Structure and intermolecular interactions of N-(3,5-di-tert-butyl-4- hydroxybenzyl)thioureas

Article abstract of DOI:10.1007/s11176-005-0092-6

The molecular and crystal structure and the hydrogen bonding in crystal and in solutions of N-phenyl-N-(3,5-di-tert-butyl-4-hydroxybenzyl)thiourea and N-(3,5-di-tert-butyl-4- hydroxybenzyl)thiourea were studied by single crystal X-ray diffraction and IR s

Full text of DOI:10.1007/s11176-005-0092-6

Russian Journal of General Chemistry, Vol. 74, No. 11, 2004, pp. 1734 1740. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004,
pp. 1864 1870.
Original Russian Text Copyright
2004 by Bukharov, Litvinov, Gubaidullin, Chernova, Shagidullin, Nugumanova, Mukmeneva.
Structure and Intermolecular Interactions
of N-(3,5-Di-tert-butyl-4-hydroxybenzyl)thioureas
S. V. Bukharov, I. A. Litvinov, A. T. Gubaidullin, A. V. Chernova,
R. R. Shagidullin, G. N. Nugumanova, and N. A. Mukmeneva
Kazan State Technological University, Kazan, Tatarstan, Russia
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received November 10, 2002
Abstract The molecular and crystal structure and the hydrogen bonding in crystal and in solutions of
N-phenyl-N-(3,5-di-tert-butyl-4-hydroxybenzyl)thiourea and N-(3,5-di-tert-butyl-4-hydroxybenzyl)thiourea
were studied by single crystal X-ray diffraction and IR spectroscopy. The intermolecular interactions of these
compounds are essentially different.
Our previous study of 3,5-di-tert-butyl-4-hydroxy-
benzyl acetate I demonstrated the possibility of self-
association of sterically hindered phenols containing
in p-positions proton-acceptor functional groups cap-
able of hydrogen bonding [1]. In this work we studied
by single crystal X-ray diffraction and IR spectros-
copy the molecular and crystal structure of N-phenyl-
N-(3,5-di-tert-butyl-4-hydroxybenzyl)thiourea II and
N-(3,5-di-tert-butyl-4-hydroxybenzyl)thiourea III. We
also studied the system of hydrogen bonds in the crys-
tals and solutions of these compounds. Compounds II
and III were prepared from benzyl acetate I by the
following scheme:
t-Bu
t-Bu 2 3
O
O
1
4
HO
t-Bu
+ RHNCNH2
HO
CH RNCNH2
2
CH3
S
S
t-Bu
I
II, III
R = Ph (II), H (III).
An X-ray diffraction study of a single crystal of II
axis (Fig. 2). The amino group is accommodated
between the tert-butyl substituents of the neighboring
molecule and is sterically blocked by them. On the
showed that, despite the presence of bulky substitu-
1
ents at the N atom, the thiourea moiety remains
planar within 0.008(4) (Fig. 1). The phenyl substit-
uent at the N atom is virtually out of conjugation
other hand, the NH group is blocked by the phenyl
substituent at the N atom. Thus, the absence of hy-
2
1
1
with the thiourea moiety: The dihedral angle between
the phenyl and thiourea planes is 71.5(2) . The geom-
etries of the aromatic substituents and thiourea moi-
ety in II are usual (the main geometric parameters of
II are given in Tables 1 and 2). The molecules of II in
the crystal are linked by the hydrogen bonds O H S.
The parameters of the hydrogen bond are as follows:
drogen bonds involving the NH group in II is due to
its steric shielding.
2
Single crystal X-ray diffraction data for thioureas
substitutes at only one nitrogen atom are scarce. By
now, crystal structures have been determined only for
1
-thiocarbamoylimidazoline-2-thione [2] and N,N-di-
8
8
1
8
8
8
1
O H S (1 + x, y, z), O H 1.08, H S 2.44,
methylthiourea [3]. The molecules of these com-
pounds have a planar conformation stabilized by the
N H S intramolecular hydrogen bonds in the thio-
8
1
8
8
1
O
S 3.346(3)
,
O H S 141 . The chains of
hydrogen-bonded molecules are arranged along the 0X
1
070-3632/04/7411-1734 2004 MAIK Nauka/Interperiodica

STRUCTURE AND INTERMOLECULAR INTERACTIONS
1735
C16
C14
C15
C17
C21
O8
C22
C8
C7
C23
C12
C13
C9
C20
C6
C10
C19
C18
C5
C4
N1
C1
N2
C3
C12
S1
Fig. 1. Molecular geometry of II in the crystal.
urea moiety. In crystals, these molecules are linked by
intermolecular N H S bonds in infinite chains. The
absence of hydrogen bonds involving the amino group
in the crystal of II does not rule out the possibility of
their formation in solutions of II. This possibility was
examined by IR spectroscopy.
Table 2. Selected bond angles ( , deg) in the molecule
of II
Angle
Angle
7
8
8
9 8 14
C O H
124
C C C
120.8(3)
121.1(3)
111.3(4)
110.8(3)
110.4(3)
106.9(4)
111.1(4)
106.3(4)
110.7(4)
109.9(3)
110.5(3)
110.5(4)
107.8(4)
107.4(4)
118.8(4)
119.4(3)
121.8(4)
118.0(4)
120.9(4)
120.6(5)
120.0(4)
118.7(4)
1
1
3
4 9 8
C N C
122.9(4)
121.8(4)
115.3(3)
115
120
123
C C C
Comparison of the IR spectra of crystalline II with
the spectra of its solutions reveals characteristic dis-
1
1
18
18
1
6 10 11
C N C
C C C
3
1
6 10 12
C N C
C C C
1
2
6
10 13
C N H
C C C
Table 1. Bond lengths (d, ) in the molecule of II
1
2
2
2
11 10 12
C N H
C C C
1
2
11 10 13
H N H
C C C
Bond
d
Bond
d
1
1
1
2
12 10 13
S C N
124.4(4)
118.8(3)
116.8(4)
111.2(3)
120.8(4)
119.0(3)
120.2(4)
121.8(4)
116.8(3)
120.8(4)
122.4(4)
122.3(3)
114.9(4)
122.7(4)
117.3(4)
121.9(4)
C C C
1
1
8 14 15
S C N
C C C
1
1
7
8
S C
1.685(5)
1.376(5)
1.08
1.338(6)
1.480(6)
1.443(6)
1.344(7)
1.15
C C
1.406(5)
1.402(6)
1.536(6)
1.531(7)
1.542(7)
1.543(7)
1.535(7)
1.523(7)
1.537(6)
1.383(5)
1.388(6)
1.390(7)
1.372(7)
1.371(6)
1.391(7)
1
1
2
8 14 16
N C N
C C C
8
7
8
8
9
O C
C C
1
3
4
8
14 17
N C C
C C C
8
8
14
O H
C C
3
4
5
15 14 16
C C C
C C C
1
1
10 11
N C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
3
4
9
15 14 17
C C C
C C C
1
3
10 12
N C
5
4
9
16 14 17
C C C
C C C
1
18
1
10 13
N C
4
5
6
1 18 19
C C C
N C C
2
14 15
N C
5
6
7
1
18 23
C C C
N C C
2
1
14 16
N H
5
6
10
10
19 18 23
C C C
C C C
2
2
14 17
N H
0.98
7
6
18 19 20
C C C
C C C
3
4
18 19
C C
1.517(6)
1.382(5)
1.378(6)
1.396(6)
1.408(6)
1.534(5)
8
7
6
19 20 21
4
5
18 23
O C C
C C C
C C
8
7
8
20 21 22
4
9
19 20
O C C
C C C
C C
6
7
8
21 22 23
5
6
20 21
C C C
C C C
C C
6
7
21 22
7
8
9
18 23 22
C C
C C C
C C C
6
10
22 23
7
8
14
C C
C C C
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 11 2004

1736
BUKHAROV et al.
Fig. 2. System of hydrogen bonds formed by molecules of II in the crystal.
tinctions (Table 3). In going from solid II to its dilute
can be decomposed into two components at 3510 and
3432 cm . The spectrum of a concentrated solution
1
solutions in CCl or CHCl , a strong band of irregular
4
3
1
shape with maxima at 3510 and 3390 cm transforms
of II in CHCl (0.3 M) contains, along with the band
3
at 3639 cm 1 [ (OH free)], also a band at 3446 cm .
This band disappears on further dilution, which allows
its assignment to associated OH groups [ (OH
bonded)]. It should be noted that, in the spectra of
both solid sample and solutions, the frequencies
(NH ) and (NH ) well obey the Puranik relation-
1
into three well-resolved relatively strong bands at
1
3
3
644, 3522, and 3399 cm (in CCl ), or at 3639,
4
1
515, and 3393 cm (in CHCl ). Apparently, the
3
high-frequency peak in each triad should be assigned
to the vibrations of free OH groups [ (OH free)], and
the other two peaks, to
and of the NH groups,
as
s 2
as
2
s
2
respectively [4 6]. in this case, an asymmetric band
with the maximum at 3510 cm in the spectrum of
ship for thioamides [7]:
confirms their assignment.
= 1.214 as 542.5, which
s
1
the solid sample can be considered as a superposition
of the
(NH ) and (OH) bands. Indeed, this band
It is noteworthy that both (NH ) bands are weakly
2
as
2
1
Table 3. Frequencies (cm ) of characteristic vibrations and relative intensities of absorption bands of N-phenyl-N-(3,5-di-
tert-butyl-4-hydroxybenzyl)thiourea II
Medium
(OH free)
(OH bonded)
3432a
as(NH2)
s(NH2)
(NH2)
1580 s
1585 vs
(C=S)
1108 s
1161 s
KBr
3632 vw
3644 s
3639 m
3510 s, 3510a
3522 s
3515 m
3390 s
3399 s
3393 m
CCl4b
CHCl3
c
3446 w
a
c
1
b
4
Determined by decomposition of the experimental unsymmetrical band with a maximum at 3510 cm
.
C
(1 6) 10 M.
II
2
1
C
2
10
3
10 M.
II
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 11 2004

STRUCTURE AND INTERMOLECULAR INTERACTIONS
1737
1
Table 4. Frequencies (cm ) of characteristic vibrations and relative intensities of absorption bands of N-(3,5-di-tert-
butyl-4-hydroxybenzyl)thiourea III
Medium
KBr
(OH free)
as(NH2)
s(NH2)
(NH)
(NH2)
1602 vs
1603 vs
(CNH)
1560 vs
1511 vs
(C=S)
1154 s
1157 s
3632 vw, 3610 vs
3642 vs
3453 vs
3515 s
3513 m
3286 s
3408 s
3401 s
3191 s
3447/3430 m
3434/3422 m
a
CCl4
CHCl3b 3637 s
a
4
b
2
C
(1 6) 10 M.
C
3
10 M.
III
III
sensitive to the state of the substance. The shift of
The IR spectrum of a crystalline sample of III in
the range 3650 3000 cm 1 contains five strong bands.
The strongest peaks, as in the case of II, are unambig-
these bands in going from the crystal of II to its solu-
1
tion in CCl is 12 ( as) and 9 cm ( ), which can be
4
s
1
accounted for by nonspecific interactions. At the same
time, the (OH) band in going from the crystalline
uously assigned to (OH) (3610 cm ), as(NH2)
1
1
(3453 cm ), and (NH ) (3286 cm ) (Table 4)
s
2
state to solutions is significantly shifted to high fre-
[4 6]. The two remaining bands can be interpreted as
1
1
follows: the band at 3191 cm with a shoulder at
quencies (by 190 cm in CHCl ), which suggests
3
1
3
3
174 cm 1 is assignable to (NH), and the band at
participation of the OH group in an intermolecular
hydrogen bond. The energy of this hydrogen bond,
056 cm , to the overtone 2 (NH) enhanced by the
Fermi resonance. In solutions, the spectral pattern is
different. The spectrum of a solution of III in CCl4
according to the Iogansen frequency rule [8], is
1
1
7 kJ mol , i.e., it is a medium-strength hydrogen
contains three strong bands at 3642 (OH), 3515, and
bond.
1
3
3
408 cm (NH ) and a medium-intensity doublet at
2
447/3430 cm 1 [ (NH)]. Since the solution concen-
tration did not exceed 6 10 M, these frequencies
According to the above single crystal X-ray diffrac-
4
tion data, the second participant of the intermolecular
hydrogen bond is the thiocarbonyl group. Correspond-
refer to the free groups. The
(NH ) and (NH2)
1
as
2 s
ingly, the strong band at 1108 cm assignable to
bands, as in the case of II, obey the Puranik relation-
ship [7].
(C=S) [5] shifts to higher frequencies in going from
solid II to its solution (Table 3). The shift of this band
1
As seen from Table 4, the band of the secondary
thioamide group (NH) is a doublet both in the solid
state and in dilute solutions in inert solvents. This
may be due to the conformational nonuniformity of
the molecules of III, e.g., with the s-cis s-trans iso-
merism in the NH C=S moiety.
[
(C=S) 53 cm ] is abnormally large for such hy-
drogen bonds {for example, in the spectrum of benzyl
acetate I containing the OH O=C hydrogen bond [1],
1
1
the shift of (C=O) is 20 cm at (OH) 115 cm }.
This inconsistency may be caused by the following
factors. The break of intermolecular contacts between
molecules of II may cause certain changes in their
electronic structure, e.g., weakening of the conjuga-
tion between the lone electron pair of the tertiary
nitrogen atom and the C=S group and correspondingly
an increase in the multiplicity of the C=S bond, i.e.,
an increase in the contribution of structure B:
The frequencies of the free NH group in III are
2
close to those in II. However, in contrast to II, both
as(NH ) and (NH ) bands of III are appreciably
2
s
2
shifted in going from the solid phase to solutions in
1
CCl (by 62 and 122 cm , respectively), suggesting
4
participation of the NH group in the hydrogen bond-
2
ing. The medium exerts a still greater effect on the
+
N=C S
N C=S
vibration frequency of the secondary thioamide group
1
in III: (NH) in CCl is 256 cm . The (NH) band
A
B
4
also undergoes an appreciable low-frequency shift (by
1
The thioamide-II band [ (NH )], like the corre-
2
49 cm ) in going from solid III to its solution in
sponding
(NH ) and (NH ) bands, are weakly
as
2 s 2
CHCl (Table 4).
3
sensitive to the phase state of II and concentration of
These data show that the primary and secondary
thioamide groups in III are involved in intermolecular
hydrogen bonding. Since, as shown above, the thio-
carbonyl group in this case does not participate in
hydrogen bonding, the most probable proton acceptors
in the hydrogen bonds are the nitrogen and oxygen
its solution (Table 3).
Thus, the IR data for II are consistent with single
crystal X-ray diffraction data and suggest formation
of the intermolecular hydrogen bond OH S=C. The
primary thioamide group remains free.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 11 2004

1
738
BUKHAROV et al.
of the thioamide groups
atoms. The values of
primary NH groups form linear pairs with the hy-
2
suggest [4] that the secondary NH groups form cyclic
dimers C or cooperative hydrogen bonds D, and the
droxyl oxygen atoms. Thus, in III there is a complex
hierarchy of intermolecular hydrogen bonds:
H
H
H
H
ORNC(S)N H
ORNC(S)NH
H H
H
H
H NC(S)NHRO H NC(S)NRO
2
HNC(S)NRO
H
H
H
H
H
C
D
Bu-t
.
R = H C
2
Bu-t
Thus, we revealed essential differences between the
patterns of intermolecular interactions in 3,5-di-tert-
butyl-4-hydroxybenzyl-substituted thioureas II and III.
Compound II in the solid phase and in concentrated
solutions forms self-associates through OH S=C
hydrogen bonds, with the primary thioamide groups
remaining virtually free. With III, the pattern is oppo-
site: Both primary and secondary thioamide groups
participate in intermolecular hydrogen bonding,
whereas the hydroxy and thiocarbonyl groups are not
bonded with each other. These differences in the
pattern of self-association of III and II may be caused
by the above-noted specific features of the crystal
packing of II. Another cause may be different hybridi-
zation of the electron orbitals in the thiourea moiety
of II and III (different contribution of structures A
and B). The phenyl substituent in II may increase the
contribution of structure A, more active in hydrogen
bonding with the sterically shielded hydroxy group.
ties of 2633 reflections, including 1300 reflections
with I 3 , were measured at 20 C (Nonius CAD-4
diffractometer, graphite monochromator, MoK radia-
tion, -scanning,
27 ). No decrease in the intensi-
ty of three check reflections was observed during the
1
measurements; the absorption ( Mo 1.6 cm ) was
neglected.
The structure was solved by the direct method
using the SIR program [9] and refined first in the
isotropic and then in the anisotropic approximation.
All the hydrogen atoms were revealed from the differ-
ential electron density series, and their contributions
to structural amplitudes were taken into account with
fixed positional and isotropic thermal parameters
2
(Biso
6
). The final divergence factors are as fol-
lows: R 0.046, R 0.054 for 1486 unique reflections
W
with F2 3 . All the calculations were performed on
a DEC AlphaStation-200 computer using the MolEN
program package [10]. The PLATON 98 program was
used to make the molecular drawings and analyze the
crystal packing [11]. The atomic coordinates in the
structure of II are given in Table 5.
EXPERIMENTAL
The IR spectra were recorded on a Bruker Vector-
2 Fourier spectrometer. The H and C NMR spec-
1
13
2
N-Phenyl-N-(3,5-di-tert-butyl-4-hydroxybenzyl)-
thiourea II. A solution of 0.3 g of benzyl acetate I and
0.165 g of phenylthiourea in 5 ml of dimethyl sulfox-
ide was allowed to stand at room temperature for
a day. Then the mixture was poured into water, and
the precipitate was filtered off, washed with water,
dried, and recrystallized from acetone. A colorless
tra were taken on a Varian Gemini-200 spectrometer
1
13
(
200 MHz for H, 50 MHz for C). The residual
proton signals of the deuterated solvents were used as
references.
Single crystal X-ray diffraction analysis. Crystals
of II, C H N OS, are triclinic. At 20 C, a 10.100(4),
crystalline substance was obtained; mp 194.5 196 C,
2
2
30
2
1
b 10.210(9), c 10.490(4) ; 102.30(6) , 99.81(3) ,
yield 65%. H NMR spectrum (CDCl ), , ppm: 1.34
3
3
9
4.53(5) ; V 1034(1) 3, d
1.19 g cm , Z 2,
s (18H, CMe ), 5.15 s (1H, OH), 5.31 s (2H, CH ),
calc
3
2
space group P1. The unit cell parameters and intensi-
6.88 7.08 m (4H, Ar H), 7.25 7.44 m (3H, Ar H).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 11 2004

STRUCTURE AND INTERMOLECULAR INTERACTIONS
1739
Table 5. Atomic coordinates in the structure of II, equivalent isotropic thermal parameters of nonhydrogen atoms
3
3
B = 4/3 i=1 j=1(a a )B(i, j) ( 2), and isotropic thermal parameters of hydrogen atoms
i j
Atom
S1
x
y
z
B, Biso
Atom
H1
x
y
z
B, Biso
0.7389(1)
1.4275(3)
0.8112(3)
0.7242(4)
0.7599(4)
0.8566(4)
1.0098(4)
1.0835(4)
1.2248(4)
1.2889(4)
1.2167(4)
1.0750(4)
1.3043(4)
1.3918(5)
1.2074(5)
1.3910(5)
1.2887(4)
1.3820(4)
1.3690(5)
1.1849(5)
0.8256(4)
0.7287(5)
0.7470(5)
0.8576(5)
0.9524(5)
0.9376(4)
0.7034(1) 0.3487(2)
0.5356(3) 0.2453(3)
0.4561(3) 0.2732(3)
0.5004(3) 0.4629(4)
0.5440(4) 0.3600(5)
0.4901(4) 0.1561(4)
0.5071(4) 0.1752(4)
0.6326(4) 0.2278(4)
0.6499(4) 0.2505(4)
0.5326(4) 0.2211(4)
0.4038(4) 0.1663(4)
0.3947(4) 0.1424(4)
0.7910(4) 0.3041(5)
0.8033(4) 0.4414(5)
0.9002(4) 0.3198(6)
0.8241(5) 0.2048(5)
0.2768(4) 0.1373(5)
0.2887(5) 0.0381(5)
0.2549(4) 0.2662(5)
0.1512(4) 0.0761(6)
0.3203(4) 0.2878(4)
0.2165(4) 0.2133(5)
0.0858(5) 0.2248(5)
0.0606(5) 0.3080(5)
0.1644(5) 0.3821(5)
0.2966(4) 0.3728(5)
4.69(3)
4.54(9)
3.28(9)
4.6(1)
3.5(1)
3.7(1)
3.1(1)
3.3(1)
3.4(1)
3.1(1)
3.0(1)
3.1(1)
3.8(1)
4.8(1)
5.3(1)
5.2(1)
3.6(1)
4.5(1)
4.2(1)
5.1(1)
3.2(1)
4.2(1)
5.3(1)
5.3(1)
4.9(1)
4.0(1)
0.7155
0.7242
1.0165
1.4972
1.0202
0.6239
0.6652
0.8621
1.0670
1.0185
0.8219
0.8139
1.3145
1.4600
1.4406
1.2791
1.1389
1.1444
1.4681
1.3352
1.4431
1.4218
1.4699
1.3128
1.4433
1.3052
1.2244
1.1307
1.1140
0.5837
0.4050
0.7253
0.6272
0.2801
0.2500
0.0014
0.0465
0.1501
0.3926
0.5872
0.4018
0.7980
0.8997
0.7089
0.9927
0.8727
0.9028
0.7710
0.8236
0.9106
0.2073
0.3731
0.2792
0.3398
0.2287
0.0694
0.1667
0.1221
0.5528
0.4654
0.2524
0.282
6
6
6
6.0
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
8
2
O
H
1
5
N
N
H
2
8
H
1
9
C
H
0.1068
0.1431
0.1684
0.3319
0.4510
0.4228
0.1449
0.0611
0.5087
0.4762
0.4602
0.3689
0.3903
0.2212
0.1984
0.1023
0.2250
0.0034
0.0837
0.0683
0.3299
0.3356
0.0587
0.0329
0.1293
3
19
C
H
4
20
C
H
5
21
C
H
6
22
C
H
7
23
C
H
8
31
C
H
9
32
C
H
1
1
1
1
1
1
1
1
1
1
2
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
111
C
C
C
C
C
C
C
C
C
C
C
C
C
C
H
112
H
113
H
121
H
122
H
123
H
131
H
132
H
133
H
151
H
152
H
153
H
161
H
162
H
1
1
1
71
72
73
H
H
H
N-(3,5-Di-tert-butyl-4-hydroxybenzyl)thiourea
III was prepared similarly from 0.3 g of benzyl acetate
I and 0.1 g of thiourea in 5 ml of dimethyl sulfoxide.
search (project no. 00-03-40133) on the base of the
Laboratory of Diffraction Methods, Arbuzov Institute
of Organic and Physical Chemistry, Kazan Scientific
Center, Russian Academy of Sciences.
1
Yield 50%, mp 196 197 C (197 198 C [12]). H
NMR spectrum (acetone-d ), , ppm: 1.42 s (18H,
6
CMe ), 4.62 s (2H, CH ), 6.03 s (1H, OH), 6.57 s
REFERENCES
3
2
1
3
(
2H, NH ), 7.20 s (2H, Ar H), 7.36 s (1H, NH).
C
2
NMR spectrum (acetone-d6), , ppm: 30.34 (CMe ),
1. Bukharov, S.V., Pod yachev, S.N., Syakaev, V.V.,
Litvinov, I.A., and Gubaidullin, A.T., Zh. Obshch.
Khim., 2001, vol. 71, no. 10, p. 1658.
C
3
3
3
5.12 (CMe ), 49.68 (CH N), 125.48 (C ), 130.24
C ), 138.32 (C ), 154.06 (C ), 185.16 (C=S). Found,
3 2
4
2
1
(
%
: C 65.53; H 9.06; N 9.23; S 10.56. C H N OS.
1
6
26
2
2. Valle, G., Cojazzi, G., Busetti, V., and Mammi, M.,
Calculated, %: C 65.26; H 8.90; N 9.51; S 10.89.
Acta Crystallogr., Sect. B, 1970, vol. 26, no. 5, p. 468.
3
. Pathirana, H.M.K.K., Weiss, T.J., Reibenspies, J.H.,
Zingaro, R.A., and Meyers, E.A., Z. Kristallogr.,
ACKNOWLEDGMENTS
1
994, vol. 209, no. 8, p. 698.
The X-ray diffraction study was performed at the
Department of X-ray Diffraction Studies, Center for
Collective Use, Russian Foundation for Basic Re-
4. Bellamy, L.J., Advances in Infrared Group Frequen-
cies, London: Methuen, 1968.
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1740
BUKHAROV et al.
5
6
. Rao, C.N.R., Chemical Applications of Infrared Spec- Viterbo, D., Acta Crystallogr., Sect. A, 1991, vol. 47,
troscopy, New York: Academic, 1963.
no. 4, p. 744.
1
1
1
0. Straver, L.H. and Schierbeek, A.J., MolEN. Structure
Determination System, Nonius B.V., 1994, vol. 1.
. Nakanishi, K., Infrared Absorption Spectroscopy,
Tokyo: Nankido, 1962.
1. Spek, A.L., Acta Crystallogr., Sect. A, 1990, vol. 46,
7
8
. Puranik, R., Nature, 1961, vol. 191, no. 4790, p. 796.
no. 1, p. 34.
. Iogansen, A.V., Spectrochim. Acta (A), 1999, vol. 55,
nos. 7 8, p. 1585.
2. Gorbunov, D.B., Voznesenskii, V.N., Ershov, V.V.,
and Nikiforov, G.A., Izv. Ross. Akad. Nauk, Ser.
Khim., 1994, no. 1, p. 98.
9
. Altomare, A., Cascarano, G., Giacovazzo, C., and
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 11 2004