Tetraphenyl-and tetratolylantimony complexes with N,N- dialkyldithiocarbamate ligands: Synthesis, X-ray diffraction analysis, and 13C and 15N CP/MAS NMR studies

Article abstract of DOI:10.1134/S1070328406060017

Crystalline tetraphenylantimony and tetratolylantimony complexes with N,N-dialkyldithiocarbamate ligands [Sb(C₆H₅) ₄(S₂CNR₂)] (R = CH₃, C ₂H₅, and C₃H₇

Full text of DOI:10.1134/S1070328406060017

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2006, Vol. 32, No. 6, pp. 387–396. © Pleiades Publishing, Inc., 2006.
Original Russian Text © V.V. Sharutin, M.A. Ivanov, A.V. Gerasimenko, A.V. Ivanov, A.P. Pakusina, O.N. Antsutkin, W. Forsling, G. Gröbner, 2006, published in Koordinatsion-
naya Khimiya, 2006, Vol. 32, No. 6, pp. 403–412.
Tetraphenyl- and Tetratolylantimony Complexes
with N,N-Dialkyldithiocarbamate Ligands: Synthesis,
X-Ray Diffraction Analysis, and 13C and 15N CP/MAS NMR
Studies
V. V. Sharutina, M. A. Ivanovb, A. V. Gerasimenkoc, A. V. Ivanovb, A. P. Pakusinaa,
O. N. Antsutkind, W. Forslingd, and G. Gröbnere
Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
a
b
Institute of Geology and Nature Management, Amur Scientific Center, Far East Division, Russian Academy of Sciences,
Blagoveshchensk, Russia
c
Institute of Chemistry, Far East Division, Russian Academy of Sciences, pr. Stoletiya Vladivostoka 159,
Vladivostok, 690022 Russia
d
Luleä University of Technology, S-971 87, Luleä, Sweden
e
Umeä University, S-901 87, Umeä, Sweden
Received April 28, 2005
Abstract—Crystalline tetraphenylantimony and tetratolylantimony complexes with N,N-dialkyldithiocarba-
mate ligands [Sb(C6H5)4(S2CNR2)] (R = CH3, C2H5, and C3H7 and R2 = (CH2)6) were synthesized by ligand
exchange reactions and studied by 13C and 15N CP/MAS NMR spectroscopy. X-ray diffraction analysis
revealed that the complex [Sb(n-CH3–C6H4)4{S2CN(C3H7)2}] exists as the single molecular form, while
[Sb(C6H5)4{S2CN(CH2)6}] exists as two molecular conformers. The 13C and 15N signals were assigned to the
positions of the atoms in the isomeric structures [Sb(C6H5)4{S2CN(CH2)6}] in terms of different degrees of
double bonding in the formally single =N−C(S)S– bond.
DOI: 10.1134/S1070328406060017
Organoantimony compounds are of interest as bio- taphenylantimony and bis(N,N-dialkyldithiocarbam-
cides, fungicides, components of catalysts, antioxi- ato-S,S')triphenylantimony.
dants, etc. [1]. That is why the synthesis of new orga-
Synthesis of (N,N-dipropyldithiocarbamato-
S,S')tetra(p-tolyl)antimony(V) (V). A solution of
penta(p-tolyl)antimony (0.65 g) in benzene was added
to a solution of bis(N,N-dipropyldithiocarbamato-
S,S')tri(p-tolyl)antimony (0.50 g) in benzene. The
reaction mixture was heated at 90°ë for 1 h and
cooled. The solvent was removed by evaporation and
the residue was recrystallized from toluene–heptane
(1 : 1). The yield of complex V was 0.90 g (78%),
Tm = 151°ë.
noantimony compounds and investigations of their
structures and properties are important lines of modern
coordination chemistry.
In this study, we obtained heteroligand complexes
of tetraphenyl-[Sb(C6H5)4(S2CNR2)] (R = CH3 (I),
C2H5 (II), and C3H7 (III) and R2 = (CH2)6 (IV)) and
tetra(p-tolyl)antimony [Sb(n-CH3–C6H4)4{S2CN(C3H7)2}]
(V) and studied them by 13C and 15N CP/MAS NMR
spectroscopy. Complexes IV and V were structurally
characterized by X-ray diffraction data. Conforma-
tional isomerism was discovered in complex IV: its unit
cell includes two molecular conformers of the complex.
The 13C and 15N signals were assigned to the structural
positions of the respective atoms of the dithiocarbamate
groups in the resolved molecular isomers of
complex IV.
For C35H42NS2Sb
anal. calcd. (%):
Found (%):
63.44;
63.06;
H, 6.34;
6.13;
2.11.
2.03.
IR (ν, cm–1): 1260 s, 1200 s, 1140 s, 1100 s, 1010 m,
910 m.
EXPERIMENTAL
(N,N-Dipropyldithiocarbamato-S,S')tetraphenyl-
Complexes I and II were synthesized as described antimony(V) (III) was obtained analogously. The
in [2, 3] and by ligand exchange reactions from pen- yield of complex III was 83%, Tm = 141°ë.
387

388
SHARUTIN et al.
π/2pulse durations were 5.4/3.5 to 5.0 µs; the
For C31H34NS2Sb
anal. calcd. (%):
Found (%):
1H−13C/1H–15N contact times were 1.5/1.5 to 2.5 ms;
the pulses were spaced at 3.0 to 8.0/3.0 to 5.0 s. Isotro-
pic 13C and 15N chemical shifts d (ppm) are referenced
to a line of crystalline adamantane used as the external
standard (δ = 38.56 ppm relative to tetramethylsilane
[5]) and to crystalline NH4Cl, respectively (δ = 0 ppm;
–341 ppm on the absolute scale [6, 7]). The width of the
reference line at δ = 38.56 ppm (2.4 Hz) for crystalline
adamantane served as an indicator of the magnetic field
uniformity.
61.39;
61.27;
H, 5.61;
H, 5.74;
N, 2.31.
N, 2.22.
IR (ν, cm–1): 1480 s, 1200 s, 1140 s, 1105 s, 1050 m,
1000 m.
(N,N-Cyclohexamethylenedithiocarbamato-
S,S')tetraphenylantimony(V) (IV) was synthesized
by a reaction between aqueous solutions of tetraphenyl-
antimony chloride and Na{S2CN(CH2)6} · 2H2O and
recrystallized from benzene–heptane (1 : 1) as
described in [2, 3]. The yield of complex IV was 57%,
Tm = 153°ë.
The δ values were corrected for drift of the magnetic
field strength during the measurements (its frequency
equivalents
for
the
13ë/15N
nuclei
were
0.098/0.033 Hz/h). The chemical shifts and the inte-
grated intensity ratios for overlapping signals in the 13C
NMR spectra were additionally refined by fragment-
by-fragment mathematical modeling with consider-
ation of the line positions and widths and the contribu-
tions from the Lorentz and Gauss components to the
line shapes.
For C31H32NS2Sb
anal. calcd. (%):
Found (%):
61.59;
61.44;
H, 5.30;
H, 5.17;
N, 2.32.
N, 2.14.
IR (ν, cm–1): 1270 s, 1200 s, 1160 s, 1060 s, 970 s,
950 s, 880 s.
X-ray diffraction analysis of complexes IV and V
was performed on a Bruker SMART 1000 CCD diffrac-
tometer (prismatic single crystals; MoKα radiation,
λ = 0.71073 Å, graphite monochromator; crystal–
detector distances 50 and 45 mm) at 296(2) and 173(1) K,
respectively. Reflections were collected in sets com-
posed of 906, 600, and 350 frames for ϕ = 0°, 90°, and
180°, respectively. In the ω scan mode, the scan step
was 0.2° and the frame exposure time was 10 s. Absorp-
tion corrections were applied from the indices of the
equivalent reflections. Structures IV and V were solved
by the direct method and refined by the least-squares
method in the full-matrix anisotropic approximation
(on F2) for non-hydrogen atoms. The hydrogen atoms
were located geometrically and refined in the rider
model. The collected data were edited and the unit cell
parameters were refined with the SMART and SAINT-
Plus programs [8]. Calculations for structure determi-
nation and refinement were performed with the
SHELXTL/PC programs [9].
The starting sodium dialkyldithiocarbamates were
characterized by 13ë and 15N CP/MAS NMR spectros-
copy:
Na{S2CN(CH3)2} · xH2O (Aldrich). 13ë NMR,
δ: 209.7 (51)*; 207.4 (43)* (–S2CN=); 47.5 (39)*;
47.0 (31)* (–CH3). 15N NMR, δ: 116.7 (=N–).
Na{S2CN(C2H5)2} · 3H2O (Fluka). 13ë NMR,
δ: 206.5 (51)* (–S2CN=); 48.6 (71)* (=NCH2–); 13.2
(–CH3). 15N NMR, δ: 139.1 (=N–).
Na{S2CN(C3H7)2} · H2O. 13ë NMR, δ: 208.3
(−S2CN=); 59.4, 57.9 (1 : 1) (=NCH2–); 22.3, 21.5
(1 : 1) (–CH2–); 12.6, 11.5 (1 : 1) (–CH3).
Na{S2CN(CH2)6} · 2H2O. 13ë NMR, δ: 206.3
(−S2CN=); 60.3, 55.5 (1 : 1) (=NCH2–); 29.8, 27.0,
26.2, 24.9 (1 : 1 : 1 : 1) (–CH2–). 15N NMR, δ: 135.2
(=N–).
IR spectra were recorded on a Hitachi-215 spec-
trometer (Nujol, NaCl plates).
13C and 15N MAS NMR spectra were recorded on
CMX-360 (Varian/Chemagnetics Infinity-Plus) and
CMX-400 pulse spectrometers (Chemagnetics Infinity)
operating at 90.52 and 40.59 MHz (superconducting
magnets with B0 = 8.46 and 9.40 T, respectively; Fou-
rier transform). The 13C–1H and 15N−1H cross polariza-
tion techniques were used; 13C–1H and 15N−1H dipolar
interactions were suppressed by proton decoupling in a
magnetic field with the corresponding proton resonance
frequency [4].
In 13C/15N MAS NMR experiments, samples
(~70/~350 mg) of the complexes were packed into
ZrO2 rotors 4.0/7.5 mm in diameter. The spinning rates
were 8500 to 9800/3450 to 3760(1) Hz; the number of
scans was 4620 to 10 000/2600 to 3700; the proton
Selected crystallographic parameters of structures
IV and V and a summary of data collection and refine-
ment are given in Table 1. Atomic coordinates and ther-
mal parameters are listed in Table 2. Bond lengths and
angles are given in Table 3.
RESULTS AND DISCUSSION
In this study, we proposed a new method for the syn-
thesis of tetraarylantimony N,N-dialkyldithiocarbam-
ates by treating bis(N,N-dialkyldithiocarbamato-
S,S')triarylantimony with pentaarylantimony in a solu-
tion of an aromatic hydrocarbon:
Ar5Sb + Ar3Sb(S2CNR2)2
2Ar4SbS2CNR2,
13 14
Ar = Ph and n-CH3–C6H4; R = CH3, C2H5, and C3H7.
*Refers to the asymmetric C– N doublets, Hz.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

TETRAPHENYL- AND TETRATOLYLANTIMONY COMPLEXES
389
Table 1. Selected crystallographic parameters and a summary of data collection and refinement for structures IV and V
Value
Parameter
IV
V
M
604.45
Monoclinic
P21/c
662.57
Crystal system
Orthorhombic
Space group
Pbca
a, Å
18.804(3)
10.324(1)
29.614(4)
91.979(2)
5746(1)
12.215(1)
b, Å
19.102(2)
c, Å
27.654(3)
β, deg
V, Å3
90
6452(1)
Z
8
8
ρ calcd, g/cm3
µ, mm–1
1.397
1.364
1.008
1.125
F(000)
2464
2736
Crystal shape (size, mm)
θ scan range, deg
Ranges of h, k, and l indices
Number of measured reflections
Number of independent reflections
Number of reflections with I > 2σ(I)
Number of parameters refined
R factors (F2 > 2σ(F2)
R factors for all reflections
GOOF
Prism (0.40 × 0.30 × 0.20)
3.80–28.01
Prism (0.32 × 0.17 × 0.10)
3.55–26.02
–24 ≤ h ≤ 23, –10 ≤ k ≤ 13, –37 ≤ l ≤ 39 –15 ≤ h ≤ 10, –20 ≤ k ≤ 23, –33 ≤ l ≤ 34
35552
34088
6338 (Rint = 0.060)
4699
13764 (Rint = 0.0381)
10784
631
358
R1 = 0.0443, wR2 = 0.0892
R1 = 0.0623, wR2 = 0.0957
1.076
R1 = 0.0482, wR2 = 0.1037
R1 = 0.0721, wR2 = 0.1156
1.031
Residual electron density (min/max),
–0.944/0.764
–0.698/1.362
e/Å3
Note that antimony derivatives of the general for- increases the shielding of both carbon and nitrogen
mula Ar4SbX (X is the monodentate organic or inor- nuclei.
ganic ligand) have been obtained analogously in [10].
The signals for the =NC(S)S– fragment are structur-
The 13C NMR spectra of crystalline antimony com- ally most informative. The 13C NMR spectra of com-
plexes I–IV (Fig. 1; Table 4) show resonance signals plexes I–III show singlets for this fragment
due to the =NC(S)S– groups and the alkyl substituents (Figs. 1a−1c; Table 4), while the corresponding signal
at the N atom in the dithiocarbamate ligands and signals in the spectrum of complex IV appears as a 1 : 1 dou-
due to the =CH– and =ë= fragments in four aromatic blet (Fig. 1d). Therefore, complexes I–III exist in sin-
rings C6H5–. The considerable broadening of the sig- gle molecular forms, while complex IV in the crystal-
nals for the C atoms directly bound to the metal (δ 163– line state is represented by two isomers. This correlates
166 ppm) is due to interactions with “quadrupole” 121Sb with the presence of a single signal in the 15N NMR
(I = 5/2, 57.25 at %) and 123Sb nuclei (I = 7/2, spectra of complexes II and III (Figs. 2a, 2b) and two
42.75 at %). A comparison of the 13C and 15N chemical signals of equal intensities in the spectrum of complex
shifts for the =NC(S)S– groups in antimony complexes IV (Fig. 2c). To verify the existence of the isomeric
and the corresponding sodium dithiocarbamates (Dtc) forms, we carried out X-ray diffraction analysis of
suggests that the covalent bonding of Dtc ligands structure IV.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

390
SHARUTIN et al.
4
Table 2. Atomic coordinates (×10 ) and isotropic equivalent thermal parameters Uequiv for structures IV and V
Atom
x
y
z
U
, Å2 Atom
x
y
z
U
, Å2
equiv
equiv
IV
Sb(1)
Sb(2)
S(1)
4692.8(1)
9845.0(1)
4245.0(5)
3665.0(5)
9321.5(6)
9028.6(6)
3020(2)
8314(2)
3586(2)
2931(2)
2484(2)
1781(3)
1854(3)
1953(2)
2389(2)
4768(2)
4643(4)
4668(4)
4832(3)
4959(3)
4920(2)
5393(2)
5378(2)
5782(3)
6174(3)
6191(2)
5815(2)
3768(2)
3688(2)
3098(3)
2595(3)
2664(2)
3252(2)
5507(2)
5450(2)
6018(2)
6644(3)
6708(3)
6139(2)
8837(2)
8117(3)
7557(4)
6899(4)
2715.2(2) 3685.53(7) 0.03986(7) C(36)
4897.9(2) 3755.63(7) 0.03796(6) C(37)
215.3(8) 3638.8(3) 0.0473(2) C(38)
2099.6(9) 4283.5(3) 0.0528(2) C(39)
7351.4(8) 3728.8(3) 0.0551(2) C(40)
5502.8(9) 4465.5(3) 0.0561(2) C(41)
6970(4)
7226(4)
6705(8)
6457(8)
7270(6)
5084(3)
4191(4)
4354(5)
5427(6)
6339(5)
6153(4)
2954(3)
2758(3)
1524(4)
472(4)
4010(3)
4507(3)
4681(2)
3116(1)
2772(1)
2365(1)
2290(2)
2624(2)
3032(1)
3997(1)
4449(1)
4622(2)
4343(2)
3895(2)
3723(1)
3441(1)
3624(2)
3418(2)
3035(2)
2847(2)
3048(1)
4139(1)
4068(1)
4304(1)
4616(1)
4687(1)
4450(1)
0.159(4)
0.130(2)
0.102(2)
0.0464(8)
0.068(1)
0.086(2)
0.079(1)
0.071(1)
0.0567(9)
0.0418(7)
0.0537(9)
0.071(1)
0.077(1)
0.069(1)
0.0557(9)
0.0491(8)
0.065(1)
0.093(2)
0.101(2)
0.090(2)
0.065(1)
0.0427(7)
0.0531(9)
0.067(1)
0.072(1)
0.072(1)
0.0563(9)
7837(3)
S(2)
10369(2)
10278(2)
10595(3)
11000(3)
11088(2)
10783(2)
10035(2)
10219(2)
10294(2)
10200(2)
10024(2)
9940(2)
S(3)
S(4)
N(1)
–90(3)
7689(3)
660(3)
4045(1)
4326(1)
3992(1)
3822(2)
3386(2)
3407(2)
3479(2)
3958(2)
4265(2)
3909(1)
4355(2)
4510(2)
4231(2)
3796(2)
3624(2)
3129(1)
2749(1)
2382(1)
2378(2)
2746(2)
3123(1)
3236(1)
2833(1)
2547(2)
2658(2)
3048(2)
3340(2)
4183(1)
4479(1)
4766(1)
4753(2)
4457(2)
4175(1)
4187(1)
4090(2)
3720(2)
3845(3)
0.0526(7) C(42)
0.0683(9) C(43)
0.0448(8) C(44)
N(2)
C(1)
C(2)
–1356(4)
–1299(5)
–590(5)
850(5)
0.066(1)
0.079(1)
0.087(1)
0.089(2)
0.085(2)
0.072(1)
C(45)
C(46)
C(47)
C(48)
C(49)
C(50)
C(3)
C(4)
C(5)
C(6)
1305(5)
402(4)
645(4)
C(7)
1869(3)
4421(3)
3493(4)
3169(6)
3803(7)
4729(6)
5039(4)
5630(3)
4983(4)
5309(4)
6302(5)
6956(4)
6630(3)
V
C(8)
4699(3)
4976(4)
6237(5)
7216(4)
6965(4)
5707(4)
2445(3)
3239(4)
2935(5)
1841(5)
1036(5)
1344(4)
3035(3)
2341(4)
2558(5)
3428(6)
4118(5)
3934(4)
2074(3)
1059(3)
728(4)
0.0532(9) C(51)
8815(2)
C(9)
0.103(2)
0.129(3)
0.098(2)
0.079(1)
0.065(1)
C(52)
C(53)
C(54)
C(55)
C(56)
8391(2)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
7739(2)
7513(3)
7929(3)
8581(2)
0.0459(8) C(57)
0.0586(9) C(58)
10776(2)
11404(2)
12027(2)
12016(3)
11406(3)
10779(2)
0.077(1)
0.080(1)
0.074(1)
C(59)
C(60)
C(61)
0.0571(9) C(62)
0.0488(8)
0.061(1)
0.079(1)
0.094(2)
0.088(2)
0.063(1)
Sb
7953.7(2) 2438.9(1) 3507.74(7) 0.02823(5)
9556.2(7) 3343.2(5) 3924.9(3) 0.0382(2)
8493.6(7) 2173.7(4) 4448.1(3) 0.0334(2)
S(1)
S(2)
N
9389(2)
9174(2)
9055(3)
7864(4)
7473(4)
10054(3)
11260(3)
11971(3)
6953(3)
6898(3)
6248(3)
5647(3)
3263(1)
2960(2)
2948(2)
3075(2)
3792(2)
3905(2)
3741(2)
4394(2)
3292(2)
3912(2)
4456(2)
4409(2)
4888(1)
4465(1)
5353(1)
5481(2)
5449(2)
4916(1)
4967(1)
4972(2)
3787(1)
3526(1)
3691(1)
4113(1)
0.0310(6)
0.0296(7)
0.0410(9)
0.068(1)
0.077(2)
0.0395(9)
0.045(1)
0.058(1)
0.0325(8)
0.0359(8)
0.0394(9)
0.0390(9)
C(1)
0.0434(7) C(2)
0.0535(9) C(3)
0.066(1)
0.075(1)
0.078(1)
0.061(1)
C(4)
C(5)
C(6)
C(7)
1407(5)
2420(5)
2759(4)
6923(3)
8890(5)
8711(7)
8015(8)
0.0508(8) C(11)
0.094(2)
0.123(2)
0.138(3)
C(12)
C(13)
C(14)
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TETRAPHENYL- AND TETRATOLYLANTIMONY COMPLEXES
391
Table 2. (Contd.)
Atom
x
y
z
U
, Å2 Atom
x
y
z
U
, Å2
equiv
equiv
C(15)
C(16)
C(17)
C(21)
5693(3)
6331(3)
4954(3)
9249(2)
3778(2)
3226(2)
5012(2)
1715(2)
1676(2)
1224(2)
790(2)
4364(1)
4203(1)
4284(2)
3310(1)
3508(1)
3316(1)
2933(1)
2744(1)
2926(1)
2716(1)
2773(1)
2580(1)
0.0397(9) C(33)
0.0392(9) C(34)
8926(3)
8015(3)
7072(3)
7034(3)
8038(3)
6676(2)
6901(2)
6095(3)
5022(3)
4779(2)
5593(3)
4153(3)
3364(2)
3339(2)
3042(2)
2788(2)
3623(2)
1668(1)
988(2)
2112(1)
1816(1)
2001(1)
2475(1)
1308(1)
3534(1)
3682(1)
3704(1)
3578(1)
3436(1)
3417(1)
3575(1)
0.0370(8)
0.0360(8)
0.0444(9)
0.0404(9)
0.051(1)
0.054(1)
C(35)
0.0293(7) C(36)
0.0363(8) C(37)
0.0414(9) C(41)
0.0374(9) C(42)
0.0375(9) C(43)
0.0338(8) C(44)
C(22) 10294(3)
C(23) 11062(3)
C(24) 10812(3)
0.0261(7)
0.0292(7)
0.0328(8)
0.0295(7)
0.0286(7)
0.0302(8)
0.0412(9)
C(25)
C(26)
9759(3)
8997(3)
815(2)
485(2)
1283(2)
288(2)
642(2)
C(27) 11643(3)
0.053(1)
C(45)
1325(2)
1835(2)
76(2)
C(31)
C(32)
7940(2)
8888(3)
2827(2)
3115(2)
0.0306(7) C(46)
0.0367(8) C(47)
Structure IV is made up of two crystallographically bond in the former case (“contamination” of the
independent molecules [Sb(C6H5)4{S2CN(CH2)6}] sp2-hybridized state of the N atom with the sp3-one).
(Fig. 3; Table 3). In either molecule, the antimony atom However, one of the carbon atoms (C(7) and C(38)) in
is in the distorted octahedral environment [C4S2]. In the both C2NC(S)S fragments deviates from its plane.
equatorial plane, the Sb atom coordinates the Dtc
A comparative analysis of the X-ray diffraction and
ligand through two S atoms and two most firmly bound
NMR data revealed a structural similarity of molecules
phenyl fragments. Two other, looser phenyl fragments
A and B and, nevertheless, allowed them to be classi-
are in the axial positions. The axial angles CSbC appre-
fied as conformational isomers (when a polyatomic
molecular system reaches equilibrium in two or more
ciably deviate from 180° in both molecules (169.0° and
169.6°).
energy-close configurations). The most substantial dif-
The bidentate coordination of the Dtc ligands gives ferences between the conformers under discussion are
rise to four-membered chelate rings SbS2C. Although in the dithiocarbamate ligands. In molecule A, the Dtc
chelate rings of this type are usually planar, the torsion ligand is coordinated in the anisobidentate manner
angles in the fragment SbS2C of structure IV indicate since one Sb–S bond (2.717 Å) is stronger than the
its substantial nonplanarity. The dihedral angles other (2.741 Å) to within the error of determination. In
between the SbSC planes are 164.0° (Sb(1) in molecule contrast, this ligand in molecule B is virtually isobiden-
A) and –168.3° (Sb(2) in molecule B). The dihedral tate (Sb–S 2.721 and 2.724 Å) and the bonds are gener-
angles between the SbS2 and CS2 planes are 160.9° (A) ally stronger (Table 3). The strengths of the correspond-
and –166.1° (B). Thus, the four-membered chelate ing carbon–carbon bonds (C(3)–C(4) and C(36)–C(37),
rings are folded along both the diagonals S–S and C(4)–C(5) and C(35)–C(36)) in the cyclic fragments
Sb–C. The distance between the opposite S atoms N(CH2)6 of molecules A and B somewhat differ as well
(S···S 2.960 and 2.965 Å) are appreciably shorter than (Table 3). The seven-membered ring in molecule B is
the Sb···C distance (3.129 and 3.131 Å). In the six- also more distorted because of the larger scatter of the
membered ë6ç5 rings, the C–C bond lengths range C–C bond lengths (1.442–1.553 Å) as compared to that
from 1.34 to 1.396 Å and the CCC angles are close to in molecule A (1.501–1.522 Å).
120°, which is characteristic of the sp2-hybridized
Structure V consists of a single independent mole-
orbitals of the C atom (117.2°–121.9°).
cule [Sb(n-CH3–C6H4)4{S2CN(C3H7)2}] (Fig. 4;
In dithiocarbamate ligands, the N–C(S)S bond is Table 3). The molecular structures of complexes V and
substantially shorter than the N–CH2 bond, which sug- IV are similar. The polyhedron [SbC4S2] of the anti-
gests a partially double character of the formally single mony atom is a distorted octahedron. Its equatorial
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

392
SHARUTIN et al.
Table 3. Bond lengths d, bond angles ω, and torsion angles ϕ in complexes IV and V
d, Å
Bond
d, Å
d, Å
d, Å
Bond
Bond
Bond
IV
Molecule A
Molecule B
Molecule A
MoleculeB
Sb(1)–C(8)
Sb(1)–C(14)
Sb(1)–C(20)
Sb(1)–C(26)
Sb(1)–S(1)
Sb(1)–S(2)
S(1)–C(1)
S(2)–C(1)
N(1)–C(1)
N(1)–C(2)
N(1)–C(7)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
C(6)–C(7)
C(8)–C(13)
C(8)–C(9)
C(9)–C(10)
C(10)–C(11)
2.156(3) Sb(2)–C(39)
2.162(4) Sb(2)–C(45)
2.179(3) Sb(2)–C(51)
2.188(3) Sb(2)–C(57)
2.7169(9) Sb(2)–S(4)
2.741(1) Sb(2)–S(3)
1.711(4) S(4)–C(32)
1.723(3) S(3)–C(32)
1.330(4) N(2)–C(32)
1.471(5) N(2)–C(38)
1.464(5) N(2)–C(33)
1.516(6) C(37)–C(38)
1.514(6) C(36)–C(37)
1.507(7) C(35)–C(36)
1.501(7) C(34)–C(35)
1.522(7) C(33)–C(34)
1.376(5) C(39)–C(40)
1.378(6) C(39)–C(44)
1.381(6) C(43)–C(44)
1.348(8) C(42)–C(43)
2.169(3)
2.155(3)
2.185(3)
2.180(3)
C(11)–C(12)
C(12)–C(13)
C(14)–C(19)
C(14)–C(15)
1.346(7) C(41)–C(42)
1.396(5) C(40)–C(41)
1.387(5) C(45)–C(46)
1.393(5) C(45)–C(50)
1.382(6) C(49)–C(50)
1.349(7) C(48)–C(49)
1.368(6) C(47)–C(48)
1.381(5) C(46)–C(47)
1.386(5) C(51)–C(56)
1.395(5) C(51)–C(52)
1.389(6) C(52)–C(53)
1.354(7) C(53)–C(54)
1.361(7) C(54)–C(55)
1.392(6) C(55)–C(56)
1.385(5) C(57)–C(58)
1.374(5) C(57)–C(62)
1.385(5) C(61)–C(62)
1.370(6) C(60)–C(61)
1.372(6) C(59)–C(60)
1.381(5) C(58)–C(59)
1.366(7)
1.374(6)
1.386(5)
1.392(4)
1.369(5)
1.370(6)
1.372(6)
1.378(5)
1.387(5)
1.369(5)
1.392(6)
1.363(8)
1.365(8)
1.382(6)
1.380(5)
1.384(4)
1.391(5)
1.355(6)
1.381(6)
1.384(5)
2.7238(10) C(15)–C(16)
2.7211(10) C(16)–C(17)
1.714(4)
1.719(4)
1.338(5)
1.471(6)
1.464(6)
1.500(8)
C(17)–C(18)
C(18)–C(19)
C(20)–C(25)
C(20)–C(21)
C(21)–C(22)
C(22)–C(23)
1.553(10) C(23)–C(24)
1.442(9)
1.489(9)
1.505(7)
1.382(5)
1.378(5)
1.369(5)
1.370(7)
C(24)–C(25)
C(26)–C(31)
C(26)–C(27)
C(27)–C(28)
C(28)–C(29)
C(29)–C(30)
C(30)–C(31)
Angle
ω, deg
ω,deg
ω, deg
ω, deg
Angle
Angle
Angle
C(8)Sb(1)C(14) 108.7(1) C(45)Sb(2)C(39) 107.5(1)
C(1)N(1)C(2)
C(7)N(1)C(2)
N(1)C(1)S(1)
N(1)C(1)S(2)
S(1)C(1)S(2)
N(1)C(2)C(3)
122.9(3) C(32)N(2)C(38)
115.3(3) C(33)N(2)C(38)
121.0(3) N(2)C(32)S(4)
119.9(3) N(2)C(32)S(3)
119.1(2) S(4)C(32)S(3)
113.5(3) N(2)C(38)C(37)
121.2(4)
116.0(4)
120.2(3)
120.3(3)
119.5(2)
113.4(5)
C(8)Sb(1)C(20)
C(14)Sb(1)C(20) 92.8(1) C(45)Sb(2)C(51)
C(8)Sb(1)C(26) 92.5(1) C(39)Sb(2)C(57)
C(14)Sb(1)C(26) 92.5(1) C(45)Sb(2)C(57)
95.0(1) C(39)Sb(2)C(51)
94.0(1)
93.6(1)
92.7(1)
91.9(1)
C(20)Sb(1)C(26) 169.0(1) C(57)Sb(2)C(51) 169.6(1)
C(8)Sb(1)S(1)
C(14)Sb(1)S(1)
C(20)Sb(1)S(1)
C(26)Sb(1)S(1)
C(8)Sb(1)S(2)
159.3(1) C(39)Sb(2)S(4)
91.98(9) C(45)Sb(2)S(4)
82.73(9) C(51)Sb(2)S(4)
87.44(9) C(57)Sb(2)S(4)
93.6(1) C(39)Sb(2)S(3)
159.70(9) C(4)C(3)C(2)
92.65(9) C(5)C(4)C(3)
116.3(4) C(38)C(37)C(36) 116.2(6)
114.1(4) C(35)C(36)C(37) 119.8(7)
116.8(4) C(36)C(35)C(34) 118.0(6)
114.8(4) C(35)C(34)C(33) 116.3(6)
82.0(1)
C(6)C(5)C(4)
89.02(9) C(5)C(6)C(7)
93.83(9) N(1)C(7)C(6)
158.61(9) C(13)C(8)C(9)
83.00(9) C(13)C(8)Sb(1)
88.66(9) C(9)C(8)Sb(1)
65.98(3) C(8)C(9)C(10)
112.0(4) N(2)C(33)C(34)
113.7(4)
C(14)Sb(1)S(2) 157.51(9) C(45)Sb(2)S(3)
118.5(4) C(44)C(39)C(40) 117.2(4)
122.9(3) C(40)C(39)Sb(2) 122.5(3)
118.6(3) C(44)C(39)Sb(2) 120.2(3)
120.6(5) C(43)C(44)C(39) 121.9(4)
C(20)Sb(1)S(2)
C(26)Sb(1)S(2)
S(1)Sb(1)S(2)
C(1)S(1)Sb(1)
C(1)S(2)Sb(1)
C(1)N(1)C(7)
C(1)N(1)C(2)
C(7)N(1)C(2)
N(1)C(1)S(1)
82.2(1) C(51)Sb(2)S(3)
89.29(9) C(57)Sb(2)S(3)
65.69(3) S(3)Sb(2)S(4)
86.8(1) C(32)S(4)Sb(2)
85.8(1) C(32)S(3)Sb(2)
86.6(1)
86.6(1)
C(11)C(10)C(9) 120.6(5) C(44)C(43)C(42) 119.7(4)
C(12)C(11)C(10) 119.6(4) C(41)C(42)C(43) 119.8(4)
C(11)C(12)C(13) 121.3(5) C(42)C(41)C(40) 120.1(4)
C(8)C(13)C(12) 119.3(4) C(41)C(40)C(39) 121.4(4)
C(19)C(14)C(15) 117.9(4) C(46)C(45)C(50) 118.0(3)
C(19)C(14)Sb(1) 118.6(3) C(46)C(45)Sb(2) 119.3(2)
121.0(3) C(32)N(2)C(33) 122.2(4)
122.9(3) C(32)N(2)C(38) 121.2(4)
115.3(3) C(33)N(2)C(38) 116.0(4)
121.0(3) N(2)C(32)S(4)
120.2(3)
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TETRAPHENYL- AND TETRATOLYLANTIMONY COMPLEXES
393
Table 3. (Contd.)
Angle
ω, deg
Angle
ω, deg
Bond
d, A
Bond
d, A
C(15)C(14)Sb(1) 123.0(3) C(50)C(45)Sb(2)
C(16)C(15)C(14) 120.4(4) C(49)C(50)C(45)
C(17)C(16)C(15) 120.7(4) C(50)C(49)C(48)
C(16)C(17)C(18) 120.0(4) C(49)C(48)C(47)
C(17)C(18)C(19) 120.3(4) C(48)C(47)C(46)
C(18)C(19)C(14) 120.5(4) C(47)C(46)C(45)
C(25)C(20)C(21) 118.6(3) C(52)C(51)C(56)
C(25)C(20)Sb(1) 121.0(3) C(56)C(51)Sb(2)
122.6(3) C(6)–C(7)
1.521(5) C(41)–C(42)
1.387(4) C(41)–C(46)
1.383(5) C(42)–C(43)
1.384(5) C(43)–C(44)
1.383(5) C(44)–C(45)
1.392(5) C(44)–C(47)
1.506(5) C(45)–C(46)
1.385(5)
1.389(4)
1.399(4)
1.377(4)
1.390(4)
1.394(4)
1.515(4)
1.392(4)
120.9(4) C(11)–C(12)
120.1(4) C(11)–C(16)
120.2(4) C(12)–C(13)
119.9(4) C(13)–C(14)
120.9(4) C(14)–C(15)
118.8(4) C(14)–C(17)
120.5(3) C(15)–C(16)
C(21)C(20)Sb(1) 120.3(3) C(52)C(51)Sb(2)
120.7(3)
Angle
ω, deg
Angle
ω, deg
C(22)C(21)C(20) 119.9(4) C(51)C(52)C(53)
C(23)C(22)C(21) 120.6(5) C(54)C(53)C(52)
C(22)C(23)C(24) 120.4(4) C(53)C(54)C(55)
C(23)C(24)C(25) 120.5(5) C(54)C(55)C(56)
C(20)C(25)C(24) 119.9(5) C(55)C(56)C(51)
C(27)C(26)C(31) 119.1(3) C(58)C(57)C(62)
C(27)C(26)Sb(1) 126.3(3) C(62)C(57)Sb(2)
C(31)C(26)Sb(1) 114.5(2) C(58)C(57)Sb(2)
C(26)C(27)C(28) 120.3(4) C(57)C(62)C(61)
C(29)C(28)C(27) 120.1(4) C(60)C(61)C(62)
C(28)C(29)C(30) 120.2(4) C(61)C(60)C(59)
C(29)C(30)C(31) 119.8(4) C(60)C(59)C(58)
C(30)C(31)C(26) 120.6(4) C(57)C(58)C(59)
120.7(5) C(21)SbC(11)
119.5(5) C(31)SbC(11)
120.6(5) C(31)SbC(21)
119.9(5) C(41)SbC(11)
120.4(5) C(41)SbC(21)
118.6(3) C(41)SbC(31)
126.2(3) C(11)SbS(1)
115.2(2) C(21)SbS(1)
120.0(4) C(31)SbS(1)
120.6(4) C(41)SbS(1)
120.4(4) C(11)SbS(2)
119.1(4) C(21)SbS(2)
121.3(4) C(31)SbS(2)
167.0(1) C(15)C(14)C(17) 121.9(3)
94.2(1) C(16)C(11)C(12) 118.9(3)
89.3(1) C(16)C(15)C(14) 121.4(3)
95.4(1) C(22)C(21)Sb
95.8(1) C(26)C(21)Sb
127.1(2)
114.3(2)
105.1(1) C(21)C(26)C(25) 121.0(3)
77.82(8) C(22)C(23)C(24) 121.4(3)
89.28(8) C(23)C(22)C(21) 120.4(3)
100.23(8) C(23)C(24)C(25) 118.2(3)
154.16(8) C(23)C(24)C(27) 122.3(3)
86.37(8) C(25)C(24)C(27) 119.6(3)
86.89(8) C(26)C(21)C(22) 118.4(3)
163.79(8) C(26)C(25)C(24) 120.6(3)
Angle
ϕ, deg
Angle
ϕ, deg C(41)SbS(2)
90.93(8) C(32)C(31)Sb
119.4(2)
C(2)N(1)C(1)S(1)
2.2(5) C(33)N(2)C(32)S(3)
1.8(5) S(2)SbS(1)
64.00(2) C(36)C(31)Sb
123.3(2)
C(2)N(1)C(1)S(2) –177.4(3) C(33)N(2)C(32)S(4) –178.0(3) C(1)S(1)Sb
C(7)N(1)C(1)S(1) –166.6(3) C(38)N(2)C(32)S(3) 172.5(1) C(1)S(2)Sb
84.7(1) C(31)C(36)C(35) 121.0(3)
88.9(1) C(32)C(33)C(34) 121.1(3)
122.2(3) C(33)C(32)C(31) 121.8(3)
121.2(3) C(33)C(34)C(35) 117.7(3)
116.5(3) C(33)C(34)C(37) 121.7(3)
121.4(2) C(34)C(35)C(36) 121.2(3)
120.0(2) C(35)C(34)C(37) 120.6(3)
C(7)N(1)C(1)S(2)
13.8(5) C(38)N(2)C(32)S(4) –7.4(5) C(1)NC(2)
Sb(1)S(1)C(1)N(1) 164.4(3) Sb(2)S(3)C(32)N(2) –168.2(3) C(1)NC(5)
Sb(1)S(2)C(1)N(1) –164.6(3) Sb(2)S(4)C(32)N(2) 168.2(3) C(5)NC(2)
S(1)Sb(1)C(1)S(2) 164.0(3) S(3)Sb(2)C(32)S(4) –168.3(3) NC(1)S(1)
Sb(1)S(1)S(2)C(1) 160.9(3) Sb(2)S(3)S(4)C(32) –166.1(3) NC(1)S(2)
V
S(2)C(1)S(1)
NC(2)C(3)
118.6(2) C(36)C(31)C(32) 117.2(3)
Bond
Sb–C(11)
d, A
Bond
d, A
113.7(3) C(42)C(41)Sb
116.9(4) C(46)C(41)Sb
120.5(2)
121.5(2)
2.179(3) C(21)–C(22)
2.171(3) C(21)–C(26)
2.162(3) C(22)–C(23)
2.147(3) C(23)–C(24)
2.8542(9) C(24)–C(25)
2.7303(8) C(24)–C(27)
1.727(3) C(25)–C(26)
1.717(3) C(31)–C(32)
1.331(4) C(31)–C(36)
1.479(4) C(32)–C(33)
1.391(4) C(4)C(3)C(2)
1.380(4) NC(5)C(6)
1.381(5) C(5)C(6)C(7)
1.381(5) C(12)C(11)Sb
1.389(5) C(16)C(11)Sb
1.519(5) C(11)C(16)C(15) 120.5(3) C(43)C(44)C(47) 120.5(3)
1.384(5) C(13)C(12)C(11) 119.9(3) C(45)C(44)C(47) 121.2(3)
1.389(4) C(13)C(14)C(15) 117.1(3) C(45)C(46)C(41) 120.4(3)
1.383(4) C(13)C(14)C(17) 120.9(3) C(46)C(45)C(44) 120.9(3)
1.379(5) C(14)C(13)C(12) 122.2(3)
Sb–C(21)
Sb–C(31)
Sb–C(41)
Sb–S(1)
Sb–S(2)
S(1)–C(1)
S(2)–C(1)
N–C(1)
111.7(3) C(42)C(41)C(46) 117.9(3)
112.8(3) C(42)C(43)C(44) 120.8(3)
118.8(2) C(43)C(42)C(41) 121.6(3)
122.3(2) C(43)C(44)C(45) 118.3(3)
N–C(2)
N–C(5)
1.472(4) C(33)–C(34)
1.382(5)
Angle
ϕ, deg
Angle
ϕ, deg
C(2)–C(3)
C(3)–C(4)
C(5)–C(6)
1.517(6) C(34)–C(35)
1.452(6) C(34)–C(37)
1.512(5) C(35)–C(36)
1.384(5) S(1)C(1)NC(2) 179.1(2) S(2)C(1)NC(5)
174.6(2)
160.7(2)
157.2(2)
1.507(5) S(1)C(1)NC(5)
1.396(5) S(2)C(1)NC(2)
–5.8(4) S(2)SbC(1)S(1)
–0.5(4) SbS(2)S(1)C(1)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

394
SHARUTIN et al.
‡
*
‡
b
b
*
*
*
*
*
c
c
140
120
δ, ppm
15
Fig. 2. N MAS NMR spectra of polycrystalline com-
plexes II–IV of the general formula [Sb(C H ) (S CNR )]:
6
5 4
2
2
R = (a) C H and (b) C H ; (c) R = (CH ) . The numbers
2
5
3
7
2
2 6
of scans/spinning rates (Hz) are (a) 3052/3450,
(b) 2600/3760, and (c) 3700/3760.
205 200
*
* * *
50
d
200
150
100
δ, ppm
0
folded along the Sb–C and S–S diagonals. The S···S
distance (2.961 Å) is shorter than the Sb···C one
(3.129 Å). In the six-membered rings p-CH3–C6H4, the
C–C bonds (1.377–1.399 Å) are on average somewhat
longer than in phenyl rings. The CCC angles are not
strictly equal to 120° (117.1°–122.3°). The fragment
C2N–C(S)S (Table 3) is virtually planar (the C(5) atom
slightly deviates from the plane) and the N–C(S)S bond
is short.
13
Fig. 1. C MAS NMR spectra of polycrystalline com-
plexes I–IV of the general formula [Sb(C H ) (S CNR )]:
6
5 4
2
2
R = (a) CH , (b) C H , and (c) C H ; (d) R = (CH ) . The
3
2
5
3
7
2
2 6
numbers of scans/spinning rates (Hz) are (a) 4560/5500,
(b) 10 000/9200, (c) 7700/9100, and (d) 10 000/8500. Side-
bands due to the spinning are asterisked.
Assignment of 13C and 15N NMR signals to the
atoms in the isomeric molecular forms of complex IV
was based on different degrees of double bonding in the
fragments =N−C(S)S– [11–14]. The partial double
bond character causes the electron density transfer
from the N atom toward the –C(S)S– group; as the
result, the electron shielding of the N nucleus dimin-
ishes, while that of the C atom increases. The
N(1)−C(1) bond in molecule A (1.330 Å) is slightly
stronger than in molecule B (N(2)−C(32) 1.338 Å).
Therefore, the bond order in molecule A is higher and
plane is made up of the bidentate N,N-dipropyldithio-
carbamate ligand and two most firmly bound monoden-
tate p-tolyl ligands. The looser tolyl ligands are in the
axial positions. The axial CSbC angle in the octahedron
is 167.0°, appreciably deviating from ideal 180°. The
dipropyldithiocarbamate ligand is coordinated in the
anisobidentate manner since one Sb–S bond (2.7303 Å)
is substantially shorter than the other (2.8542 Å). The
coordination of the dithiocarbamate ligand gives rise to
a four-membered chelate ring SbS2C.
the electron density shift =N
C(S)S– is more con-
The torsion angles in this ring suggest its nonplanar
geometry (Table 3). This is confirmed by the dihedral
angles between two SbSC planes (160.7°) and between
the SbSS and SSC planes (157.3°). As with complex
siderable. Thus, the 15N NMR signal at δ 123.0 ppm
should be assigned to the less shielded N(1) atom,
while the signal at δ 120.0 ppm, to the N(2) atom. Anal-
IV, the four-membered chelate ring in complex V is ogously, the 13C NMR signals at δ 201.4 and 201.9 ppm
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

TETRAPHENYL- AND TETRATOLYLANTIMONY COMPLEXES
(a) (b)
395
C(54)
C(23)
C(24)
C(25)
C(53)
C(52)
C(22)
C(21)
C(55)
C(56)
C(36)
C(5)
C(4)
C(35)
C(34)
C(37)
C(38)
C(3)
C(2)
C(47)
C(51)
C(16)
C(6)
C(7)
C(20)
C(50)
C(45)
C(49)
C(48)
C(15)
C(17)
C(18)
C(13)
C(14)
C(19)
S(1)
N(1)
S(4)
C(1)
C(32)
C(33)
Sb(1)
Sb(2)
N(2)
C(41)
C(42)
C(40)
C(39)
C(44)
C(43)
C(12)
C(11)
C(10)
C(46)
C(57)
C(8)
C(9)
S(2)
S(3)
C(26)
C(31)
C(27)
C(28)
C(58)
C(61)
C(62)
C(59)
C(30)
C(29)
C(60)
Fig. 3. Structures of two molecules (a) A and (b) B in complex IV.
C(17)
C(14)
C(15)
C(4)
C(13)
C(16)
C(3)
C(12)
C(45)
C(11)
C(2)
C(46)
C(41)
N
C(5)
C(47)
S(2)
Sb
C(44)
C(43)
C(1)
C(36)
C(7)
C(6)
C(35)
C(31)
C(34)
S(1)
C(42)
C(32)
C(21)
C(37)
C(33)
C(22)
C(23)
C(26)
C(25)
C(24)
C(27)
Fig. 4. Structure V with atomic thermal displacement ellipsoids (50% probability).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

396
SHARUTIN et al.
Table 4. 13C and 15N chemical shifts δ (ppm) for complexes I–IV with reference to TMS and NH4Cl, respectively
δ13C
δ15N
Complex
–S2CN=
201.7
=NCH2–
49.3
–CH2–
–CH3–
C6H5–
–N=
[Sb(C6H5)4{S2CN(CH3)2}]
47.3, 46.1 166, 147.1, 139.9, 135.3,
(1 : 1) 131.4, 128.8, 125.3
(I)
[Sb(C6H5)4{S2CN(C2H5)2}]
198.9
201.2
14.4, 12.8 163, 144.5, 143.2, 136.4,
(1 : 1)
127.3
123.3
(II)
134.0, 130.2, 129.8,
128.47, 128.1, 126.9
[Sb(C6H5)4{S2CN(C3H7)2}]
57.4, 56.7
(1 : 1)
20.9, 20.1 12.2, 11.3 *, 147.1, 143.8, 135.9,
(1 : 1)
(III)
(1 : 1) 134.0, 132.2, 129.8, 129.0,
128.3, 126.6
[Sb(C6H5)4{S2CN(CH2)6}] 201.9, 201.4 59.1, 58.5,
28.4, 27.4,
163, 146.9, 146.6, 145.2, 123.0, 120.0
(IV)
(1 : 1)
56.8, 55.7 26.4, 24.5, 23.9
(1 : 1 : 1 : 1) (1 : 1 : 2 : 2 : 2)
140.5, 136.6, 135.8, 134.3,
131.3, 130.7, 130.0, 129.0,
128.4, 127.2, 126.8, 126.2
(1 : 1)
* The chemical shift was not determined because of broadening of the 13C NMR signal for the ≡C–Sb group.
5. Earl, W.L., VanderHart, D. L., J. Magn. Reson., 1982,
were assigned to the more and less shielded carbon
nuclei (C(1) and C(32), respectively).
vol. 48, no. 1, p. 35.
6. Ratcliffe, C.I., Ripmeester, J.A., and Tse, J.S., Chem.
Phys. Lett., 1983, vol. 99, no. 2, p. 177.
7. Mason, J., Encyclopaedia of Nuclear Magnetic Reso-
nance, Grant, D.M. and Harris, R.K., Eds., New York:
Wiley, 1996, vol. 5, p. 3222.
8. SMART and SAINT-Plus. Versions 5.0, Data Collection
and Processing Software for the SMART System, Bruker
AXS Inc., Madison (WI, USA), 1998.
9. SHELXTL/PC. Versions 5.10. An Integrated System for
Solving, Refining and Displaying Crystal Structures
from Diffraction Data, Bruker AXS Inc., Madison (WI,
USA), 1998.
ACKNOWLEDGMENTS
A.V. Ivanov acknowledges the financial support of
the Agricola Research Center at the Luleä University of
Technology (Sweden).
This work was supported by the Far East Division of
the RussianAcademy of Sciences (grant no.-05-III-G-04-060
for basic and applied research of young scientists
(2005)).
10. Sharutin, V.V., Senchurin, V.S., Sharutina, O.K., et al.,
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