Synthesis and structure of tetraphenylantimony N,N-diethyldithiocarbamate

Article abstract of DOI:10.1023/A:1021613526421

Tetraphenylantimony chloride was reacted with sodium N,N-diethyldithiocarbamate in water to obtain tetraphenylantimony N,N-diethyldithiocarbamate in 98% yield. According to X-ray diffraction data, the configuration of the molecule of tetraphenylantimony diethyldithiocarbamate is distorted octahedron, and the Sb-S bond lengths are 2.705(2) and 2.771(2) A.

Full text of DOI:10.1023/A:1021613526421

Russian Journal of General Chemistry, Vol. 72, No. 9, 2002, pp. 1379 1382. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 9, 2002,
pp. 1465 1467.
Original Russian Text Copyright
2002 by Sharutin, Sharutina, Platonova, Pakusina, Krivolapov, Gubaidullin, Litvinov.
Synthesis and Structure
of Tetraphenylantimony N,N-Diethyldithiocarbamate
V. V. Sharutin, O. K. Sharutina, T. P. Platonova, A. P. Pakusina,
D. B. Krivolapov, A. T. Gubaidullin, and I. A. Litvinov
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received August 3, 2000
Abstract Tetraphenylantimony chloride was reacted with sodium N,N-diethyldithiocarbamate in water to
obtain tetraphenylantimony N,N-diethyldithiocarbamate in 98% yield. According to X-ray diffraction data,
the configuration of the molecule of tetraphenylantimony diethyldithiocarbamate is distorted octahedron,
and the Sb S bond lengths are 2.705(2) and 2.771(2)
.
The synthesis and structure of many oxygen-
containing aryl compounds of pentavalent antimony
Note that the inequality of the Sb S distances and
the reverse redistribution of the C S bond lengths
of the general formula Ar4SbX (where X is an oxygen- (longer Sb S distance relates to shorter C S bond)
containing radical) have been described [1 4].
Analogous derivatives of antimony with sulfur-con-
taining ligands X have never been obtained.
provide further evidence for this resonance structure.
The geometry of the diethyldithiocarbamate group
shows that the nitrogen lone pair is conjugated with
the C=S bond (the nitrogen atom has a planar trigonal
coordination, the S2CN fragment is planar, and the
C1 N1 bond is strongly shortened). The crystal
packing of compound I is mainly determined by dis-
persion interactions (Fig. 2).
We found tetraphenylantimony chloride with reacts
with sodium N,N-diethyldithiocarbamate in water to
give tetraphenylantimony N,N-diethyldithiocarbamate
Ph4SbSC(S)NEt2 (I).
Ph4SbCl + NaSC(S)NEt2
Ph4SbSC(S)NEt2 + NaCl.
EXPERIMENTAL
Attempted synthesis of triphenylantimony bis-
(N,N-diethyldithiocarbamate) from triphenylantimony
dichloride and sodium N,N-diethyldithiocarbamate in
toluene at elevated temperature did not give the target
product. Instead, reduction of triphenylantimony di-
chloride to triphenylstibine and dimerization of N,N-
diethyldithiocarbamate groups took place.
The IR spectra were recorded on a Hitachi-215
spectrometer for suspensions in Vaseline oil between
sodium chloride plates.
C21
C20
C15
C14
C19
C22
C23
Ph3SbCl2 + 2NaSC(S)NEt2
+ [SC(S)NEt2]2 + 2NaCl.
Ph3Sb
C16
C18
Sb1
C11
C17
C5
C13
C4
According to X-ray diffraction data, the antimony
atom in compound I has a distorted octahedral co-
ordination (Fig. 1). The Sb S bonds are strongly
C12
S2
C1
C10
C9
N1
lengthened [2.705(2) and 2.771(2)
, Table 2],
C2
S1
because they are evidently coordination in nature.
Hence, complex I can be characterized by the follow-
ing resonance structure.
C24
C29
C28
C1
C8
C25
Ph
S
Sb
Ph
Ph
+
NEt2
27 C26
C
S
Ph
Fig. 1. Geometry of complex I in crystal.
1070-3632/02/7209-1379$27.00 2002 MAIK Nauka/Interperiodica

1380
SHARUTIN et al.
Fig. 2. Crystal packing of molecules I as viewed along the 0y axis.
Table 1. Bond lengths (d, ) and bond angles ( , deg) in
structure I
X-ray diffraction analysis of crystals of tetra-
phenylantimony N,N-diethyldithiocarbamate (I).
C29H30NS2Sb. The unit cell parameters and the in-
tensities of 5749 reflections, 2212 of which had I >
2 , were measured on an Enraf Nonius CAD-4
automatic four-curcle K-diffractometer at 20 C
(MoK radiation, MoK 0.71073 , graphite mono-
Bond
d,
Bond
d,
Sb1 S1
Sb1 S2
Sb1 C6
Sb1 C12
Sb1 C18
Sb1 C24
2.705(2)
2.771(2)
2.161(6)
2.160(6)
2.170(7)
2.197(7)
S1 C1
S2 C1
N1 C1
N1 C2
N1 C4
1.717(7)
1.706(7)
1.330(8)
1.481(9)
1.457(9)
chromator, /2 scanning,
< 29.96 ). Rhombic
crystals; at 20 C, a 16.820(3), b 9.455(3), c
33.934(9) , V 5397(3) 3, Z 8, dcalc 1.42 g/cm3.
Space group Pbca. Empirical absorption corrections
1
( Mo 11.93 cm ) were included. The structure was
solved by the direct method by the SIR program [5]
and refined first isotropically and then anisotropically.
Hydrogen atoms were located by difference synthesis
and refined isotropically in the final stage to R 0.033
and RW 0.037 on 2079 unique reflections with F2 > 3 .
The atomic coordinates are listed in Table 1, and the
principal geometric parameters, in Table 2. All cal-
culations were carried out by means of the MolEN
complex of programs [6] on DEC Alpha Station.
Analysis of molecular contacts and molecular draw-
ings were performed be means of the WINPL98
program [7].
Angle
, deg
Angle
, deg
S1Sb1S2
S1Sb1C6
S1Sb1C12
S1Sb1C18
S1Sb1C24
S2Sb1C6
65.50(6)
94.1(2)
C12Sb1C18
C12Sb1C24
C18Sb1C24
Sb1S1C1
Sb1S2C1
C1N1C2
94.4(2)
91.8(2)
168.5(2)
88.3(2)
86.3(2)
121.3(5)
160.7(2)
83.0(2)
87.9(2)
159.6(2)
S2Sb1C12
S2Sb1C18
S2Sb1C24
C6Sb1C12
C6Sb1C18
C6Sb1C24
95.3(2)
83.4(2)
86.4(2)
105.1(2)
94.8(2)
92.9(2)
C1N1C4
C2N1C4
S1C1S2
S1C1N1
S2C1N1
123.1(5)
115.6(5)
119.8(4)
119.2(5)
121.0(5)
Tetraphenylantimony N,N-diethyldithiocar-
bamate (I). To a solution of 1.00 g of tetraphenylanti-
mony chloride in water, a solution of 0.42 g of so-
dium N,N-diethyldithiocarbamate in water was added.
A colorless precipitate formed and was filtered off,
dried, and crystallized from a toluene heptane mixture
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 9 2002

SYNTHESIS AND STRUCTURE OF TETRAPHENYLANTIMONY N,N-DIETHYLDITHIOCARBAMATE 1381
3
Table 2. Atomic coordinates, equivalent isotropic thermal parameters of non-hydrogen atoms B = 4/3
3(aiaj)B(i, j)
i=1 j=1
(
2), and isotropic thermal parameters of hydrogen atoms in structure I
Atom
x
y
z
B
Atom
x
y
z
B
Sb1
S1
0.96060(3)
1.1058(1)
1.0866(1)
1.2254(3)
1.1468(4)
1.2783(4)
1.2953(5)
1.2654(4)
1.2861(5)
0.8973(4)
0.9185(5)
0.8808(5)
0.8228(5)
0.8012(5)
0.8411(4)
0.8692(3)
0.7919(4)
0.7329(4)
0.7540(4)
0.8307(5)
0.8874(4)
0.9761(3)
0.9653(4)
0.9749(4)
0.9916(5)
1.0009(4)
0.9925(4)
0.9704(4)
1.0351(5)
1.0291(5)
0.9618(6)
0.8980(5)
0.19505(5)
0.1246(2)
0.2929(2)
0.2115(6)
0.2100(7)
0.1484(8)
0.252(1)
0.2792(8)
0.1762(9)
0.0909(7)
0.1216(9)
0.0548(9)
0.0395(9)
0.0713(8)
0.0090(8)
0.2813(7)
0.2403(8)
0.3031(8)
0.4063(8)
0.4500(8)
0.3875(8)
0.0044(7)
0.0064(8)
0.118(1)
0.12359(1) 4.387(8) C29
0.09558(6) 6.00(5) H7
0.16862(6) 5.66(5) H8
0.9033(5)
0.953(3)
0.894(4)
0.801(4)
0.773(3)
0.825(3)
0.780(2)
0.678(3)
0.712(3)
0.843(3)
0.937(3)
0.956(2)
0.964(2)
0.989(3)
1.010(3)
0.998(3)
1.085(3)
1.085(3)
0.961(4)
0.858(3)
0.851(5)
1.240(4)
1.323(3)
1.319(4)
1.240(3)
1.311(3)
1.335(4)
1.234(3)
1.315(5)
1.253(3)
1.325(4)
0.4701(8)
0.189(5)
0.088(7)
0.088(8)
0.148(5)
0.028(5)
0.186(4)
0.272(5)
0.444(6)
0.520(6)
0.416(6)
0.089(5)
0.107(5)
0.334(5)
0.331(5)
0.131(6)
0.392(6)
0.562(6)
0.718(8)
0.642(6)
0.431(9)
0.275(7)
0.219(6)
0.331(6)
0.348(6)
0.326(5)
0.098(8)
0.140(6)
0.204(8)
0.065(5)
0.130(6)
0.0886(2)
0.036(1)
0.016(2)
0.004(2)
0.059(1)
0.107(1)
0.142(1)
0.182(1)
0.220(1)
0.229(2)
0.190(2)
0.211(1)
0.241(1)
0.217(1)
0.153(1)
0.112(1)
0.074(1)
0.035(2)
0.032(2)
0.065(2)
0.100(2)
0.066(1)
0.062(2)
0.090(2)
0.183(1)
0.161(1)
0.192(2)
0.213(1)
0.215(2)
0.101(1)
0.126(1)
7.6(2)
6(1)
10(2)
11(2)
5(1)
4(1)
S2
N1
0.1396(2)
0.1354(2)
0.1094(2)
5.9(1)
5.4(2)
7.5(2)
H9
C1
H10
H11
H13
H14
H15
H16
H17
H19
H20
H21
H22
H23
H25
H26
H27
H28
H29
H31
H32
H33
H41
H42
H51
H52
H53
H211
H212
C2
C3
0.0771(3) 11.4(3)
1.8(9)
C4
0.1726(2)
0.2046(3)
0.0764(2)
0.0381(2)
0.0072(2)
0.0143(2)
0.0515(2)
0.0826(2)
0.1613(2)
0.1598(2)
0.1817(2)
0.2078(2)
0.2111(2)
0.1879(2)
0.1584(2)
0.1985(2)
0.2199(2)
0.2018(2)
0.1621(2)
0.1401(2)
0.0906(2)
0.0695(3)
7.0(2)
9.1(3)
4.6(2)
7.3(2)
8.6(3)
8.7(3)
7.1(2)
6.1(2)
4.3(2)
6.2(2)
6.4(2)
7.0(2)
7.0(2)
6.0(2)
4.7(2)
6.0(2)
7.6(2)
6.9(2)
6.6(2)
5.5(2)
5.4(2)
8.6(2)
5(1)
7(2)
9(2)
8(2)
4(1)
4(1)
5(1)
7(2)
6(1)
6(1)
8(2)
11(2)
9(2)
16(3)
9(2)
8(2)
11(2)
7(2)
7(2)
12(2)
7(2)
15(3)
4(1)
8(2)
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
0.2418(8)
0.2456(8)
0.1246(8)
0.3942(8)
0.4407(9)
0.563(1)
0.0471(3) 10.3(3)
0.6377(9)
0.5937(9)
0.0455(2)
0.0666(3)
9.7(3)
9.7(3)
to obtain 1.23 g (98%) of compound I, mp 148 C. IR
spectrum, , cm : 1430 s, 1305 w, 1272 v.s., 1212 s,
1180 s, 1142 s, 1065 v.s.
ACKNOWLEDGMENTS
The X-ray diffraction analysis was carried out at
1
the Department of X-ray studies, Spectral Analytical
Center for Collective Use, Russian Fundation for
Basic Research (project no. 96-03-40006).
Reaction of sodium N,N-diethyldithiocarbamate
with triphenylantimony chloride. A mixture of
1.12 g of triphenylantimony dichloride, 1.35 g of
sodium N,N-diethyldithiocarbamate, and 10 ml of
toluene was heated for 3 h at 100 C. The solvent was
removed, and the residue was crystallized from
hexane to obtain 0.65 g (83%) of yellow crystals, mp
62 C. The residue dissolved in hexane was chromato-
graphed on a column with aluminum oxide. Elution
with hexane gave 0.85 g (91%) of triphenylstibine,
mp 48 C.
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