I I)
(2)-N (21)
(3;- N (31)
1.679(11)
1.315(11)
I.372(11)
1.532(10)
Bond angles for the 1,2,4 TMB-thiourea adduct structure.
-■I
Table 3.
Bond angles
SX I I- C 11)-N ill)
N I'M I-C (I.)-H U 2)
S (2)-C (2)-N (22)
S <3.i-C (3)-N (31)
N (31)-C (3)-N (32)
i'0)
123.6(7)
I15.4(10)
122.6(7)
121.4(7)
118.0(B)
S
I'I i'-C (I)-N (12)
S <2)- C (2)- N (21)
N 121 j-C (2) -N (22)
S (3) -C (3) -N (32)
C <2 )—H (21a )-N (21)
121.0(7)
121.3(7)
I16. I (91
120. to16)
79. to(to)
I
Table 28.
F(Obs).and sigma (F) for the 1,2,4 THB-thiourea adduct structure.
F(obs) and Sigrna(F)
-6
-5
-4-3
-2
-I
0
I
2
3
—9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
-9
-8
-7
-6
-5
-4
-3
-2
-I
0
I
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
I- IOFo
10s
h
k
117
468
35
104
187
58
35
146
108
I 17
II I
53
150
51
63
90
35
254
160
332
205
127
79
134
94
102
275
36
338
77
80
309
82
167
22
8
-70
24
15
-32
-49
16
25
23
26
-52
18
-50
-42
28
-70
II
18
15
9
21
-37
21
29
26
11
-71
9
—33
21
7
23
17
-8
-7
-6
-5
-4
-3
-2
-I
0
I
2
-8
-7
-6
-5
-4
-3
-2
-I
0
I
-7
—6
-5
-4
-3
-2
-I
0
I
—6
-5
-4
-3
6
6
6
6
6
6
6
6
6
6
6
7
7
7
7
7
7
7
7
7
7
8
8
a
8
8
8
8
8
8
9
9
9
9
10
10
10
10
10
10
10
10
10
10
10
to
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10 •
10
10
10
I IOFo
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
fo
10
10
10
10
10
10
to
10
10
10
10
10
10
10
10
10
10
38
85
I13
120
36
324
247
35
120
I07
98
33
237
I 12
36
36
211
66
83
75
68
68
87
94
109
268
100
101
248
37
94
37
145
81
10s
-76
33
24
22
-71
10
11
-49
16
19
28
-76
13
24
-73
-72
13
-39
28
25
-28
-42
31
29
24
II
26
25
18
-52.
30
-74
19
-33
h
k
I IOFo
-2 9 10
-I 9 10
0 9 10
-5 10 10
-4 10 10
-3 10 10
-2 10 10
-I 10 10
. -9 I 11
-8 I 11
-7 I 11
—6 I It
-5 I 11
-4 ‘ I 11
—3 I 11
-2 I 11
-I
I 11
0 ."I 11
I I 11
2 I 11
-8 '2; 11
-7 "2 11
—6 2 11
-5 2 11
-4 2 11
-3 2 11
-2 2 11
-I 2 11
0 2 11
I 2 11
2 2 11
-8 3 11
-7 3 11
—6 3 11
105
58'
90
38
97
37
101
37
53
54
36
128
36
109
217
35
146
428
I16
98
70
95
123
I 12
91
278
67
35
93
161
65
I18
37
96
IOs
26
-36
24
-76
29
-74
27
-52
-41
-39
-51
31
—50
17
21
-50
9
4
12
28
-40
28
22
23
28
10
—38
-50
■22
12
-43
24
-74
.78
h
k
-5 3
-4 3
-3 3
-2 3
-I . 3
0 3
I 3
-8 4
-7 4
-6 4
-5 4
-4 4
-3 4
-2 4
-I 4
0 4
I 4
-8 5
-7 5
-6 5
-5 5
-4 5
—3 5
-2 5
-I 5
0 5
I 5
-7 6
-6 6
-5 6
-4 6
-3 6
-2 6
-I 6
I IOFo
10s
74
36
345
36
ItiO
161
173
132
37
72
86
171
362
36
203
93
78
88
121
65
79
150
67
36
164
135
91
38
109
232
80
117
100
81
-35
-71
9
-72
11
12
14
23
-74
-38
31
16
9
-71
10
24
29
33
24
—4 1
-34
18
-39
-72
II
14
27
-75
26
13
-32
23
26
30
11
11
11
11
11
11
11
11
11
11
11.
11
11
11
11
11
11
11
11
II
11
11
11
11
ii
11
11
11
ii
ii
11
11
ii
ii
h
I;
I IOFo
0 6 11
-7 7 11
-6 7 11
-5 7 11
-4 7 11
-3 7 11
-2 7 11
-I ,7 11
. 0 7 11
—6 a 11
-5 8 11
-4 8 11
-3 8 11
—2 a 11
-I 8 11
—4 9 11
-3 9 11
-8 0 12
-7 0 12
-6 0 12
-5 0 12
—4 0 1.2
-3 (I 12
-2 0 12
-I 0 12
0 0 12
-8 I 12
-7 I 12
—6 I 12
-5 I 12
-4. I 12
-3 I 12
-2 I 12
-I I 12
36
38
38
37
IOti
108
86
296
105
80
172
148
37
37
61
38
37
58
37
103
37
37
36
101
64
Jtil
67
37
69
92
441
48
36
65
IOs
-52
-75
-75
-75
26
25
31
13
21
-37
17'
20
-74
—74
-32
-75
-74
-50
-75
27
-73
-73
-72
26'
-29
.1.2
-34
-53
-28
21
9
-40
-51
24
J
k
T r imethyLbenzene Thiourea Adduct
116
h
(-sigma = unobserved):
Table 28.
(Continued)
h
I:
I IOFo
IOs
h
h
—6
-5
-4
-3
-2
-I
0
. I
2
3
4
-10
-9
-a
-7
—6
-5
—4
-3
-2
-I
0
I
2
3
4
-9
-8
-7
—6
-5
-4
—3
-2
I
I
I
I
I
I
I
I
I
I
I
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
9
84
9
75
9 624
9
65
9 209
9 219
9 279
9
72
9
35
9 130
9
37
9
38
9 149
9
92
9 275
9
64
9
35
9 ' 281
9
CjO
9 168
9 256
9
95
9 141
9
84
9 506
9
52
9
57
.9 134
9
36
9
35
9 152
9
59
9
90
9 544
21
25
6
25
9
9
7
23
-50
15
-52
-76
19
28
II
-40
-69
10
-38
14
7
20
14
30
8
-52
-49
20
-72
~ 7 1
17
-41
26
8
-I
0
I
2
3
4
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
-9
-8
-7
-6
-5
-4
-3
-2
-I
0
I
2
3
-9
k
I IOFo
3 9
3 9
3 9
3 9
3 9
3 9
4 9
4 9
4 9
4 9
4 9
4 9
4 9
■4 9
4 9
4 9
4 -9
4 9
4 9
4 9
5 9
5 9
5 9
5 9
5 9
5 9
5 9
5 9
5 9
5 9
5 9
5 9
5 9
6 '9
426
34
120
65
142
37
65
36
203
231
35
35
79
35
34
163
70
61
296
I18
105
37
36
155
65
326
126
504
222
188
235
36
36
126
10s
k
I IOFo
6
-8 6 9
37
-48
-7 6 9
53
28
—6 6 9
59
-39
-5 6 9 338
19
-4 6 9 209
-74
-3 6 9
60
-43
-2 6 9 •163
-72
-I 6 9
35
13
0 6 9
77
12
I 6 9 461
-71
2. 6 9
36
-70
3 6 9
99
30
-8 ' 7 9 H O
-70 • -7 7 9
37
-48
—6 7 9
36
II
-5 7 9 160
25
-4 '
::7 9 205
-41
-3 7 9
35
10
-2 7 9
95
24
-I ,7 9
35
28
. o 7 9 I10
-74
I 7 9 203
-72
2 7 9
36
17
3 7 9
86
-40
—8 8 9
38
9
-7 8 9
80
—6 8 9 178
19
8
-5 a 9
36
13
-4 8 9 166
II
-3 8 9
53
13
8 9
92
- 2.
-71
-I 8 9
57
-73
0 a 9
35
23
I a 9 355
10s
-74
-49
-44
9
13
-42
16
-49
23
7
-72
27
25
-73
-72
17
13
-70
27
-49
26
10
-73
32
-75
-35
16
-72
16
-43
28 -34
-50'
12
h
k
2
-7
—6
-5
-4
-3
-2
-I
0
I
2,
—6
-5
-4
-3
-2
-I
0
I
-5
-4
-3
-2
-I
0
-3
-9
-a
-7
—6
-5
-4
-3
-2
8
9
9
9
9
9
9
9
9
9
9
10
10
10
10
10
10
10
10
II
11
II
11
II
11
12
0
O
0
0
0
0
0
0
I IOFo
9
9
9
9
9
9
9
9
9
9
9
9
9
16 1
38
72
98,
36
63
479
I0 ?.
71
123
37
213
37'
9
67
9
59
9
56
9
36
9
70
9
92
68
9
9
76
9
36
9 225
9
36
9 105
9
93
10
37
10
37
10
35
60
10
10
53
10
58
10
35
10 563
IOs
18
-75
-39
27
-72
-40
8
21
-30
16
-74
14
-74'
-40
—44
-43
-50
-31
28
-42
-37
-73
13
-51
24
29
-74
-74
-71
-42
-48
-43
-70
8
h
-I
0
I
2
3
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
-9
-8
-7
I:
I IOFl-I
IOs
0 10
34
0 to
35
0 10
35
0 10 IP,3
0 10
37
I 10
37
I 10 114
90
I 10
I, 10
62
I 10 30 1
I 10 140
I 10
58
I 10 156
I to 109
I 10
35
I 10 205
I 10 318
I IO
37
2 10
37
89
2 10
2 10 100
2 10 156
2 10 175
2 10
90
2 10 200
2 to 263
2 10 21,6
2 10 189
2 10 121
2 10
87
2 10
37
3 10
76
3 10
37
3 10 135
-49
-4 9
-49
15
-74
-52
17
27
-33
26
13
-33
12
13
16
9
-52
-75
30
26
17
15
28
14
JI
8
10
15
30
—74
-38
-74
20
J
TrimethyLbenzene Thiourea Adduct
1 1 7
F(obs) and sigma (F) (-sigma = unobserved):
Table 28.
(Continued)
F (obs; and s Igrna(F) (-sigrna = unobserved) :
Tr Imet h / Ibenzene Thiourea Adduct
h
h
k
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
a
8
8
8
8
8
93
93
516
32
158
86
120
35
663
■37
38
102
183
• 51
303
65
219
32
95
173
295
468
179
75
471
53
\ 37
) 58
103
35
35
34
119
704
IOs
23
22
7
-45
12
22
20
-70
8
-74
-53
20
20
-36
38
-29
10
-45
16
7
5
7
11
29
7
-40
-75
-46
25
-70
-69
-67
18.
7
h
-2
-I
0
I
2
3
4
5’
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
k
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
I IOFo
8
8
8
8
S
a
8
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
IOs
195
12
131
14
116
14
161
18
89
28
57 —43
296
10
62 -44
37 -75
222
13
I10
24
36 -71
58 -42
68 -34
216
11
156
15
33 -65
141
13
90
■25
538
16
273
11
108
23
36 -73
38 -75
38 -76
124
22
75 -35
83
32
170
16
66 -36
426
8
462
7
71 -31
159
13
I:
I -IOFo
IOs
h
k
I IOFo
0 4
I 4
2 4
3 4
4 4
5 4
-9 5
-8 5
-7 5
-6 5
-5 5
-4 5
-3 5
-2 5
-I 5
0 5
I :'5
2 5
3 5
4 ,5
. -9 6
-8 6
-7 6
—6 6
-5 6
-4 6
-3 6
-2 6
-I 6
0 6
I 6
2 6
3 6
. 4 6
8
33
8 174
8
90
8 1.29
8 123
8
,38
8
37
8 21 I
8 233
a 337
8 156
3
35
8 170
8
34
8 198
a 164
8
94
a 439
8
35
8
74
8
69
8
37
8 I16
8
80
8 128
a 291
8
34
R
34
8 579
8 200
8
50
8
60
8
36
8 1.54
-47
12
28
20
22
-75
-74
13
12
9
16
—69
14
-67
9
16
21
8
-71
-36
-41
-73
23
-33
20
10
-68
-68
21
12
-37
-42
-72
18
-9
-8
-7
—6
-5
—4
-3
-2
-I
0
I
2
3
4
-8
-7
—6
-5-4
-3
-2
-I
0
I
2
3
-8
-7
—6
-5
-4
-3
-2
-I
7
7
7
7
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
8
8
8
8
8
9
9
9
9
9
9
9
6
8
96
8
37
. 8 151
8 19?
8 214
a 237
8 129
8 181
8 496
8
91
8 132
8 134
8 162
8
97
8
74
84
8
8
96
8 107
8 232
8 14 7
8
78
8 381
8 206
8
35
8 181
8
37
8 148
8
37
8
36
8
96
8 193
8
36
8
65
8 203
t
IOs
h
k
30
0
-73
L
18
2
14
3
13
-7
1.2
-6
20
-5
15
—4
14
-3
19
-2
13
-I
19
O
17
I
28
2
-38
-6
32
-5
28
—4
24
-3
13
-2
18
-I
-32
O
9
I
10
-5
-49
-4
15
-3
-73
-2
20
-I
—74 •
O
-73
-3
27
-2
14
-10
-71
-9
-39
. —8
9
-7
9
9
9
9
10
10
10
10
IO
10
10
10
10
10
11
11
11
11
11
11
11
11
12
12
12
12
12
12
13
13
I
I
I
I
I IOFo
I0 7,
8
91
21
8
78
28
8 371
9
8 113
23
8
77 -37
8 123
7.3
8
36 -73
10
8 282
8
63 -39
a
36 -71
8
73
26
35 -50
8
8
36 -50
8
57 —43
8
75 -38
8
37 -75
8
37 -73
8
53 -4 9
8
87
31
3 193
10
8
36 -51
3 117
18
8 I09
27
8
37 -75
8
92
29
8 103
27
8 221
17
89
8
28
8
38 -75
8 122
23
9
99
21
9
37 -52
9 140
21
9
73 -29
118
-4 0
-3 0
-2 0
-I 0
0 0
I' 0
2 0
3 0
4 0
5 0
-10 I
-9 I
-8 I
-7 I
-6 I
-5 I
-4 I
-3 I
-2 I
-I
I
0 I
I I
2 I
3 I
4 I
5 I
-10 2
-9 2
-8 2
-7 2
-6 2
-5 2
-4 2
-3 2
I IOFo
Table 28.
(Continued)
Tr imeth-y Lbenzene Thiourea Adduct
h
k
4
5
6
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
I
I
I
-2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
3
3
I ■-1OFo
IOs
7
74
29
7 364
15
7
54 -40
7
73 -38
7
36 -72
7 198
14
7 138
18
7 136
18
7 214
II
7
32 —64
7 287
8
7 134
15
7 589
5
7
31 -43
7 230
7
7 438
8
7
35 -69
7
35 -70
7 120
23
7
38 —76
7 158
18
7
65 -41
7
77 -33
20
7 123
7
34 —68
7 600
7
7
31 -62
7 144
14
7 265
9
7 460
9
85
7
23
7
83
18
7
92
25
7
35 -70
h
I:
I IOFo
IOs
h
4 3
5 3
6 3
-10 4
-9 4
-8 4
-7 4
—6 4
-5 4
-4 4
-3 4
-2 4
-I 4
0 4
I 4
2 4
3 4
4 4
5 4
-10 5
-9 5
-8 5
-7 5
—6 5
-5 5
—4 5
-3 5
-2 5
-I 5
0 5
I 5
2 5
3 5
4 5
7
73
7 462
7
38
7 203
7
66
7 176
7 158
7 170
7 323
7 122
7
31
7 433
7 520
7 373
7 209
7 307
7
99
7
81
7 112
7
94
7
37
7
36
7
79
7 150
7 139
7 172
7 659
7 306
7 289
7 160
7 180
7 147
7 187
7 254
-35
8
-76
15
-41
16
16
15
9
17
-63
7
13
6
11
10
26
32
24
31
-74
-72
—33
17
18
14
7
9
10
14
10
17
14
11
5 5
-9 6
-8 C
-7 6
—6 6
-5 6
-4 6
-3 6
-2 6
-I 6
0 6
I 6
2 6
3 6
4 6
5 6
-9 -7
-8 7
-7 7
—6 ,7
. -5 7
—4 7
-3 7
-2 7
-I 7
0 7
I 7
2 7
3 7
4 7'
5 7
-9 8
-8 8
-7 8
k
d
I IOFo
IOs
7 125
23
37 -75
7
7 227
13
7 157
17
7
75 -34
7 214
12
7
61 -37
7
34 -67
7 184
13
7
90
17
7 226
12
7 207
8
•7 254
II
7 223
12
7
36 -72
7
37 -74
7
37 -75
7
37 -73
7 101
26
7
36 -72
7 198
14
7 I12
21
7 886
2
7 373
8
7 121
26
7
58 -32
7 121
22
35 -70
7
7 271
11
7 I 15
23
7
38 -75
7
69 -42
7
37 -74
7 205
14
h
k
—6 8
-5 8
-4 8
-3 8
-2 8
-I 8
0 8
I a
2 8
3 8.
4 8
-8 9
-7 9
—6 9
-5 9
-4 9
-3 9
-2 9
-I 9
0 9
I 9
2 9
3 9
4 9
-8 10
-7 10
—6 10
-5 10
-4 10
•-3 10
-2 10
-I 10
0 10
I 10
I IOFo
IOs
h
I:
7 193
7
36
7
35
7 404
7 144
7 164
7 447
7 127
7
35
7 235
7 255
7 I12
7
91
7 197
7
36
7
36
7 127
7
66
7
73
7 146
7
72
7
35
7
36
7 168
7
95
7
70
7
95
7
36
7
80
7
35
7
35
7
58
7 594
7 102
14
-71
-70
9
17
10
6
15
-70
12
12
25
30
14
-72
-71
20
-37
24
12
24
-70
-72
17
30
-40
29
-72
32
-70
-71
-33
8
25
2
3
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
-6
-5
-4
-3
-2
-I
0
I
2
-5
-4
-3
-2
-I
0
-10
-9
—8
-7
—6
-5
10
10
11
11
11
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
12
17
13
13
13
13
13
13
0
0
0
0
0
0
I IOFn
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
a
8
K
8
8
36
36
120
143
158
36
247
35
112
36
73
36
155
38
37
1.67
36
?9
85
71
99
14 I
38
76
235
I16
107
102
90
36
61
35
303
33
1 OS
-71
-73
24
20
18
-72
II
-70
16
-50
29
-72
18
-76
-74
17
-72
29
21
-30
20
20
-76
-37
12
24
21
27
31
-72
-41
-70
9
—66
119
F(obs) and sigma CF) (—sigma = unobserved) :
Table 28.
(Continued)
Trimethylbenzene Thiourea Adduct
h
In'
IOs
h
k
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
-10
-9
-S
-7
-6
-5
3
3
3
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
6 145
18
6 140
17
6
79
29
6 121
18
6
30 -61
6 388
7
6 151
22
6 561
6
6 229
8
6 183
13
6
98
25
6
86
29
6
36 -73
6 152
19
6
72 -41
6
75 -37
6
65 -41
6 196 ' 14
6
86
28
6 359
a
6 429
7
6
32 -63
6
78 .25
6 405
5
10
6 161
6
97
25
6 120
20
6
35 -70
6 103
24
6 471
8
6 120
24
6 238
13
6
37 -73
6
75 -36
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
-9
-8
-7
—6
-5
-4
-3
-2
."I
0
I
2
3
4
5
-8
-7
—6
-5
—4
-3
-2
7
7
7
7
7
7
7
7
7
7
7
7
'8
8
8
8
'.8
-4
-10
-9
—S
4
4
4
4
4
4
4
4
4
5
5
5
6
6
6
6
6
h
k
350
9
251
10
51 -39
167
12
165
11
538
6
430
6
347
5
138
17
241
11
477
8
35 -70
36 -72
96
28
88
32
120
22
36 -72
186
15
279
9
32 -65
199
10
29 -59
499
6
145
10
183
8
57 -24
93
24
570
7
35 -70
93
28
163
18
122
24
170
17
■ 70 -37
-7
—6
-5
-4
-3
-2
."I
0
I
2
3
4
5
6
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
■4
5
6
-9
-8
-7
5
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
7
7
7
I IOFo
a
a
8
8
8
8
8
8
8
a
9
9
9
9
9
9
9
I IOFo
IOs
6
35 -71
6
35 -69
6 157
16
34 -68
6
6
96
24
6 221
8
6
33 -46
6 588
II
6
77
30
6
65 -38'
6 117
22
6
84
33
6
38 -76
6
63 -44
6 150
18
6
36 -72
6 309
10
6
69 -35
6
34 -67
7
6 565
6
84
24
6
71
22
6 164
11
6
35
6
22
6 176
15
6 301
II
6
98
29
6 123
22
6 133
20
6 127
21
6 246
II
6
91
26
6 697 . 8
Hl
1
6
4
4
4
6
6
6
6
6
6
6
O
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
IOs
0
N
-3
-2
-I
0
I
2
3
4
5
4
I IOFo
h
k
-I 9
0 9
I 9
2" 9
3 9
4 9
5 9
-8 10
-7 10
—6 10
-5 10
-4..10
-3 10
-2 10
-I 10
0 10
I 10
2 10
3 10
4 10
-7 I I
-6 11
-5 II
-4 11
-3 II
-2 11
-I II
0 II
I 11
2 II
3 11
—6 12
-5 12
-4 12
I IOFo
IOs
h
k
6
94
24
-3
6
34 -43
-2
6 233
9
-I
6 206
O
10
6
72 -34
I
2
6
36 -72
6 153
19
3
-5
6
56 -52
6
37 -74
-4
6 149
18
-3
6 114
23
-2
6
82
31
—1
6 116
22
0
6 448
8
I
6 118
15
2
6 122
16
-4
6 I10
16
-3
6 139
18
-2
6 128
20
-I
6 152
18
0
6
38 -75
-10
6
37 -74
-9
6 145
18
-8
6
36 -71
-7
6
35 -70
-6
6 440
8
-5
6 108
22 . -4
6 144
13
-3
6 292
8
—2
6
36 -71
-I
6
36 -72
.0
6 140
20
I
6 243 • 12
2
6
64 -42
3
12
12
12
12
12
12
12
13
13
13
13
13
13
13
13
14
14
14
14
14
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I IOFo
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
7
■p
7
7
7
7
7
7
7
7
7
7
7
7
IOs
95
26
167
16
35 -71
63 -28
107 . 18
36 -73
99
27
38 -75
37 •974
I1.3
23
36 -73
77
29
149
13
213
I0
102
27
127
23
157
18
96
29
78
27
74 -31
130
16
36 -51
96
27
134
23
136
13
4 17
57
158
9
67
23
268
10
483
8
60
19
76
18
443
74
23
120
F(obs) and sigma'(F) (-sigma = unobserved):
Table 28.
(Continued)
F (obs) and Sigma(F)
k
-4
-3
-2
-I
0
I
2
3
4
5
6
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
-9
-8
-7
-6
-5
-4
—3
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
8
8
8
8
8
8
8
I IOFo
IOs
h
k
5 481
7
5 141
14
5 293
8
5 813
10
5
45 -31
5 314
6
5 150
15
5 142 • 17
5 124
20
5
74 -35
5
98
29
5 123
23
5
36
-73
5 245
12
5
77 -32
5 I 15
20
5 272
10
5 181
12
5 166.
13
5 223
8
5 469
9
5 120
26
33 —66
5
5 438
8
5 212
13
5
36 -72
5
55 -52
5 ‘126
22
5
77 -35
36 -72
5
5 154
17
35 -69
5
5
34 -67
5 177
13
-2
-I
0
I
2
3
4
5
6
-9
-8
-7
-6
■ -5
-4
-3
-2
-I
0
I
2
3
4
5
-8
-7
-6
-5
-4
-3
-2
-I
0
'I
8
8
8
8
8
8
8
8
8
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
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
108
780
108
97
169
59
35
36
184
38
119
154
201
317
591
34
70
76
141
68
408
181
35
37
121
139
107
190
108
49
34
231
249
102
IOs
T rimethyI benzene Thiourea Adduct
h
k
20
2
6
3
4
14
21
5
15
-7
-42
—6
-71
-5
-4
-72
16
-3
-76
-2
24
-I
18
0
14
I
10
2
8
3
-68
4
-32
-7
21
-6
12
-5
-28
-4
8
-3
14
-2
-71
-I
-74
0
24
I
20
2
25
3
15
4
24
-6
-48
-5
-68'
-4
8
-3
8 • -2
20
-I
10
10
10
10
11
11
II
II
11
II
11
II
11
II
11
II
12
12
12
12
12
12
12
12
12
12
12
12
13
13
13
13
13
13
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
397
177
36
71
37
II I
90
328
68
102
158
68
56
185
202
54
129
100
36
36
35
154
479
47
83
139
63
37
114
63
74
35
134
35
IOs
h
9
15
-72
-39
-75
24
29
9
-37
24
II
-30
—34
14
13
-50
23
27
-73
-72
-70
17
13
—38
26
19
-42
-75
25
-44
-37
-71
20
-50
0
I
2
3
-5
—4
-3
-2
-I
0
I
-2
-I
-T 0
-9
-8
-7
—6
-5
—3
-2
-I
0
I
2
3
4
5
6
7
-10
k
I IOFo
13 5
13 5
13 5
13 5
14 •5
14 5
14 5
14 5
14 5
14 5
14 5
15 5
15 5
0 6
0 6
0 tt
0 6
0 6
0 6
0 6
0 6
0 6
0 6
0 6
0 6
0 6
0 6
0 6
0 6
0 6
I 6
-9
I 6
-8 I 6
-7 I 6
60
82
130
125
38
63
62
160
177
79
53
109
67
37
70
78
34
I 19
30
28
73
27
320
33
65
140
35
36
409
67
139
138
35
61
IOs
h
k
I. IOFo
IOs
-33
-6
23
-5
21
-4
22
-3
—76
-2
—44
-I
-42
0
18
I
11 ■
2
29
3
-39
4
25
5
-32
6
—74
7
-36
-10
-32
-9
-67
-8
18
-7
—60
-6
-56
-5
22
-4
-39
-3
15
-2
-34
—I
-32
0
18
I
-70
2
3
-72
9
4
-4 3
5
15
6
15
-10
-50
; -9
-28
-8
I
I
I
I
I
I
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
3
3
3
6 278
6
90
6
84
6
73
6 179
49
6
6 1531
6 289
6 183
6 334
6
35
6
62
6 148
6
49
6
37
6 102
6
35
6 796
6 108
6 431
6 716
6 344
6 223
6 300
6 184
6 206
6 103
6 868
6 177
6
58
6 120
6
37
6 112
6 153
45
19
15
20
7
-20
18
4
9
6
-49
-33
24
—44
-74
26
-71
10
20
7
6
.7
8
to
26
13
20
9
15
-45
23
-74
23
17
I
121
h
(-sigma = unobserved):
Table 28.
(Continued)
F(obs) and Sigrna(F) (-si grna = unobserved) :
TrirnethyLbenzene Thiourea Adduct
h
k
IOs
h
Ir
0
-7
“6
—5
-4
—3
-2
-I
0
—7
I
2
2
2
2
2
2
2
2
3
141
20
37 -74
144'
19
37 -73
125
23
201
10
96
20
95
31
145
20
38 -75
-4
—3
—2
-I
—6
-5
-4
-3
-2
-I
4
4
4
4
5
5
5
5
5
5
I IOFo
12
12
12
12
12
12
12
12
12
12
52
S3
174
.37
97
36
37
296
36
68
IOs
h
I:
-29
-34'
16
-73
28
-72
-73
7
-.52
-42
-6
-5
-4
-3
-2
-I
0
-7
-6
-5
3
3
3
3
3
3
3
4
4
4
I. IOFo
12
12
12
12
12
12
12
12
12
12
I IOFo
12
12
12
12
12
12
12
12
12
12
IOs
h
k
I IOFo
IOs
h
k
129.
21
37 -73
153
18
219
10
152
20
38 -76
174
17
I 15
74
37 -74
178
12
-6
-5
-4
-3
-2
-4
—3
—6
-5
6
6
6
6
6
7
7
I
I
12
38
12 105
12 ' 38
12
54
12
87
12 . so
12
BO
13
33
13
73
-76
27
-75
-51
33
-36
-36
-53
-33
-4
-3
-2
-5
-4
-3
-5
-4
-3
I
I
I
2
2
2
3
3
3
I IOFo
13
13
13
13
13
13
13
13
13
126
37
165
186
38
9?
60
38
38
10 *i
21
-5%
j5
16
-75
29
-49
-76
-76
122
Table 28.
(Continued)
F(obs) and Sigma(F)
k
0
I
2
3
45
6
7
a
7
7
7
7
7
7
7
7
7
a
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
9
9
9
9
9
9
9
9
-9
-8
-7
—6
—5
-4-3
-2
-I
0
I.
2
3
45
6
7
-8
-7
—6
—5
-4
-3
-2-I
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
2
2
2
2
2
492
67
122
391
121
95
136
'37
38
80
144
309
87
34
189
31
157
546
342
248
31
568
34
35
111
97
78
197
71
35
677
32
209
499
10s
4
22
15
7
20
26
20
-73
-76
-37
19
10
30
—69
12
-62
12
6
5
7
-62
8
—68
-71
24
28
-35
14
-37
-70
7
-64
11
6
h
k
0 9
I 9
2 9
3 9
'4 9
5 9
6 9
7 9
-8 10
-7 10
—6 10
-5 10
-4 10
-3 10
-2 10
-I 10
0 10
I 10
2 10
3 10
4 10
5 10
6 10
7 10
-7 II
-6 11
-5 II
-4 11
—3 II
-2 II
-I I I
0 II
I II
2 11
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
2
2
2
2
2
371
184
122
136
' 75
36
543
38
38
37
36
I 12
307
82
398
273
356
135
489
224
122
61
94
87
37
36
36
372
73
I 19
I 10
57
172
93
IOs
TrimethyLbenzene Thiourea Adduct
h
k
5
3
8
4
19
5
17
6
-32
-7
-72
—6
8
-5
-75
—4
—7k>
-3
-73
-2
-72
-I
23
' 0
9
I
27
2
8 •
3
7
4
5
5
28
-6
8 . -5'
12
-4
21
-3
-4 2
-2
30
-I
' 33
0
-74
I
-72
2
-72
.3
9
4
-32
5
20
-5
14
-4
-28
-3
10
-2
26
-I
II
11
II
11
12
12
12
12
12
12
12
12
12
12
12
12
12
13
13
13
13
13
13
13
13
13
13
13
13
14
14
14
14
14
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
2
2
2
2
2
132
85
36
30 I
127
100
36
84
35
67
345
177
147
86
414
36
37
73
96
107
35
293
269
I72
35
108
140
16 1
90
157
37
124
74
120
IOs
h
k
19
0
31
I
-72
2
11
'3
23
.4
27
-4
-72
-3
30
-2
-70
-I
-37
■0
9
I
10
2
27
3
29
-2
8
-I
-71
0
-74
-10
-38
-9
28 ' —8
24
-7
-70
—6
10
-5
9
—3
10
-2
-49
-I
23
I
19
2
17
3
31
4
18
5
-74
6
21
7
-34
8
21
-10
14
14
14
14
14
15
15
15
15
15
15
15
15
16
16
16
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
2
I IOFo
2
2
2
2
2
2
'2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
.3
3
3
3
3
3
3
3
3
IOs
h
I;
69
27
126
17
97
26
36 -72
145
20
,137
21
104
26
36 -73
71 -30
108
26
56 -36
36 -73
128
21
73 -38
63 -34
37 -52
104
22
101
26
144
13
482
13
78
23
504
34
710
12
140
II
476
12
563
8
27 -38
534
7
261
7
220
8
167
12
121
26
92
28
142
21
-9
-8
-7
-6
-5
-4
-3
-I
0
I
2
3
4
5
6
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
8 2
-10 3
-9 3
-a 3
-7 3
—6 3
-5 3
—2 3
-I 3
0 3
2 3
4 3
5 3
6 3
7 3
8 3
-10 4
-9 4'
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
64
111
109
74
289
448
372
70
888
96
236
357
208
221
92
4 10
81
74
121
141
779
37
29
518
69
121
789
196
102
35
83
95
79
64
IO <3
-41
23
22
26
7
5
6
J6
5
12
a
I0
11
27
9
-34
-39
22
19
7
—64
-58
6
20
9
6
11
24
—7 0
32
30
-37
—4 1
1 2 3
h
(-sigma = unobserved):
Table 28.
(Continued)
F (obs) and sigma(F)
h
-a
Ic
i IOFo
IOs
h
k
87
30
127
19
97
22
376
7
221
9
462
5
80
18
781
14
160
7
202
9
128
15
165
13
I10
22
255
II
328
10
241 ■ 13
75 -39
97
28
295
II
2.37
12
125
18
452
7
153
10
543
6
127
8
1019
10
132
8
269
8
255
9
49 -43
173
14
7ti -34
136
20
73 -39
-9
—8
-7
-6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
7
8
-9
-8
-7
-6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
6
6
6
6
6
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
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
203
151
244
'104
313
220
844
701
SI
769
272
64
113
I12
542
194
87
184
206
99
158
35
489
146
620
30
205
298
640
81
296
270
3t>5
36
IOs
14
18
12
23
9
.9
7
7
17
14
6
-27
18
21
8
14
31 .
16
14
27
17
-69
' 7
15
6
-59
7
5
12
25
9
10
9
-71
T rimethyI benzene Thiourea Adduct
h
k
7
-9
-8
-7
—6
-5
-4
-3
-2
—I
0
I
2
3
4
5
4
7
-8
-7
-6
-5
—4
-3
-2
—I
0
I
2
3
4
5
6
7
7
8
8
8
8
8
8
8
8
8
8
8
a
8
8
8
8
8
9
9
9
9
9
9
9
9
9
9
9
9
9
9
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
68
I16
163
97
35
317
107
57
786
105
133
411
83
134
158
390
36
38
128
106
113
I60
34
238
32
206
43
230
659
81
35
I18
37
'38
IOs
-40
25
17
27
-70
9
21
—34
7
13
10
5
25
17
17
9
-72
-75
22
24
23
16
-67
10
—64
18
-34 ■
7
7
28
-71
22
-73
-76
*
h
I;
I IOFo
-8 10
-7 10
. -6 10
-5 10
-4 10
-3 10
-2 10
-I 10
0 10
I 10
2 10
3 10
4 10
5 10
6 10
-7 11
-6 11
-5 11
-4 11
-3 11
-2 11
-I 11
0 11
I 11
2 11
3 11
4 11
5 11
6 11
-7 12
—6 12
-5 12
-4 12
-3 12
3
79
3
36
3
36
. 3 128
3
35
3 101
'3 864
■3 147
3
94
3 152
3
86
3 101
3
87
3
83
3
37
3 129
3 " 193
3 296
3
63
3
34
3 123
3 120
3 103
3 364
3 378
3
35
3 134
3 283
3
89
3
74
3
37
3 181
3 175
3 I 15
IOs
-36
-73
-72
20
-69
22
7
10
18
20
27
24
29
32
-75
22 '
14
10
-39
-69
20
14
21
8
9
-69
19
II
32
-39
-74
15
15 1
22
h
k
-2 12
-I 12
0 12
I 12
2 12
3 12
4 12
5 12
-6 13
-5 13
-4 13
-3 13
-2 13
-I 13
0 13
I 13
2 13
3 13
4 13
-5 14
-4 14
-3 14
-2 14
-I 14
0 14
I 14
2 14
3 14
—4 15
-3 15
-2 15
-I 15
0 15
I 15
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
223
133
24-7
150
221
35
68
215
SI
is::
62
89
79
57
168
184
52
U 2
109
I I8
61
91
193
35
188
124
136
62
38
I07
36
106
150
36
IOs
13
25
11
12
12
-70
-38
14
-35
16
-41
28
32
-33
18
Io
-40
23
25
24
-45
28
14
— 19
10
16
20
—44
-75
25
-73
I7
14
-51
1 2 4
4 3
4 3
-6 4 3
-5 4 3
-4- 4 3
-3 4 3
-I 4 3
0 4 3
I 4 3
2 4 3
3 4. 3
4 4 3
5 4 3
6 4 3
7 4 3
a 4 3
-10 5 3
-9 5 3
-8 5 3
—7 5 3
—6 5 3
-5 5 3
—3 5 3
-2 5 3
. -I 5 3
0 5 3
I 5 3
2 5 3
3 5 3
4 5 3
5 .5 3
6 5 3
7 5 3
a 5 3
-7
(— sigma = unobserved):
Table 28.
(Continued)
F (obs) and sigma(F)
h
k
I IOFo
2 15 3
-10 0 4
-9 0 4
-8 0 4
-7 0 4
—6 0 4
-5 0 4
-4 0 4
-3 0 4
-2 0 4
-I 0 4
0 0 4
I 0 4
2 0 4
3 0 4
4 0 4
5 0 4
6 0 4
7 0 4
8 0 4
-10 I 4
-9 I 4
-8 I 4
-7 I 4
-6 I •4
—5 I 4.
-4 I 4
-3 I 4
-2
I 4
-I
I 4
0 I 4
I I 4
2 I 4
3 I 4
IOs
37 -74
18
161
64 —40
607
7
33 —66
300
8
28 -56
135
II
26 ' -53
7
300
19
55
824
9
26 -37
882
8
29 -58
237
10
109
22
253
12
36 -73
38 -76
83
30
97
19
544
15
73
23
32 -45
404
44
9
319
7
296
971
7
1111
6
585
4
127
6
345
6
73
22
C-sigma = unobserved):
h
4
5
-6
7.
8
-10
-9
—8
-7
—6
-5
—4
-3
-2
-I
0
I
2
3
4
5
6
7
8
-10
-9
-8
-7
—6
-5
-4
—3
-I
0
k
I IOFo
IOs
I
I
I
I
I
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
32
4 275
4 283
4 158
4 • 87
4 158
4
96
4 232
4 190
4 168
4 584
4
41
4 ■ 43
4" 462
4 285
4 182
4
26
4 433
4
51
4 137
4 529
4
36
4
36
4
38
4 21 I
4 121
4 229
4
34
4 134
4 149
4 466
4 531
4 1753
4 502
-45
13
14
14
25.
18
27
12
13
13
6
-37
-34
6
10
9
-37
6
-35
16
8
-72
-73
-75
14
22
13
-68
17
13
6
6
6
11
T r imethyI benzene Thiourea Adduct
h
■
k
I IOFo
I 3 4 377
2 3 4 117
3 3 4
52
4 3 4 132
5 3 4 425
6 3 4 151
7 3 4 149
38
8 3 4
-10 4 4
38
-9 4 4
88
-8 4 4 228
34
-7 4 4
—6 4 4 382
-5. 4 4 786
—4- 4 4 247
-3 4 4 707
-2 4 4 433
-I . 4 4 359
0 4 4 278
I 4 .4 630
2 4 4 1074
3 4 4 348
4 4 4 424
5 4 4 316
6 4 4 147
7 4 4 163
-10 5 4 167
-9
5 4
36
-8 5 4 122
-7 5 4
35
—6 5 4 218
-5 5 4 192
-4 5 4
76
-3 5 4 439
IOs
h
4
-2
-I
15
-35
0
18
I
9
2
17
3
19
4
—76
5
—76
6
30
7
12
-10
-9
-69
8
-8
7
-7
8
-6
-5
6
-4
6
-3
14
5
-2
4
-I
8
0
7
I
8
2
10
3
18
4
18
5
18 •
6
-73
7
22
-9
-70
—8
11
-7
12
—623
-5
6
-4
k
I IOFo
5 4
5 4
5 4
5 4
5 4
5 - .+
5 4
5 4
5 4
5 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6
4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
6 4
7 4
7 4
7 4
7 4
7 4
7 4
170
524
384
461
502
. 80
184
151
36
21 I
•86
95
186
108
98
32
30
680
90
72
55
260
868
297
244
63
81
81
53
131
36
148
109
462
IOs
h
10
4
5
4
6
27
14
17
-72
14
34
29
15
24
24
-65
—6 1
7
19
16
-23
7
8
9
II
-40
32
-35
-53
20
-71
17
21
7
-3 7
-2 7
-I 7
0 7
I 7
2 7
3 7
4 7
5 7
6 7
7 7
-9 8
-8 8
-7 8
—6 8
-5 8
—4 8
-3 8
-2 8
-I ti
0 8
I S
2
8
3 R
4 8
5 8
6 8
-9 9
-8 9
-7 9
— CD
9
-5 9
. -4 9
—3 9
f-
i
I;
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
IOs
993
7
115
15
233
6
54 -26
392
II
63 -31
83
27
66 —37
107
25
86
31
338
II
71 -40
37 -73
171
16
272
II
81
29
33 -66
366
8
57 -34
138
to
106
14
605
12
33 —66
453
8
358
9
36 -72
81 -34
131
23
37 -74
36 -72
36 -73
82
30
34 —68
279
10
Table 28.
(Continued)
F(obs) and sigma(F) (-sigma = unobserved):
Tri methyl benzene Thiourea Adduct
h
h
k
I IOFo
9 4
-I 9 4
O 9 4
I 9 4
2
9 '4
3 9 4
4- 9 4
5 9 4
6
9 '4
—
8 10
4
-7 10 4
—
6 10
4
-5 10 4
-4 10 4
-3 10 4
4
- 2 10
-I 10 4
O 10 4
I 10 4
4
2 10
3 10 4
4 10 4
5 10 4
6 10
4
- 8 11
4
-7 I I 4
- 6 11
4
-5 II 4
-4 11 4
-3 II 4
- 2 II 4
-I II 4
O II 4
I 11 4
-2
47
94
614
86
62
247
69
36
37
143
37
403
75
35
34
60
BI
355
128
90
■ 35
432
37
96
87
37
36
175
167
291
78
159
490
267
IOs
h
-45
2
k
I. IOFo
IOs
4
53 —46
20 .
4 107
23
•6
4 167
16
25
4 ■ 77 -36
-38
4 113
25
Ii
4
65 -42
-37 .
4 117
22 '
-72
4 214
13
-75
4 328
9
20
4
76 -53
-73
4 120
23
8
4 149
12
-34
4 153 '22
-69
4
63 -40
-6 8
4 188
14
-38
4
37 -74
20
4
38 -75
6
-5 13 4 I12
24
-4 13 4
13
36 -72
27
-3 13 4 279
10
-70
- 2 13
4
36 -71
49
8
-I 13 4
35 —
-73
0 13
4
35 -49
30
I 13 4
93
24
34
2 13
4
55 -47
-75
3 13 4
36 t 73
-73
4 13 4
38 -75 .
15
-5 14 4
38 -75
16
-4 14 4 113
24
10
-3 14 4 I II
24
31
- 2 14
4
36 -71
II
-I 14 4 137 ’ 17
0 14
4 179
11
6
7
66
-27
I 14 4
11
3 11
■ 4 11
5 11
-7 12
- 6 12
-5 12
-4 12
-3 12
- 2 12
-I 12
0 12
I 12
2 12
3 12
4 12
—
6 13
k
14
-3 15
- 2 15
-I 15
0 15
I 15
-1 0
I
-9 I
—
8
I
-7 I
-6
I
-5 I
-4 I
-3 I
-2
I
—t I
0 ■ I
I I
2 'I
3 I
4 I
5 I
6
I
7 I
2
-1 0
-9
-8
-7
-6
-5
-4
-3
-2
-I
2
2
2
2
2
2
2
2
2
2
I IOFo
4.
4
4
4
4
4
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
IOs
h
k
197
15
37 -73
37 -74
193
10
67 -34
56 -37
37 -52
36 -51
173
11
103
16
619
83
219
19
542
27
325
6
386
9
386
5
95
14
287
4
50 -24
173
10
990 ' •3
122
15
36 -51
130
15
37 -74
323
to
74 -35
34 -6 8
255
9
152
12
183
10
777
7
427
6
561
4
0
2
2
2
2
2
2
2
2
I
2
3
4
5
6
7
-10
-9
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
6
7
-10
-9
-8
-7
—
6
-5
-4
—3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
I IOFo
10s
h
I;
5 843
9
-2
5 975
15
—I
5 151
12
0
5 118
17
I
54 -44
5
2
74 —34
5
3
5 220
13
4
5 170
17
5
5
78 —36
6
5
37 -73
7
5
79 .-32
-1 0
-■-1
5
88
27
5
33 -65'
-8
5 372
7
-7
5 271
8
-6
5 811
7
-5
5 131
12
■-4
5 215
7 . -3
5 182
11
-2
5 II 12
17
-I
5 ■365
7
0
5 144
16
I
5
91
26
2
5 ( 60 -42
3
5 146
19
4
5 I17
24
5
5
80 -35
6
5 263
II
7
5 143
19
-1 0
5 235
12
-9
5
34 -6 8
-8
5 125
17
-7
5 416
6
-6
5 375
6
-5
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
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.
470
43
278
703
127
54
35
57
292
144
38
37
123
77
456
236
227
64 I
207
237
59
191
217
197
466
36
355
38
77
37
56
198
165
34
IOs
6
-28
5
6
16
-40
-69
-4 5
II
20
-76
-73
21
-33
7
IU
9
7
9
8
23
II
I2
8
-72
9
-75
-38
-74
—46
14
15
-6 8
Table 28.
(Continued)
F(Obs) and sigrna(F) (-sigma = unobserved):
h
k
I IOFo
22
23
15
18
-49
7
11
30
17
20
-51
20
14
-71
11
-32
-49
—36
-71
28
29
31
-49
10
13
-32
16
28
-74
II
-38
-52
22
-72
h
—8
-7
-6
-5
-4
-3
-I
0
I
2
3
4
5
6
7
8
9
-10
-9
-8
-7
—6
-5
-4
-3
-I
0
I
2
3
4
5
6
7
k
I IOFo
IOs
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
.1
I
2 112
77
2
2 655
27
2
88
2
2
54
18
2
2 229
2 ' 162
2 570
27
2
2 979
31
2
2 163
66
2
2 350
38
2
72
2
2 136
2 103
2 137
2 411
2 298
2 163
2 861
40
2
2 300
2 445
2 248
64
2
2 1289
2 223
34
2
2 136
23
29
7
-55
16
-26
-25
4
5
6
—54
8
-63
16
-39
10
-77
28
14
26
12
16
13
7
6
II
5
3
6
17
13
8
-48
14
h
k
I IOFo
IOs
7
8 I 2 364
23
90
9 I 2
69 -41
-10 2 2
9
-9 2 2 -122
14
-7 2 2 187
8
—6 2 2 294
8
-5 2 2 256
6
—4 2 2 583
6
-3 2 2 653
5
-I 2 2 313
4
0 2 2 787
5
I 2 2 2594
6
2 2 2 1161
6
3 2 2 766
7
4- 2 2 708
32 —64
■5 .. 2 2
34 -69
6 2 2
36 -71
'7, 2 2
12
8 2 2 259
20
9 2 2 154
83 -35
-10 3 2
—'•9 3 2 228
13
78 -33
-8 3 2
II
-7 3 2 259
9
—6 3 2 285
7
-5 3 2 307
6
-4 3 2 558
7
-3 3 2 916
72
14
-I 3 2
5
0 3 2 306
5
I 3 2 404
6
2 3 2 384
7
3 3 2 241
9
4 3 2 221
h
5
6
7
8
9
-10
-9
-8
-7
—6
-5
—4
-3
-2
.-I
0
I
2
3
4
5
6
7
8
-10
-9
-8
-7
—6
-5
-Z
-Z
-I
I
k
I IOFo
3 '2 230
3 2 406
3 2 170
69
3 2
85
3 2
38
4-- 2
4 ' 2 253
61
4 2
36
4 2
4 2 283
4 2 350
4 2 312
4 2 522
4 2 492
69
4 2
73
4 2
4 2 1513
4 2 679
53
4 2
4 2 383
4 2 (102
68
4 2
36
•4 2
37
4 2
77
5 2
5 2 190
61
5 2
5 2 186
5 2 366
31
5 2
5 2 445
5 2 156
5 2 927
5 2 294
h
IOs
II
8
16
-39
-35
-76
12
—‘13
-72
9
7
6
6
6
19
17
7
6
-30
7
22
—36
-72
-74
-38
'15
-43
15
8
—61
6
II
14
5
i. '
I
k
I IOFo
2 5 2 182
3 5 2 169
4 5 2 286
35
5 5 2
6 5 2 469.
62
7 5 2
8 5 2 197
37
-9 6 2
36
-8 6 2
-7 6 2 580
-6 6 2 369
-5 ■6 2
33
88
-4 6 2
6 2 14'1
-Z
-2 6 2 124
-I 6 2 1316
0 6 2 262
I 6 2 155
2 6 2 264
3 6 2 314
4 6 2 362
5 6 2 34-1
6 6 2 181
36
7 6 2
8 6 2 150
-9 7 2 107
59
-8 7 2
69
-7 7 2
35
—6 7 2
33
-5 7 2
32
-4 7 2
—3 7 2 205
-2 7 2 901
-I 7 2 1331
IOs
9
II
9
-69
8
-42
.15
-74
-72
7
a
—66
22
12
13
6
7
16
8
8
8
9
.15
-72
19
27
-44
-38
-70
—67
-64
9
7
7
1 2 7
-4 13 I 115
I 107
- Z 13
-2 13 I 175
99
-I 13 I
34
O 13 I
I 13 I 282
2 13 I 253
83
I
Z 13
4 13 I 158
5 13 I 140
55
-5 14 I
-4 14 I 141
-3 14 I 189
35
-2 14 I
-I 14 I 158
62
O 14 I
35
I 14 I
70
2 14 I
36
3 14 I
97
4 14 I
99
-4 15 I
87
-3 15 I
54
-2 15 I
-I 15 I 197
O 15 • I 150
67
I 15 I
2 15 I 176
97
3 15 I
37
-2 16 I
-I 16 I 178
54
O 16 I
37
I 16 I
-10 O 2 126
36
—9 O 2
10s
Trimethylbenzene Thiourea Adduct
Table 28.
(Continued)
F(obs) and sigma(F) (-sigma = unobserved):
T r imethy Ibenzene Thiourea Adduct
h
h
k
IOs
h
-9 3 "I 181
-8 3 I
36
-7 3 I 134
-6 3 I 588
-5 3 I 148
-4 3 I 199
-3 3 I 539
-I 3 I 3020
0 3 I 246
I 3 I 312
2 3 I
92
3 3 I 407
4 3 I 297
5 3 I 210
6 3 I
34
7 3 I 129
8 3 I
71
9 3 I 348
-9 4 I
69
-8 ’ 4 I 157
-7 4 I .35
-6 4 I 497
-5 4 I 272
-4 4 I 321
-3 4 I 259
-2 4 I 363
-I 4 I 2598
0 4 I 710
I 4 I 247
2 4 I 380
3 4 I 510
4 .4 I 439
5 4 I 614
6 4 I 389
16
-72
19
7
13
9
6
45
4
5
18
6
7
11
—68
20
-38
10
-40
17
-69
7
8
6
7
6
5
4
6
6
6
7
7
8
7
8
9
-9
-8
-7
—6
-5
-4
-3
-2
0
I
2
3
4
5
6
7
8
9
-9
-8
-7
-6
-5
-4
-2
-I
0
I
2
3
4
k
I IOFo
4 I
4 I
4 I
5 I
5 I
5 I
5 I
5 I
5 I
5 I
5 .1
5 I
5 I
5 I
5 I
5 I
5 I
5 I
5 I
5 I
5 I
6 I
6 I
6 I
6 I
6 I
6 I
6 I
6 I
6 I
6 I
6 I
6 I
6 I
59
52
89
37
303
35
490
168
81
104
I14
1290
761
927
29
48
99
35
305
37
125
130
67
111
301
275
259
121
26
655
157
2/7
520
221
IOs
-44
-50
32
-75
10
-71
7
13
20
15
14
5
10
7
-57
-38
22
-70
10
-74
24
22
-39
23
10
9
9
13
-37
5
12
7
7
10
k
I IOFo
IOs
h
5 6
6 6
7 6
8 6
-9 7
-8 7
-7 7
—6 7
-5 7
-4 7
—3 7
-2 7
-I 7
0 7
1- 7
2 7
3" 7
4 7
5"7
6 7
7 7
8 7
-8 8
-7 8
—6 8
-5 8
-4 8
-3 8
-2 8
-I 8
0 8
I 8
2 8
3 8
I
63
I 262
I 396
I
37
I 168
I 214
I
70
I 215
I
57
1- 51
1 571
I 315
I
88
I 382
I 1065
I 184
I 108
I
72
I
86
I 231
I 251
I
37
I 100
I
36
I 274
I
85
I
92
I 934
I 402
I I 15
I 416
I 237
I
77
I 258
-37
12
9
-74
18
14
-37
13
-39
-40
6
7
19
12
24
10
17
-31
27
12
12
-75
27
-72
11
28
23
8
7
II
5
6
23
10
4 8
5 8
6 8
7 8
8 8
-8 9
-7 9
—6 9
-5 9
-4 9
-3 9
-2 9
-I 9
0 9
I 9
2 9
3 9
4 9
5 9
6 9
7 9
-8 10
-7 10
—6 10
-5 10
• -4, 10
—3 10
-2 10
-I 10
0 10
I 10
2 10
3 10
4 10
k
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
I
I
I
I
I
I
I
I
I
IOs
h
k
I IOFo
546
7
5 10 I
131
19
6 10 I
65 -40
7 10 I
' 394
9
-7 11 I
86
34
—6 11 I
-5 11 I
/ 37 -75
77 -35'
-4 11 I
380
9
-3 11 I
183
15
-2 11 I
50 —45
-I 11 I
59 -36
0 11 I
167
13
I 11 I
30 -42
2 11 I
743
9
3 11 I
154
10
4 11 I
157
14
5 11 I
237 . 11
6 11 I
7 11 I
446
8
125
20 ' -7 12 I
36 -72
—6 12 ,1
62 -45
-5 12 I
96
30
-4 12 I
70 -39
-3 12 I
413
9
-2 12 I
36 -71
-I 12 I
34 -69
0 12 I
89
25
I 12 I
117
19
2 12 I
85
26
3 12 I
65 -26
4 12 I
218
8
5 12 I
83
27
6 12 I
161
15
-6 13 I
600 -■ 8
-5 13 I
i
i
?
70
36
38
54
144
67
127
34
148
231
286
335
34
35
217
63
55
I II
64
87
100
1)2
444
117
45
88
HO
74
35
147
131
37
38
37
IOs
-36
-73
-75
-52
1.9
-39
20
-68
17
13
7
6
-68
-69
13
-41
-49
27
-46
32
26
22
8
21
-38
19
17
-33
-70
18
21
-75
-75
-74
128
I IOFo
Table 28.
(Continued)
F Cobs) and Sigma(F)
k
2
3
4
5
6
7
a
9
i
2
3
4
5
6
7
8
0
0
0
(i
0
0
0
0
I
I
I
I
I
I
I
I
I
I IOFo
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
9
0
0 2 0
I 2 0
2
2
0
3 2 0
4
0
2
5 2 0
6 2 0
7 2. 0
8 2 0
9
2 0
I 3 0
2. 3 0
3 3 0
4 ■3 0
5
3 0
6 3 0
7 3 0
IOs •
800
5
54 -27
188
9
29 -57
375
8
35 -69
143
18
37 -73
130
5
479
5
983
17
388
9
267
6
313
12
338
7
151
13
72
27
669
4
•18 -26
147
9
986
7
27 —55
56 -31
33 —66
481
8
36 -72
94
29
48
19
658
7
1369
7
161
10
213
10
34 -68
467
8
h
k
I IOFo
IOs
8 3
9 3
0 4
I 4
2 4
3 4
4 4
5 4
6 4
7 4
8 4
9 4
I 5
2 5
3 5
4 5
5 5
6.5
7 5
8
5
5
9
0 6
I 6
2
6
3 6
4
6
5 6
6 6
7 6
8
6
9 6
I 7
2 7
3 7
0
53
0
67
0 938
0 1537
0 963
0 328
0
68
0
31
0
56
0 331
0 339
0
67
0 314
0 731
0 254
0 403
0 561
0
34
0
36
0 180
0 126
0 289
0 230
0 420
0
72
0 226
0 256
0
53
0 134
0 118
0 140
0 169
0
74
0 141
-49
-42
6
20
7
7
24
-62
-43
10
9
-42
5
6
7
6
7
-68
-72 '
I6
22
6
8
6
23
9
11
-46
20
23
22
7
23
13
T r imethyI benzene Thiourea Adduct
h
k
4 7
5 7
6 7
7 7
8 7
9 7
0 8
I 8
2 8
3 8
4 8
5 8
6 8
7 B
8 -8
L 9
2 9
3 -•?
4 '9
5 9
6 9
7 9
8
9
0 10
I 10
2 10
3 10
4 10
5 10
6 10
7 10
I II
2 II
3 11
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
193
941
78
166
99
38
595
109.
897
139
352
35
92
136
208
100
572
60
103
268
36
84
38
328
168
629
33
71
36
80
37
216
347
165
IOs
h
12
7
-32
16
28
-76
6
II
■7
15
8
-69
28
20
14
13
7
—36
23
II
-72
31
—76
4
5
6
7
0
I
2
3
4
5
6
I
2
3
4
5
6
0
I
2
3
8
9
7
—66
-34
-72
-33
-74
4
5
I
2
3
0
I
2
-10
-9
8
-8
9
15
-7
—6
I;
I IOFo
IOs
11 0
78
11 0 369
11 0
37
II 0
38
12 0 427
12 0 160
12 0 156
12 0
85
12 ■ 0
35
12 0
36
12 0 156
13 0
35
13 0
35
13 0
35
13 0
36
13 0 237
13 0
69
14 0 246
14 0 172
14 0 136
14 0
58
14 0
37
14 0
38
15 0
36
15 0
86
15 0 207
16 0
37
16 0
37
16 0
37
I 'I
69
I
62
I I 699
I I
34
I I 458
-32
9
-73
—76
a
18
16
' 29
-70
-73
18
-49
-70
-70
h
k
-5 I
-4 I
-3 I
-2 I
-I
I
I I
2 I
4 I
5 I
6 I
7 I
a I
9 I
— 10 2
— 7'2
-9 2
13
-8
-42
-7 2
U . —6 2
11
-5 2
19
—4 2
-43
-3 2
-73
-2 2
-76
-I 2
-50
0
30
I 2
14
2
2
-73
3 2
-52
4 2
-74
5 2
-30
6
-31
7
2
16
8 2
-48
9 2
12
-10 3
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
I
I
I
I
I
I
I
I
I
10s
176
10
91
21
380
6
II
59
564
19
268
3
2262
5
396
5
255 ' 7
19
85
35 -50
128
15
189
16
102
2.8
36 -72
'71 -36
78
31
190
12
629
6
690
6
4d 5
6
540
5
1377
4
18 -25
169
5
537
6
546
6
244
8
808
8
115
21
296
10
36 -72
139
21
150
20
129
h
(-sigma = unobserved)i
Table 29.
Observed and calculated structure factors for the 1,2,4 TMB-thiourea adduct structure
Observed and calculated structure factors:
h
I;
-I
0
I
3
4-
-7
-5
-4
-2
8
8
8
8
-I
0
I
2
3
4
8
a
8
8
8
8
38
48
3
3 461 429
3 163 177
68
4ti
3
3
67 ■ 42 '
3 325 345
3 116 131
4
52
3
3 111 104
3 '124 I 15
19
3
59
81
95
3
3 294 334
80
88
3
—1
3 372
3 123 129
3 179 173
3 384 407
49 . 59
3
3 177 190
3 162 155
3 219 221
46
3
69
98 102
3
27
58
3
184
191
3
66
64
3
471 463
3
85
63
3
63
80
3
3 246 252
50
46
3
58
80
3
95 I 18
3
h
k
5 8
-8 9
-7 9
—6 9
-5 9
-3 9
-I 9
I 9
2 9
3 9
5 9
-5 10
-3 10
-2 10
-I 10
0 10
I 10
2 10
3 10
4 10
5 10
-7 11
—6 11
-5 11
-2 11
-I 11
0 11
I 11
2 II
4 11
5 II
6 II
-5 12
-4 12
I IOFo IOFc
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
234
77
64
68
96
143
124
138
396
49
71
77
60
518
88
56
91
52
60
52
50
77
116
178
74
72
62
219
227
80
170
53
108
105
h
249
-3
-2
42
-I
45
0
55
I
87
2
147
5
117
130
-5
-3
405
-2
32
0
60
I
43
11
3
509
4
-5
79
48
-3
89
-2
0
32
I
23
2
37
5 . -377
-I
88
0
174
-10
104
-8
79
—6
46
-4
-2
236
233
-I
0
70
155
2
17
4
5
I11
107
6
k
h
51
139
80
153
87
148
124
121
54
47
99
101
53
26
38
43
106
I16
76
85
59
61
93
-10
-9
-8
-7
-5
-4
-3
-2
-I
0
I
2
3
5
6
7
8
-9
—8
-7
—6
-5
I 4
I 4
I ,4
I 4
I 4
I 4
I 4
I 4
I 4
I 4
I 4
I 4
I 4
I 4
I 4
I 4
I 4
2 4
2 4
2 4
2 4
2 4
2 4
-2
-I
0
2
4
2
2
2
2
2
2
3
3
3
3
3
12
12
12
12
12
12
12
13
13
13
13
13
13
13
14
14
14
14
14
14
1.5
15
15
3
3
3
3
3
3
3
0
0
0
0
0
4
4
4
4
4
0
0
0
0
4
4
4
4
4
4-
0
0
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
69
134
80
143
90
132
129
109
53
48
101
HO
67
66
71
54
I16
113
74
81
64
64
90
-.10
96
66
364
180
359
200
81
100
180
33
494
529
142
192
0
456
521
161
5
-10
-9
-8
66
0
-6
152
157
-5
k
I. IOFo IOFc
I' IOFo IOFc
50
58
326
44242
192
178
583
667
351
76
207
44
165
170
95
52
95
57
139
I14
101
351
4 277
4
171
4
I09
260
4
482
4 317
4 127
4
72
4 137
80
4
89
4
h
k
7
49
294
51
243
174
184
605
625
340
76
202
19
147
177
106
54
59
35
141
125
143
423
291
134
-4
-3
-I
0
I
2
4
5
6
7
-9
-8
-6
-5
-4
-3
-2
-I
0
I
2
3
4
3
3
3
3
3
3
3
3
101
7
274
85
331
106
41
147
99
113
-10
5
4
-8
-6
-5
-4
-3
. -2
-I
5
5
5
5
5
5
5
4
73
4 131
4 115
4
46
4 7.64
4 102
4- 315
5
6
I IOFo IOFc
4
44
44
4
4
43 4
3 4
4 4
4 4
4 4
4 4
4 4
4 4
4 4
4 4
4 4
4 44 4
4- 4
4 4
4- 4
279
319
1052
301
226
70
79
255
91
89
53
137
229
472
148
4-25
260
.3)5
167
378
644
209
254
1.90
326
332
947
293
227
82
90
252
39
8448
138
265
569
157
428
239
204
I70
353
636
208
273
4
88
4- 4
98
72
Re,
103
73
142
137
9
759
95
4
100
177
3Ki
130 'I
6
6
6
6
6
5 6
6
6
7
6
8 6
-9 7
-B
7
-7 7
-5 7
-4 7
-3 7
-I 7
0'7
I 7
2 7
3 7
4 7
5' 7
-9 a
-8 8
I IOFo IOFc
Trimethylbenzene Thiourea Adduct
Table 29.
(Continued)
Observed and calculated structure factors:
h
k
i IOFo IOFc
-2
-I
0
I
2
3
4
5
6
6
6
6
6
6
6
2
2
2
2
2
2
2
2
2
a
Cd
-9
-3
-2
-I
0
I
2
3
4
5
6
-8 a
—7 a
—6 a
-4 a
-2 a
-I 8
0 8
I 8
3 a
'6 8
7 a
-7 9
-4 9
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
-I
0
I
2
3
6
-5
-4
-3
-2
-I
0
I
2
3
4
6
7
-4
-2
-I
I
2
3
4
6
-7
-6
-4
-I
0
I
2
k
h
I;
6
3 12 2 249 248
1.3
7
-5 13 2
58
64
63
8
—4 13 2
-10
-2 13 2 176 172
173
-8
-I 13 2 161
-7
0 13 2 103 I15
—6
65
56
2 13 2
-5
3 13 2
84 101
-4
96
92
4 13 2
54
I
-3
5 13 2
81
-I
-5 14 2
94
-3 14 2
74
84
0
72 ' 94 '
I
-I 14 2
41
19
2
0 14 ■2
76
76
3
I 14 2
2 14 2
53
25
4
5
4 14 2 . 87 107
-4" 15 2
82
79
6
-3 15 2
62
47
7
40
-9
0 15 2
65
-8
56 .
3-, 15 2
77
71
I 3
63
68
-7
64
-10
96
-9 I 3
61
47
-2
42
—8 I 3
87
09
-I
0
69
-7 I 3 289 272
47
2
43
—6 I 3
46
4
177
-5 I 3 302 301
-3 I 3 426 403
5
85
50
-2 I 3
84
69
7
8
21
-I
I 3 286 199
-8
216
I I 3 338 336
110
3 I 3 320 324
-7
—6
73
4 I 3 156 1
' 151
-5 I 3 132 133
-5
46
I
I
I
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
I IOFo IOFc,
9 2
9 2
9 2
9 2
9 2
9 2
9 2
10 2
10 2
10 2
10 2
10 2
10 2
10 2
10 2
10 2
10 2
.10 2
10 2
11 2
11 2
II 2
11 2
II 2
11 2
11 2
11 2
12 2
12 2
12 2
12 2
12 2
12 2
12 2
125
299
222
I10
73
82
326
67
184
49
239
164
213
81
294
134
73
56
52
223
72
66
103
56
79
51
180
76
60
51
207
106
88
52
109
287
213
102
77
74
324
75
204
36
247
155
212
54
300
123
102
30
42
214
h
k
I' IOFo IOFc
I IOFo IOFc
3 100
73
3
. 3 • 55
3
85
3
67
65
•3
3 '45
3 173
3 269
3 223
3
42
3 533
58
3
3 142
3 214
3 125
3 132
3
55
3 246
72
3
3
85
3 468.
3 31 I
3
41
3
72
3 474
3 118
61
3
3
50
57
3
52
3
.3
76
58
3
3 225
89
43
27
67
51
30
20
198
288
246
91
536
43
135
208
121
135
53
243
54
59
458
284
51
59
475
118
105
37
56
47
56
46
246
I
h
I-
-4
-3
-I
O
I
2
3
45
6
7
8
-9
-3
-7
—6
-5
-3
-2
-I
0
I
2
3
5
7
-9
-8
-7
—6
-5
-4
-3
-2
4
44
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
I IOFo IOFc
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
133
277
48
469
96
1.21
77
99
66
153
197
145
58
177
142
75
271
92
326
76
612
79
161
153
I04
82
122
91.
146
63
188
132
507
421
167
271
28
444:
I09
126
32
92
53
152
198
142
46
171
159
45
291
87
314
80
567
10.5
189
I35
I 13
101
93
90
II I
'83
21 I
134
433
401
131
6
6
6
7
7
7
7
7
7
7
7
7
7
7
74
73
790 76*
157 179
93
79
158 153
188 192
217 201
205 214
109
96
' 90
89
18
64
123 121
541 490
799 775
29e> 284
33
40
73
80
235 236
73 . 91
31
57
82
71
87
72
185 201
52
50
113 112
94 100
328 325
206 205
149 154
341 349
66
36
58
24
118
97
406 408
h
T r imetby Ibenzene Thiourea Adduct
Table 29.
(Continued)
Observed and calculated structure factors:
T r imethy Ibenzene Thiourea Adduct
h
k
h
7
—9
-a
—6
-3
-2
-I
0
I
2
3
6
7
7
7
7
7
7
7
7
7
7
7
7
7
a
a
a
a
a
8
a
'a
a
a
a
a
a
a
a
9
9
9
9
9
5
6
7
-a
—6
-5
-4
-3
-2
-I
0
I
2
3
4
5
7
a
—6
-5
-2
0
I
i IOFo
IOFc
i 238
240
i
101
85
i
128
129
i
129
128
i 343
340
i
189
183
i
53
6
i 229
212
i 639
615
i ' I 10
117
i
65
28
i
52
69
i
139
123
i
150
141
i
60 ■ 42
i
164
183
i
51
7a
i
55
27
i 561
539
I 241
221 ,
i
69
61
i 250
265
i
142
136
i
46
38
i
155
172
i 328
329
i
79
60
i 237
224
24
i
52
i 228
226
i
H O ' 118
i
100
76
i 446
448
i
93
I 12
h
k
2
3
4
5
-8
—6
-3
-2
-I
I
2
3
4
—6
-4
-2
-I
0
I
9
9
9
9
10
to
10
10
10
10
10
10
10
II
II
11
11
11
II
4 11
7 II
-6 12
-5 12
-4 12
-3 12
-2
0
I
4
5
-4
-3
12
12
12
12
12
13
13
-2 13
-I 13
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
i
i
i
i
i
i
i
i
i
95
142
268
75
58
248
54
70
51
131
50
96
360
86
76
89
139
172
201
130
66
52
60
67
266
70
53
66
88
79
69
64
105
60
IOFc
83
I
146
2
271
3
4
67
31
5
243
-4
72
-3
o7
-I
75
4
130
-4
28
-3
85
-I
362
0
101
2
82
3
-V
97
159
-10
183
-8
177
-7
134
— 6i
73 . -4
58
0
85
I
60
2
276
4
11
6
71
a
72
-10
74
-9
59
-a
65
-7
14
—6
I 14
-5
50
—4
I' IOFo
IOFc
13
I
169
13
I
152
13
I
50
1.3 I
95
13
I
84
I
14
85
14
I
113
I ■ 95
14
14
I
58
15
I
60
15
I
52
15
I
I 18
15
I
90
15
I I 05
15
I
58
16
I
107
0 2
76
0 2
67
0 2
46
0 2
393
0 2
53
0 2
137
0 2
97
0 2
■742
0 2
588
0 2
98
0 2 210
I 2
43
I 2
82
I 2
62
I 2
82
I 2
247
I 2
179
I 2
98
176
131
.26
80
75
96
134
94
57
13
. 44
97
92
I05
50
106
20
77
0
I:
362
54
IH
0
349
591
99
201
7
66
38 '
75
240
174
93
h
I:
—3
I
-I ’ I
0
I
I I
2
I
3
I
4
I
5
I
7
I
8
I
9
I
-9
2
-7
2
-6
2
-5
2
—4 2
-3
2
—I 2
0 2
I 2
2 2
3 2
4 2
8 2
9 2
-9 3
3
-7
—6 3
-5
3
-4
3
3
-3
-I
3
0 3
I 3
I IOFo
IOFc
h
k
2
516
507
2
24
4
2 ' 180
171
2 267
232
2
149
155
39
2
52
2
774
693
2
134
139
2
82
78
2 218
2Uo
2
54
51
2
253
238
2
I 12
82
2
176
158
2
153
162
2
350
348
2
392
408
2
183
195
2
472" 585
2 1556 1404
2
697
650
2
460
477
2
425
403
2
155
146
2
92
92
137
2
I 17
155
2
149
171
2
185
2
184
172
2
335
349
2
550
563
29
2
43
184
2
221
2
242
212
2
3
4
5
6
7
-9
—6
-5
-4
-3
-2
-I
0
I
2
4
5
-9
3
3
3
3
3
3
4
4
4
4
4
44
4
4
4
4
4
-7
—6
-3
-2
-I
I
2
3
4
6
8
-7
'-6
.-4
-3
5
5
5
5
5
5
5
5
5
5
5
I IOFo
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
•■s
2
2
2
2
2
2
2
2
2
2
2
2
2
5 2
6 2
6 2
6■ 2
6
2
231
145
132
139
244
I02
152
170
210
187
313
295
41
44908
4 07
230
61
I 14
112
220
267
94
556
176
109
101
172
281
I 18
348
IOFc
53
231
14-3
123
167
243
75
128
I88
198
187
293
287
12
25
866
389
234
6
93
121
227
270
153
544
165
91
100
171
303
I 16
334
231
60
86
77
222
Table 29.
(Continued)
,
Observed and calculated structure factors:
h
I. IOFo IOFc
h
0
0
0
0
I
I
I
I
I
I
I
I
I
2
2
2
2
9
2
I 3
2 3
3 3
4'3
5 3
7 3
0 4
I 4
2 4
3 4
4 4
7
4
8 4
I 5
2 5
3 5
0 480 557
0 I 13 I 19
0 225 202
86
54
0
78
83
0
0 287 314
0 ■ 590 521
0 233 234
0 160 154
0 188 175
0 203 198
90
77
0
43
11
0
0 402 403
88
56
0
0 591 582
0 289 266
0
57
25
29 . 36
0
0 395 322
0 822 765
0
96 . 98
0 128 125
0 280 27-3
0 563 554
0 922 873
0 578 592
0 197 218
49
41
0
0 199 173
0 203 168
0 188 172
0 439 486
0 152 126
4 5
5 5
8 5
9 5
0 6
I 6
2 6
3 6
4 6
5 6
7 6
8 6
9 6
I 7
2 7
3 7
4 7
5 7
7 7
8 7
0 ■8
I 8
2 8
3 8
4 8
6
8
7 8
8 8
I 9
2 9
4 9
5 9
7 9
0 10
2
4
6
a
I
2
3
4
5
6
7
a
9
0
2
3
7
k
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
O
0
0
0
0
0
0
0
0
h
I
242 236
337 331
2
108 114
I
35
2
75
3
173 196
5
138 135
■252 251
0
15
I
43
2
135 159
3
153 151
80
6
81
71
45
5
84
97
b
i
102 103
44
9
2
69
2
84
3'
I 16 119
-8
565 567
94
—6
100
59
80
-5,
357 367 . -4
65
63
-3
538 539
-2
83
82
-I
I
21 I ' 231
55
48
2
81
■4
70
125 132
5
6
60
59
343 341
8
52
9
62
161
156
-10
51
18
-7
-6
197 203
k
I' IOFo IOFc
10
10
11
11
11
11
12
12
12
12
12
13
14
14
14
15
15
I
I
I
I
I
I
I
I
I
I
I
I
I
I
2
2
2
0 101
92
0 377 383
0 130 133
0 203 193
0
99 101
0 221 229
0 256 245
96
81
0
94
96
0
0
51
35
94 107
0
0 142 152
0 148 155
0 ' 103 109
0
82
78
52
42
0
0 124 126
I 420 376
I 275 248
I 106 110
I
55
47
I 223 199
I
35
39
I 338 341
I 161 105
I 1358 1240
I 237 224
I 153 154
I
51
65
40
I
77
I I13 104
I
61
47
I
52
47
I I14
BS
h
I;
I IOFo IOFc
h
I;
I IOFd IOFe
-5 2 I 378 368
-2 4 - I
-4 2 I 414 44 6
-I 4 I
—3 2 ■ I 279 31 I
0 4 I
-2 2 I 324 338
I 4 I
-I 2 I 827 830
2 4 I
I 2 I 102
97
3 4 I
2 2 I 322 291
4 4 I
3 2 I 328 295
5 4 I
4 2 I 147 138
6 4. I
5 2 I 485 454
9 4 •1
6 2 I
69
69
-8 5 I
7 2 I 177 I70
-6 5 I
83
76
9 2 I
-5 5 I
— 10 3 I
90
58
—4 5 I
84
-3 5 I
-9 3 I 109
-7 3 I
80
86
-2 5 I
—6 3 I 353 343
0 5 I
8'3
86
I 5 I
-5 3 I
-4 3 I 119 104
2 5 I
-3 3 I' 324 30 I
5 5 'I
-I 3 I 1812 1666
7 5 I
0 3 I 147 164
9 5 I
I 3 I 187 119
-9 6
I
55
24
-7 6
I
2 3 I
3 3 I 244 218
—6 6 I
4 3 I 178 185
-5 6 I
5 3 I 126 107
.—4 6 I
78
6 ' -2 6 I
7 3
I
0 '6 I
9 3 I 209 195
87
-8 4 I
94
I 6 I
—6 4 I 298 289
2 6
I
3 6 I
-5 4 I 163 157
—4 4 I 193 167
4 6
I
-3 4 I 155 188
6 6 I
.218
1559'
426
1.48
228
306
264
363
234
54
182
294101
4-9
63
69
774
157
556
59
183
75
78
67
181
165
155
72
393
94
166
312
132
157
228
1360
383
121
211
293
270
375
227
6
173
289
88
53
58
91737
427
564
28
160
52
45
56
169
167
162
102
369
73
142
31 I
138
169
1 3 3
k
Trimethylbenzene Thiourea Adduct
Table 29.
(Continued)
h
k
I IOFo IOFc
h
k
I. IOFo IOFc
h
k
-4
-3
-I
0
I
2
3
-9
-7
—6
“4
-3
-I
I
2
3
4
-S
-7
—6
-5
-3-I
0
I
2
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5'
5
5
5
5
5
5
5
a
3
8
8
8
8
8
8
8
8
8
6
6
—6
-5
-4
"3
-2
-I
0
I
2
3
4
-7
—6
-5
—4
-3
-I
0
2
-8
-5
-4
-I
0
I
2
3
7
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
-7
8 130 152
8
94
86
8
84
88
8
54
32
8 323 330
8 164 155
8
65
58
8
74
70
50
55
8
8 ' 102 I 15
8 255 275
8 277 267
8
95
86
91
8 104
54
55
8
8
78
94
68
8
74
8 127 118
8 140 . 154
a 202 198
8
94
89
8 102 100
8 119 122
8
99 I14
56
51
8
8 263 310
29
8
o9
79
8
77
8 175 160
a 347 372
8 120 112
8
92
74
58
8
27.
8
91
97
116
-3
I16
-2
142
-I
84
0
112
-2
290
-10
65
-8
—6
75
-5
63
107
-4
66
—3
18
-2
58 ■
-I
55
0
141
I
86
3
222
-9
125
-8
96
-7
79
-4
75 .
-2
I18
-I
111
0
50
I
31
2
224
3
47
-8
79
-5
166
-3
58
-2
-I
57
110
I
66
3
58
-7
12
12
12
12
13
I
I
I
I
I
I
I
I
I
I
I
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
4
-5
-4
—I
6
4
—9
-7
6
6
6
6
7
7
-6
-4
-I
-2
-I
I
-5
B
9
9
9
9
9
9
9
9
10
10
10
11
II
11
12
118
129
142
77
108
298
54
79
80
97
58
a
50
8
58
8
64
B
139
88
a
8 229
8 124
8 109
8
89
8
58
3. I 16
8 122
55
a
8
47
8 223
8
68
74
8
8 169
44
8
8
52
8 116
8
70
8
66
I IOFo IOFc
8
S
8
8
8
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
55
67
' 62
92
133 130
54
8
54
73
59
42
84
77
50
63
45
30
375 351
39
23
1.26 124
132 ' 134
168 158
43
33
73
44
91
89
55
34
165 194
169 182
101 I17
154 167
57
41
85
90
50
28
303 314
SI
85
91
II I
54
45
327 322
■256 260
72
35
85
41
122 121
h
I:
—6
-3
0
I
.3
4
-9
—6
-4
-3
-2
-I
0
I
-9
-5
-4
-2
. 0
I
3
-8
-5
-4
-2
0
I
3
-6
-4
-2
I
2
-5
4
4
4.
4
4
4
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
7
7
7
7
7
7
7
8
8
a
8
8
9
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
9
9
9
9
9
9
9
9
9
9
9
138
48
98
.42
178
71
'63
93
196
.76
302
1.33
113
141
76
203
-125
98
46
277
60
66
96
123
57
66
122
52
107
100
55
213
96
59
130
23
83
12
190
93
70
66
183
60
288
127
129
153
66
211
135
35
34
283
16
47
93
I18
47
15
127
28
84
85
33
237
113
23
I
h
I;
-2
I
I
-6
I
-2
0
-3
-2
2
-8
-7
-5
—4
-2
-I
0
I
2
-8
-7
—6
-5
-4
-3
-2
-I
0
I
2
-7
—6
, -5
-3
9
9
9
10
10
1.1
11
1.2
0
0
I
I
I
I
I
I
I
I
I
2
2
—
?
2
2
2
2
2
2
2
2
3
3
3
3
I. IOFo IOFi9 287
9
61
9
74
9 128
9
55
9 155
9
63
9
56
10 341
10 Ito
10
69
10
54
10 181
10
84
10
94
10
65
10
51
10 .123
10 191
54
10
10
60
1O
94
10 105
IO
54
10 120
IO 158
10 130
10 I 1.3
10
73
10
52
10
81
to
70
10 281
to
62
273
39
60
92
21
I19
59
2
325
71
87
41
177
76
83
48
49
H 5
199
66
28
53
95
48
106
1.56
118
1.25
73
25
103
59
287
70
I
T r imethyLbenzene Thiourea Adduct
1 3 4
Observed and calculated structure factors:
Table 29.
(Continued)
Observed and calculated structure factors:
h
k
4
—5
-2
-I
0
I
-6
-5
-3
-2
I
3
-3
-I
0
I
2
-4
“3
-2
-I
-10
-8
-7
10
11
11
11
11
11
12
12
12
12
12
12
13
13
13
13
13
14
14
14
14
I
I
I
I
I
I
I
I
I
I
I
I
I
- 6
-5
-4
-3
-2
-I
0
I
2
3
I IOFo IOFc
h
k
I IOFo IOFc
91
91
93
87
264 251
65
53
87
83
175 175
84
42
146 148
9
57
85
100
64
92
60
67
68
41
46
28
89 109
128 130
61
36
83
76
94 ■ 88
58
47
47
19
61
78
44
57
80 100
56
82
250 278
95
80
40
44
161 165
290 304
36
6
45
41
266 243
44
37
4
5
-8
-7
—6
-5
-3
-2
-I
I
2
5
-10
-7
-5
-3
-2
-I
0
I
2
5
-10
-8
-7
—6
-5
—4
-2
-I
0
I
2
3
I
I
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
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
7
7
7
6
6
6
6
6
6
6
6
6
6
6
6
6
6
Cd
6
6
6
6
6
6
7
7
7
7
7
7
7
7
7
7
7
7
7
44
218
119
83
82
128
172
81
354
138
263
72
95
74
360
87
159
276
51
50
55
277
122
106
95
102
194
73
260
312
224
125
184
59
TrimetbyIbenzene Thiourea Adduct
h
4
24
5
221
-10
124
—6
I17
-5
I15
-4
163
175
-3
81
-2
-I
345
0
131
I
267
2
54
72
3
4
113
5
379
86
-8
-7
153
-5
256
-2
47
32
-I
29 .
0
305
I
98
2
102
3
51
-7
-5
I18
-4
201
-3
75
-2
253
293
-I
228
I
130
3
4
186
51
-7
k
I IOFo IOFc
h
48
67
38
' 67
37
57
90
82
84
61
I03
74
396 407
1.04. 176
173 164
96 101
108 112
50
88
112 ' H O
152 162
75 106
136 140
94 ■ 96
128 139
I10 107
47
54
135 135
124 131
153 152
134 147
48
61
119 115
67
45
532 516
227 214
73
90
45
72
163 180
69
13
123 121
—6
-3
-2
-I
0
I
3
4
-8
-7
—6
-3
-I
.0
I
4
-8
-6
-4
O
I
-7
—6
-5
-3
-I
I
3
-4
-2
-I
I
2
-3
4 7
4 7
5 7
5 7
5 7
5 7
5 7
5 7
5 7
5 7
5 7
5 7
5 7
5 7
5 7
6 7
6 7
6 7
6 '7
6'7
6 7
6.7
6 7
6 7
7 7
7 7
7 7
7 7
7 7
7 7
7 7
7 7
7 7
8 7
k
I IOFo IOFc
8 7
8 7
8.7
8 7
8 7
8 7
8 7
8 7
9 7
9 7
9 7
9 7
9 7
9 7
9 7
9 7
10 7
10 7
10 7
10 7
10 7
11 7
II 7
II 7
II 7
11 7
II 7
II 7
12 7
12 7
12 7
12 7
12 7
13 7
116
243
86
98
268
76
141
153
67
55
119
77
44
88
43
101
57
57
48
357
61
72
86
95
148
67
44
93
100
54
51
59
85
141
h
139
232
79
I II
274
77
153
171
43
7
129
59
19
84
29
I.13
9
65
21
372
57
39
85
85
128
66
2
90
91
33
46
41
59
139
k
-2 13
-I 13
0 13
-10
0
—6 0
-4 O
-3 0
-2 O
0 0
I 0
2 0
4 0
-9 I
-R I
-6 I
-4 I
-2 I
-I
I
0 I
I I
2 I
3 I
4 I
-3 2
-4 2
-3 2
-2 2
-I 2
0 2
I 2
2 2
4 2
:-9 3
-S 3
r
I IOFo IOFe
7
7
7
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
3
8
8
8
8
8
8
8
8
S
8
8
8
69
64
61
54
182
56
56
310
95
52
72
3»8
61
110
182
131
57
1.04
177
281
108
45
283
62
71
422
117
79
70
97
53
178
133
66
73
43
29
15
205
56
0
298
93
0
52
412
54
116
200
I43
67
98
175
275
11 I
26
299
33
75
44 I
125
70
70
6485
153
122
67
Table 29.
(Continued)
Observed and calculated structure_factors* __ ]rimethyI benzene Thiourea Adduct
k
-9
-6
-3
-2
-I
0
I
2
6
-8
-7
—6
-5
-+
-I
0
2
3
—8
-7
-6
-5
-4
-I
0
I
2
3
“6
-5
-4
-2
-I
2
8
8
8
8
8
a
8
8
8
9
9
9
9
9
9
9
9
9
10
10
10
10
10
10
10
10
10
10
II
II
11
11
II
II
I IOFo IOFc
h
k
76
40
65
92
106
97
65
23
468 458
65
66
52
58
I0 I 105
83
I II
78
71
74
92
120 138
190 192
355 370
23
46
85
72
245 258
109 105
72 . 84
77
83
64
75
98
I14
65
83
139 127
149 142
15
61
238 238
106 I 10
37
67
33
54
197 185
61
23
93
95
121
111
3
-7
—6
-2
-I
I
2
-6
-2
I
2
3
-2
-I
0
11
12
12
12
12
12
12
13
13
13
13
13
14
14
14
15
0
0
0
0
0
I
I
I
I
I
I
I
I
I
I
I
I
2
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
S
5
5
5
5
5
5
5
5
-2
—6
-2
0
3
6
-10
—9
-6
-5
-4
-3
-2
0
I
2
3
6
-9
I IOFo IOFc
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
O
6
6
6
6
6
6
6
6
Cd
121
77
60
93
287
50
83
68
80
49
78
75
96
106
47
65
72
44
192
84
245
83
83
167
54
51
44
107
919
173
HO
231
89
61
122
50
35
80
274
54
106
50
79
42
75
92
103
105
7
49
31
67
160
0
256.
66
74
176
35
62
48
HO
870
IT'S
118
216
96
45
h
I:
I IOFo IOFc
-7
—6
-5
-4
-3
-2
-I
O
I
2
3
4
6
-9
-8
-7
-6
-4
-3
-2
-I
O
I
2
2
2
2
2
2
2
2
2
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
2
3
6
-10
-9
-7
-6
-4
-2
-I
O
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
6
178
65
259
429
207
134
180
I 10
123
62
521
106
72 '
67
95
210
151
too
99
323
258
209
83
144
286
58
53
72
111
167
I19
299
87
I 10
209
63
263
449
206
162
155
24
132
68
516
154
60
61
110
246
178
101
I15
323
277
20 I
134
158
296
12
15
72
136
186
117
308
86
104
h
k
I IOFo IOFc
h
k
I IOFo IOF.-:
2
3
5
6
-10
-9
-7
—6
-5
-4
-2
-I
0
I
2
3
4
6
-7
-6
-5
-4
-2
-I
O
I
2
4
5
6
-9
-4
-2
-I
4
4
4
4
5
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
7
7
7
7
6
56
6 342
6
56
98
6
6
73
6 102
6
87
84
6
47
6
6
73
6 233
90
6
6 336
6 137
6 I10
59
6
6
52
6 ■ 91
6 118
52
6
6 215
6 257
47
6
6 243
97
6
6
58
72
6
62
6
6 283
72
6
6 143
6
94
58
6
6 133
87
357
20
99
65
87
103
76
86
92
225
59
339
148
112
77
60
98
136
72
233
251
50
231
94
63
75
7
297
BI
127
82
29
HO
I
2
4
5
—7
-5
-2
-I
0
I
3
4
5
-8
-7
7
7
7
7
8
8
8
8
8
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
—6
-5
-4
-3
-2
-I
I
2
5
—6
-5
-4
-3
-2
-I
0
I
a
8
8
8
9
9
9
9
9
9
9
9
9
9
9
10
to
10
10
10
10
10
10
2 10
3 10
353
46
70
50
90
185
339
51
43
99
67
106
181
59
74
80
76
147
55
41.9
56
140
172
92
89
63
49
70
269
71
73
60
83
77
357
50
91
19
91
173
313
43
13
88
49
1.24
181
67
4
66
79
125
50
413
10
154
196
5-1
92
54
7
83
256
72
77
67
80
73
1 3 6
h
Table 29.
(Continued)
Observed and calculated structure factors:
I:
I IOFo IOFc
h
k
0
I
2
3
4
5
■7
-10
-9
-a
-7
—6
-3
-2
-I
I
2
3
4
6
5
5
5
5
5
5
5
6
6
6
6
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
230 230
277 293
301 281
48
78
110 128
91
92
126 148
51
33
10
57
I 12 115
65
57
59 ■ 44
408 411
54
48
43
35
156 172
521 542
178 194
147 161
49
48
79
62
89 102
66 112
277 282
596 569
69
49
140 143
235 252
50
26
64
85
52
54
203 208
102
98
163 .178
-5
-3
-I
0
I
3
4
-9
-5
-3
-I
0
I
3
-8
—6
-I
0
I
2
4
6
-8
-5
-4
-3
-2
-I
0
I
3
4
8
a
8
8
8
8
a
9
9
9
9
9
9
9
10
10
10
10
10
-B
—6
-5
-4
-3
-2
-I
I
3
5
6
7
-7
—6
6
6
6
6
6
6
6
6
6
7
7
7
7
7
7
7
7
7
7
7
7
B
8
4
4
4
4
4
4
4
4
to
10
10
II
11
II
11
11
11
11
11
11
II
-7 12
-5 12
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
4
4
4
4
49
220
83
64
363
272
215
78
49
167
56
368
52
148
86
242
48
213
77
54
259
58
52
105
100
175
47
95
294
160
64
100
68
70
43
236
88
47
368
268
21 I
44
12
161
49
379
38
149
46
255
44
220
94
48
271 .
19
35
85
I19
159
40
90
313
170
61
104
47
29
k
T IOFo IOFc
h
k
I IOFo IOFc
12
12
12
12
12
3 12
-5 13
-3 13
I 13
—4 14
-3 14
-I 14
0 14
2 14
-I 15
—8 I
-7 ■ I
—6 I
-5 I
-4 I
-3 I
-2 I
-I
I
0 I
I I
3 I
4 I
5 I
7 I
-9 2
-6 2
-5 2
4 129 I14
4 '197 191
4
72
62
4
89 I15
87
4
92
4 I13 11.3
43
4
67
4 167 172
4
56
36
68
48
4
4
67 . 70
4
82
68
4 108 ' 116
4 I18 I12
4 119
99
5 104 115
5
62
94
5 371 39?
5 131 140
5 325 348
5 195 193
5 232 235
5 231 223
5 • 57
8
5 172 175
97
5 I04
5 594 604
5
73
54
5
78
87
5 194 175
5 153 173
91 III
5
5
I 10
132
5 466 473
-2
—1
0
I
2
3
6
7
-7
-5
-4
-3
-2
-I
0
I
2
3
4
6
7
-9
-8
-7
-5
-4
-3
-2
0
I
2
6
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
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
7
-3
4
5
5
5
h
-4
—3
-I
0
I
-4
-3
2
2
5
256
337
506
585
91
71
132
102
53
223
162
487
78
129
109
668
219
86
55
37
70
158
86
141
75
250
225
282
167
422
76
175
87
74
h
k
I IOFo IOFc
—6
-5
-4
-3
-2
—I
0
I
2
3
4
6
-7
-6
-4
-3
-2
-I
I
2
3
4
6
-9
-7
-5
-4
-3
■;.'tj7
-2
167
416 - -I
76
0
I
182
3
85
4
61
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
6
6
5
5
5
5
5
288
361
516
612
105
58
141
103
43
259
178
470
78
130
95
639
227
83
32
101
32
156
100
156
87
268
210
6
7
7
7
7
7
7
7
7
7
7
7
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
274
142
136
385
124
142
36
I14
130
I 18
280
213
I19
9»
288
85
176
488
189
90
85
75
59
74
147
69
163
109
100
134
281
77
263
12.7
277
1.77
132
405
111
1.26
32
89
142
135
277
242
136
II I
287
79
156
485
175
102
91
62
63
61
157
85
179
I02
76
123
274
70
277
136
137 I
h
TrimethyIbenzene Thiourea Adduct
Table 29.
(Continued)
Observed and calculated structure factors:
Trimethylbenzene Thiourea Adduct
h
k
h
-2
I
2
3
-9
-7
-4
-2
-I
0
I
2
3
3
3
3
4
4
4
4
4
4
4
4
5
5
5
-8
-7
-6
-5
-3
-I
0
I
2
-7
-6
-5
—3
5
5
5
5
5
5
6
6
6
6
I IOFo 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
112 104
88 tot
65
87
70
40
67
38
90
72
54
24
153 135
96
98
199 213
123 128
76
67
so
49
56
61
61
28
165 159
203 196
48
9
185 .209
49
74
100
96
51
56
68
31
83
72
195 181
h
k
-2
0
I
2
-7
-6
-3
-I
0
—6
-5
-4
-3
-2
-I
0
—6
-4
-2
0
-4
-2
-6
-4
6
6
6
6
7
7
7
7
7
8
8
8
8
8
8
8
9
9
9
9
10
to
I
I
I IOFo IOFc
10
1010
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
IO
11
11
148
72
64
59
142
67
127
50
45
52
56
e>5
161
60
61
149
57
87
63
54
58
61
77
65
157
80
69
61
127
39
131
II
10
30
12
59
136
35
20
145
52
50
21
29
47.
20
74
36
-3
—I
0
I
2
-7
—6
-5
-4
-3
0
I
-8
—6
-3
-I
'-"O
I
-8
-5
-4
-3
-I
0
k 'I
. IOFo IOFc
I
I
I
I
I
2
2
2
2
2
2
2
3
3
3
3
3
3
4
4
4
4
4
4
II 130
I1
88
I I 257
II
69
11
59
I1
57
II
74
It
67
II
54
II 167
II
56
II
96
II
71
II
58
II 207
II
96
II
97
II 104
79
II
II
52
II 102
II •2)7
II 122
II
56
h
133
I
89
-8
265
-7
58
-4
37
-I
0
37
67 '
I
45
-6
49
-5
157
'-3
40
-2
.99
-I
69
-4
89
-3
174
-2
83
-I
105
0
102
-5
57
-4
23
-6
92 . -2
203
0
I12
-5
58
-4
k ■ I IOFo IOFc
4
5
5
5
5
5
5
6
6
6
6
6
7
7
7
7
7
a
8
0
0
0
I
I
11
47
11
53
11
73
11
90
11
98
11 . 81
11
55
11
65
11 139
11
70
11
60
11
48
11
63
11
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MONTANA STATE UNIVERSITY LIBRARIES
StkS N378.W6318
RL
The X-ray crystallographic structure stu
3 1762 00512720 2
yain
N378
W6318
cop. 2