Mono- and bis(dialkyl/aryl dithiocarbamato) complexes of 1,1,2,3,4,5,6-heptahydro-1,1-dihalido telluranes: Synthesis, spectroscopy, structures and cleavage reaction

Article abstract of DOI:10.1016/j.poly.2010.04.020

Reactions of 1,1,2,3,4,5,6-heptahydro-1,1-dihalido telluranes [(C ₅H₁₀TeX₂), X = Cl, Br, I] with sodium/ammonium (dialkyl/aryl dithiocarbamates) viz. NaS₂CN(C₂H ₅)₂, NH₄S₂CNC₄H ₈O, NH₄S₂CNC₅H₁₀, NH ₄S₂CNHC₆H₅ yield new [C ₅H₁₀TeI{S₂CN(C₂H₅) ₂} (1), C₅H₁₀TeI(S₂CNC ₄H₈O) (2), C₅H₁₀TeI(S ₂CNC₅H₁₀) (3), C₅H ₁₀TeBr{S₂CN(C₂H₅)₂} (4), C₅H₁₀TeBr(S₂CNC₄H₈O) (5), C₅H₁₀TeBr(S₂CNC₅H₁₀) (6), C₅H₁₀TeCl{S₂CN(C₂H ₅)₂} (7), C₅H₁₀TeCl(S ₂CNC₄H₈O) (8), C₅H ₁₀TeCl(S₂CNC₅H₁₀) (9), C ₅H₁₀TeCl(S₂CNHC₆H₅) (10), C₅H₁₀Te{S₂CN(C₂H₅) ₂}₂ (12), C₅H₁₀Te(S ₂CNC₄H₈O)₂ (13), C₅H ₁₀Te(S₂CNC₅H₁₀)₂ (14)] complexes. The substitution reaction of C₅H₁₀TeCl ₂ with NH₄S₂CNHC₆H₅ yields complex (10) along with the cleaved product SC(NHC₆H ₅)₂ (11). In such type of substitution reaction, the formation of SC(NHC₆H₅)₂ H₅C ₆HN-C^S∥-NHC₆H₅ (11) is uncommon. The probable pathway for obtaining the cleaved product has been postulated on the basis of a comparative account with other similar type of cleavage reactions. The intermolecular Te?S secondary bonds and/or C-H?X (X = O, Cl, I) hydrogen bonds lead to the formation of (stairs, zig-zag ribbons), trimeric, tetrameric, hexameric and decameric supramolecular assemblies. The complexes have been characterized by elemental analysis, IR and (¹H, ¹³C, ¹²⁵Te) NMR spectroscopy and single crystal X-ray crystallography of 1, 2, 4, 7, 8, 9 and 11.

Full text of DOI:10.1016/j.poly.2010.04.020

Polyhedron 29 (2010) 2202–2212
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Mono- and bis(dialkyl/aryl dithiocarbamato) complexes of
1,1,2,3,4,5,6-heptahydro-1,1-dihalido telluranes: Synthesis, spectroscopy,
structures and cleavage reaction
a
a
b
Prakash C. Srivastava a, , Shrinkhala Dwivedi , Vikas Singh , Ray J. Butcher
*
a Department of Chemistry, Lucknow University, Lucknow 226007, India
b Department of Chemistry, Howard University, Washington, DC 20059, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
Reactions of 1,1,2,3,4,5,6-heptahydro-1,1-dihalido telluranes [(C5H10TeX2), X = Cl, Br, I] with sodium/
ammonium (dialkyl/aryl dithiocarbamates) viz. NaS2CN(C2H5)2, NH4S2CNC4H8O, NH4S2CNC5H10
NH4S2CNHC6H5 yield new [C5H10TeI{S2CN(C2H5)2} (1), C5H10TeI(S2CNC4H8O) (2), C5H10TeI(S2CNC5H10
(3), C5H10TeBr{S2CN(C2H5)2} (4), C5H10TeBr(S2CNC4H8O) (5), C5H10TeBr(S2CNC5H10 (6), C5H10Te-
Cl{S2CN(C2H5)2} (7), C5H10TeCl(S2CNC4H8O) (8), C5H10TeCl(S2CNC5H10) (9), C5H10TeCl(S2CNHC6H5) (10),
C5H10Te{S2CN(C2H5)2}2 (12), C5H10Te(S2CNC4H8O)2 (13), C5H10Te(S2CNC5H10 2 (14)] complexes. The sub-
Received 18 March 2010
Accepted 13 April 2010
Available online 29 April 2010
,
)
)
Keywords:
Self assembly
Organotellurium(IV)
Dithiocarbamate
Cleavage reaction
Crystal structure
)
stitution reaction of C5H10TeCl2 with NH4S2CNHC6H5 yields complex (10) along with the cleaved product
SC(NHC6H5)2 (11). In such type of substitution reaction, the formation of SC(NHC6H5)2
S
C
(11) is uncommon. The probable pathway for obtaining the cleaved product has
NHC6H5
H5C6HN
been postulated on the basis of a comparative account with other similar type of cleavage reactions.
The intermolecular TeÁÁÁS secondary bonds and/or C–HÁÁÁX (X = O, Cl, I) hydrogen bonds lead to the forma-
tion of (stairs, zig-zag ribbons), trimeric, tetrameric, hexameric and decameric supramolecular assem-
blies. The complexes have been characterized by elemental analysis, IR and (1H, 13C, 125Te) NMR
spectroscopy and single crystal X-ray crystallography of 1, 2, 4, 7, 8, 9 and 11.
Ó 2010 Elsevier Ltd. All rights reserved.
1. Introduction
of enzymes by coordination of Pt(II) to thiol groups and diethyldi-
thiocarbamate ions (Et2NCS2)À [9–11] containing soft sulfur atoms
Dithiocarbamates have been widely used as versatile ligands in
Tellurium/organotellurium coordination chemistry [1] and in most
of the cases the N,N-dialkyldithiocarbamates behave as dithio
ligands [2–6], whereas, to our knowledge, the reports related to
halido derivatives of the type Me2TeXL (X = Cl, Br, I) (L = dial-
kyldithiocarbamates) and C4H8TeI(S2CNEt2) are restricted to two
reports only [3d,5] apart from the mention of C5H10TeI(S2CNC4-
H8O) characterized through single crystal X-ray diffraction data
only in our earlier report [6] where dithiocarbamate groups act
as monothio ligands. The dithiocarbamate ligands lead to the inter-
esting supramolecular arrays and the use of optical and analytical
properties of dithiocarbamate complexes in constructing sensor for
guest molecules and their capability of introducing functionality
has been reported [7]. The chemotherapeutic use of cis-diamine di-
chloro platinum(II) and related drugs consists of some negative
side effects including nephrotoxicity [8] because of the inactivation
have been used as ‘‘rescue agents” for the protection of these thiols.
On the other hand, there is considerable interest in organotellu-
rium compounds because of their utility in organic synthesis, nu-
clear medicine, conductive materials and precursors for metal
organic chemical vapour deposition (MOCVD) [6]. In addition to
these potential utilities, there has been a significant interest in
exploiting remarkable structure plasticity of organotelluriums
[2,6,12] possibly because of the interest in the usefulness of supra-
molecular associations of organometallic compounds in non-linear
optics, solid state electrical conductivity and molecular sieves [6].
Apart from specific intermolecular non-covalent interactions
[13–16], the hydrogen bonds with well characterized geometry
and robustness are also frequently used in designing supramolec-
ular arrays [17–20] and amongst hydrogen bonds, C–HÁÁÁX (X = O
or Cl or I) hydrogen bonds play a dominant role in the stability
and possibly even in the activity of biological macromolecules,
organometallic crystals and molecular recognition processes [21].
In view of the usefulness of C–HÁÁÁX (X = O, Cl, I) hydrogen
bonds; the remarkable utilities of dialkyl/aryl dithiocarbamate
* Corresponding author. Tel.: +91 522 2358473.
E-mail address: pcsrivastava31@rediffmail.com (P.C. Srivastava).
0277-5387/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2010.04.020

P.C. Srivastava et al. / Polyhedron 29 (2010) 2202–2212
2203
groups coupled with their coordination characteristics and the
potentials, organotelluriums, have exhibited; we in the present
investigation report the supramolecular associations of hitherto
unknown mono- and bis(dialkyl/diaryl dithiocarbamates) of
ato) tellurane C5H10Te-Br(S2CNC5H10
)
(6), 1,1,2,3,4,5,6-hepta-
hydro-1-chloro-1-(diethyldithiocarbamato) tellurane C5H10TeCl-
{S2CN(C2H5)2} (7), 1,1,2,3,4,5,6-heptahydro-1-chloro-1-(morpho-
line dithiocarbamato) tellurane C5H10TeCl(S2CNC4H8O) (8),
1,1,2,3,4,5,6-heptahydro-1-chloro-1-(piperidine dithiocarbamato)
X
Te
1,1,2,3,4,5,6-heptahydro-1,1-dihalido
tellurane
[
,
X
tellurane C5H10TeCl(S2CNC5H10) (9), 1,1,2,3,4,5,6-heptahydro-1-
chloro-1-(aniline dithiocarbamato) tellurane C5H10TeCl(S2CNH-
C6H5) (10), 1,1,2,3,4,5,6-heptahydro-1,1-(diethyldithiocarbamato)
tellurane C5H10Te{S2CN(C2H5)2}2 (12), 1,1,2,3,4,5,6-heptahydro-
1,1-bis(morpholine dithiocarbamato) tellurane C5H10Te(S2CNC4-
H8O)2 (13), 1,1,2,3,4,5,6-heptahydro-1,1-(piperidine dithiocarbam-
(X = Cl, Br, I)] built up through intermolecular TeÁÁÁS secondary
bonds and/or C–HÁÁÁX (X = O, Cl, I) hydrogen bonds. They have been
characterized through (1H, 13C, 125Te) NMR spectroscopy and/or
single crystal diffraction studies. On the basis of a comparative ac-
count of the cleavage reactions, the possible pathway for the
Cl
ato) tellurane C5H10Te(S2CNC5H10)2 (14) were prepared by stirring
1,1,2,3,4,5,6-heptahydro-1,1-dihalido telluranes with freshly pre-
pared sodium/ammonium salts of diethyl-, morpholine-, piperi-
dine- and aniline dithiocarbamates in 1:1 and 1:2 M ratio in
acetone (Scheme 1).
cleaved product (11) obtained in the reaction of
Te
with
Cl
NH4S2CNHC6H5 is postulated.
Complex (1) was prepared by stirring C5H10TeI2 (2.00 g,
4.43 mmol) in acetone (ꢀ25 ml) with freshly prepared sodium salt
of diethyldithiocarbamate (0.99 g, 4.43 mmol) in 1:1 M ratio at
room temperature (25 °C). After ꢀ4 h the reaction mixture was fil-
tered to eliminate the unidentified material. The filtrate was con-
centrated to ꢀ10 ml under reduced pressure and kept overnight.
Yellow crystals were obtained and they were analysed through ele-
mental analysis, FT-IR, 1H NMR and single crystal X-ray diffraction
studies. These yellow crystals corresponded to C5H10TeI{S2CN
(C2H5)2} (1). Complexes 2–14 were obtained by the reaction of
C5H10TeX2 (X = Cl, Br, I) and corresponding dithiocarbamates fol-
lowing the same procedure as in (1).
The complexes 2, 4, 7, 8 and 9 also yield their crystals which
were analysed through single crystal X-ray diffraction studies.
The reaction of C5H10TeCl2 with NH4S2CNC6H5 gives yellow colour
solid complex (10) with few transparent crystals. These transpar-
ent crystals were analysed through single crystal X-ray diffraction
studies only and corresponded to the cleaved product (11) (Fig. 13
and Table 1) indicating cleavage of Te–C, Te–Cl and Te–S bonds
and, probably, some sort of rearrangement.
2. Experimental
1,1,2,3,4,5,6-Heptahydro-1,1-diiodo
[22,23], 1,1,2,3,4,5,6-heptahydro-1,1-dibromo
tellurane
[C5H10TeI2]
tellurane
[C5H10TeBr2] [24] and 1,1,2,3,4,5,6-heptahydro-1,1-dichloro tellu-
rane [C5H10TeCl2] [25], were prepared by literature method. Tellu-
rium, 1,5-pentanediol, potassium iodide, o-phosphoric acid, P2O5
and silver nitrate were commercially obtained from Aldrich and
used as received. Diethylamine, morpholine, piperidine, aniline
and carbon disulfide (Aldrich) were distilled before use. Acetone,
ethanol, solvent ether, petroleum ether, were dried by standard
procedures and freshly distilled before use. Sodium/ammonium
salts of diethyl-, morpholine-, piperidine- and aniline dithiocarba-
mates were freshly prepared. Melting points were recorded in cap-
illary tubes and are uncorrected. Elemental analyses for C, H and N
were carried on an Elemental Analyser Heraeus Carlo Erba 1108.
Tellurium content was determined volumetrically in the laboratory
[26]. IR spectra were recorded using a Shimadzu 8210 PC FT-IR
spectrometer in the frequency range 4000–350 cmÀ1 with the
samples in KBr discs. 1H, 13C and 125Te NMR spectra were recorded
at 300.13 MHz in CDCl3 solutions containing tetramethyl silane as
internal standard on a Bruker DRX 300 or Varian VXR 3005
spectrometer.
The analytical and spectroscopic data for the complexes 1–14
are given as follows:
1,1,2,3,4,5,6-Heptahydro-1-iodo-1-(diethyldithiocarbamato)tellu-
rane C5H10TeI{S2CN(C2H5)2} (1 ): yield: 1.00 g (48%), m.p. 110 °C.
Anal. Calc. for C10H20INS2Te: C, 25.39; H, 4.23; N, 2.96; Te, 26.9.
Found: C, 25.38; H, 4.20; N, 2.94; Te, 26.9%. FT-IR (KBr, cmÀ1):
2.1. Synthesis of C5H10TeL2, C5H10TeXL and SC(NHC6H5)2 [X = Cl, Br, I;
L = S2CN(C2H5)2, S2CNC4H8O, S2CNC5H10, S2CNHC6H5]
1494 vs 1424 s (mCN); 995 s (mCS); 500 s (m
TeCH2). 1H NMR (CDCl3)
d ppm: 3.37 [t, 4H, Te(CH2)2], 2.31 [m, 4H and 2H, TeCCH2 and TeC-
CH2CH2], 3.71 [m, 4H, (–CH2)2N], 1.28 [m, 6H, (–CH3)C].
1,1,2,3,4,5,6-Heptahydro-1-iodo-1-(diethyldithiocarbamato)
tellurane C5H10TeI{S2CN(C2H5)2} (1), 1,1,2,3,4,5,6-heptahydro-1-
iodo-1-(morpholine dithiocarbamato) tellurane C5H10TeI(S2CNC4-
H8O) (2), 1,1,2,3,4,5,6-heptahydro-1-iodo-1-(piperidine dithio-
1,1,2,3,4,5,6-Heptahydro-1-iodo-1-(morpholine dithiocarbamato)
tellurane C5H10TeI(S2CNC4H8O) (2): yield: 1.90 g (88%), m.p. 186 °C.
Anal. Calc. for C10H18INOS2Te: C, 24.66; H, 3.69; N, 2.87; Te, 26.2.
Found: C, 24.63; H, 3.67; N, 2.86; Te, 26.2%. FT-IR (KBr, cmÀ1):
carbamato) tellurane C5H10TeI(S2CNC5H10
)
(3), 1,1,2,3,4,5,
tellurane
1428 m, 1381 m (mCN); 1038 s (mCS); 585 s (m
TeCH2); 1H NMR
6-heptahydro-1-bromo-1-(diethyldithiocarbamato)
(CDCl3) d ppm: 3.66 [t, 4H, (CH2)2Te], 2.33 [m, 4H and 2H,
TeCCH2 and TeCCH2CH2], 4.14 [t, 4H, (–CH2)2N], 3.87 [t, 4H,
(–CH2)2O].
C5H10TeBr{S2CN(C2H5)2} (4), 1,1,2,3,4,5,6-heptahydro-1-bromo-1-
(morpholine dithiocarbamato) tellurane C5H10TeBr(S2CNC4H8O)
(5), 1,1,2,3,4,5,6-heptahydro-1-bromo-1-(piperidine dithiocarbam-
Scheme 1. Method of preparation of complexes 1–14.

2204
P.C. Srivastava et al. / Polyhedron 29 (2010) 2202–2212
Table 1
Crystal data and structure parameters for complexes 1, 2, 4, 7, 8, 9 and 11.
1
2
4
7
8
9
11
Empirical formula
Formula weight
T (K)
C
10H20INS2Te
C10H18INOS2Te
486.87
293(2)
C10H19BrNS2Te
424.89
200(2)
C10H20ClNS2Te
381.44
200(2)
C10H18ClNOS2Te
395.42
296(2)
C11H20ClNS2Te
393.45
110(2)
C13H12N2S
228.31
200(2)
472.89
103(2)
Wave length (Å)
Crystal system
Space group
0.71073
orthorhombic
P212121
0.71073
monoclinic
P2(1)/n
0.71073
orthorhombic
P212121
0.71073
orthorhombic
Pbca
0.71073
triclinic
P1
0.71073
monoclinic
P121/c1
0.71073
orthorhombic
Pnma
Unit cell dimension
a (Å)
b (Å)
c (Å)
6.6612(8)
10.2132(13)
22.665(3)
90
90
90
11.0450(5)
11.4427(5)
12.4484(5)
90
90
90
6.6031(3)
10.1476(4)
22.2337(9)
90
90
90
12.1485(3)
10.6964(3)
22.4477(6)
90
90
90
6.8744(4)
9.4989(5)
11.8929(7)
87.142(5)
73.531(5)
81.320(5)
736.19(7)
2
6.53301(17)
19.7309(5)
11.2816(3)
90
96.494(3)
90
7.8552(6)
25.5231(8)
5.6920(5)
90
90
90
a
(°)
b (°)
(°)
c
Volume (Å3)
Z
1542.0(3)
4
1561.41(12)
4
1489.78(11)
4
2916.97(13)
8
1444.88(7)
4
1141.18(14)
4
Calculated density
2.037
2.071
1.894
1.737
1.784
1.809
1.329
(mg/m3)
Absorption coefficient 4.177
(mmÀ1
F(0 0 0)
4.133
920
4.932
820
2.482
1504
2.467
388
2.508
776
0.255
480
)
896
Crystal size (mm3)
h Range for data
collection (°)
0.40 Â 0.45 Â 0.65 0.20 Â 0.44 Â 0.72 0.53 Â 0.38 Â 0.22 0.46 Â 0.25 Â 0.22 0.52 Â 0.37 Â 0.12 0.47 Â 0.35 Â 0.12 0.53 Â 0.38 Â 0.19
1.80–28.28
11 605
97.3
2.33–28.32
11 984
98.6
4.79–32.54
10 219
98.7
4.68–32.47
17 111
99.0
4.68–32.47
6254
4.78–32.71
10 566
99.2
4.70–32.44
8782
Reflection collected/
unique (Rint
)
Completeness to hmax
(%)
85.1
99.4
Maximum and
minimum
0.894386 and
0.609696
0.928068 and
0.650419
1.00000 and
0.19244
1.00000 and
0.54887
1.00000 and
0.39785
1.00000 and
0.53811
1.00000 and
0.81722
transmission
Refinement method
Data/restraints/
parameters
full-matrix least squares on F2
3723/0/139
3837/0/145
4731/0/134
1.052
4844/0/147
0.934
3911/0/145
1.020
4757/0/145
0.999
1971/0/76
1.086
Goodness-of-fit (GOF)
1.243
1.066
on F2
Final R indices
R1 = 0.0227,
wR2 = 0.0567
R1 = 0.0230,
wR2 = 0.0568
R1 = 0.0302,
wR2 = 0.0799
R1 = 0.0393,
wR2 = 0.0828
R1 = 0.0484,
wR2 = 0.1169
R1 = 0.0611,
wR2 = 0.1240
R1 = 0.0272,
wR2 = 0.0525
R1 = 0.0651,
wR2 = 0.0596
R1 = 0.0732,
wR2 = 0.2085
R1 = 0.0972,
wR2 = 0.2238
R1 = 0.0283,
wR2 = 0.0583
R1 = 0.0397,
wR2 = 0.0606
R1 = 0.0419,
wR2 = 0.1128
R1 = 0.0631,
wR2 = 0.1195
[I > 2r(I)]
R indices (all data)
Largest difference peak 1.299 and À0.785 0.962 and À0.728 1.790 and À1.744 1.367 and À0.706 3.946 and À1.114 1.242 and À0.688 0.385 and À0.207
and hole (e ÅÀ3
)
1,1,2,3,4,5,6-Heptahydro-1-iodo-1-(piperidine dithiocarbamato)
tellurane C5H10TeI(S2CNC5H10) (3): yield: 0.50 g (23%), m.p. 150 °C.
Anal. Calc. for C11H20INS2Te: C, 29.23; H, 3.24; N, 2.84; Te, 25.9.
Found: C, 29.21; H, 3.22; N, 2.83; Te, 25.8%. FT-IR (KBr, cmÀ1):
1,1,2,3,4,5,6-Heptahydro-1-bromo-1-(piperidine dithiocarbama-
to) tellurane C5H10TeBr(S2CNC5H10) (6): yield: 0.23 g (19%), m.p.
170 °C. Anal. Calc. for C11H20BrNS2Te: C, 30.02; H, 4.55; N, 3.18;
Te, 29.0. Found: C, 30.01; H, 4.52; N, 3.15; Te, 29.0%. FT-IR (KBr,
1439 m, 1354 m; (
m
CN); 1010 m (
m
CS); 616 w (
m
TeCH2). 1H NMR
cmÀ1): 1459 s, 1432 s (
mCN); 1029 s, 999 m (mCS); 513 m (mTeCH2);
(CDCl3) d ppm: 3.64 [t, 4H, –(CH2)2Te], 2.32 [m, 4H and 2H, TeCCH2
and TeCCH2CH2], 3.86 [s,4H, (–CH2)2N], 1.95,1.80 [m, 4H,
(–CH2)2C].
1H NMR (CDCl3) d ppm: 3.19 [t, 4H, (–CH2)2Te], 1.96 [m, 4H and 2H,
TeCCH2 and TeCCH2CH2], 4.09 [m, 4H, (–CH2)2N], 1.70 [d, 4H,
–CH2(a) and –CH2(b)].
1,1,2,3,4,5,6-Heptahydro-1-bromo-1-(diethyldithiocarbamato) tel-
lurane C5H10TeBr{S2CN(C2H5)2} (4): yield: 1.10 g (92%), m.p. 115 °C.
Anal. Calc. for C10H20BrNS2Te: C, 28.19; H, 4.69; N, 3.29; Te, 30.0.
Found: C, 28.15; H, 4.64; N, 3.27; Te, 29.9%. FT-IR (KBr, cmÀ1):
1,1,2,3,4,5,6-Heptahydro-1-chloro-1-(diethyldithiocarbamato)tel-
lurane C5H10TeCl{S2CN(C2H5)2} (7): yield: 0.70 g (49%), m.p. 145 °C.
Anal. Calc. for C10H20ClNS2Te: C, 31.48; H, 5.24; N, 3.67; Te, 33.0.
Found: C, 31.45; H, 5.22; N, 3.66; Te, 33.0%. FT-IR (KBr, cmÀ1):
1499 m, 1428 s (
mCN); 1011 m, 960 s (
mCS); 501 m (
m
TeCH2). 1H
1494 s, 1423 s (mCN); 1010 w, 985 m (mCS); 562 w (m
TeCH2). 1H
NMR (CDCl3) d ppm: 3.44 [m, 4H, –(CH2)2Te], 2.20 [m, 4H TeCCH2],
1.84 [m, 2H, TeCCH2CH2], 3.88 [q, 4H, (–CH2)2N], 1.28 [t, 6H,
(–CH3)2C]. 13C{1H} NMR (CDCl3) d ppm: 31.70 (TeCH2), 21.97 (TeC-
CH2), 26.22 (TeCCH2CH2), 49.26 (NCH2), 12.09 (NCCH3), 193.13
(S2CN).
NMR (CDCl3) d ppm: 3.40 [q, 4H, –(CH2)2Te], 1.76–2.42 [m, 4H
and 2H, TeCCH2 and TeCCH2CH2], 3.88 [q, 4H, (–CH2)2N], 1.30 [t,
6H, (–CH3)C]. 13C{1H} NMR (CDCl3) d ppm: 33.04 (TeCH2), 26.34
(TeCCH2), 21.75 (TeCCH2CH2), 48.96 (NCH2), 11.98 (NCCH3),
193.32 (S2CN). 125Te NMR (CDCl3, 25 °C) d ppm: 592.0.
1,1,2,3,4,5,6-Heptahydro-1-bromo-1-(morpholine dithiocarbama-
to) tellurane C5H10TeBr(S2CNC4H8O) (5): yield: 0.75 g (61%), m.p.
155 °C. Anal. Calc. for C10H18BrNOS2Te: C, 27.30; H, 4.10; N, 3.18;
Te, 29.0. Found: C, 27.28; H, 4.10; N, 3.17; Te, 29.0%. FT-IR (KBr,
1,1,2,3,4,5,6-Heptahydro-1-chloro-1-(morpholine dithiocarbama-
to) tellurane C5H10TeCl(S2CNC4H8O) (8): yield: 1.90 g (72%), m.p.
140 °C. Anal. Calc. for C10H18ClNOS2Te: C, 30.37; H, 4.55; N, 3.54;
Te, 32.0. Found: C, 30.35; H, 4.54; N, 3.51; Te, 32.0%. FT-IR (KBr,
cmÀ1): 1463 m, 1425 s; (
m
CN); 1024 s, 988 s (
m
CS); 540 s (
m
TeCH2).
cmÀ1): 1459 s, 1428 m (
mCN); 1026 s, 990 s (mCS); 547 s (mTeCH2);
1H NMR (CDCl3) d ppm: 3.40 [t, 4H, (–CH2)2Te], 2.16 [m, 4H and 2H,
TeCCH2 and TeCCH2CH2], 4.17 [t, 4H, (–CH2)2N], 3.70 [m, 4H,
(–CH2)2O].
1H NMR (CDCl3) d ppm: 3.30–3.60 [m, 4H, (CH2)2Te], 1.70–2.44 [m,
4H and 2H, TeCCH2 and TeCCH2CH2], 4.16 [t, 4H, (–CH2)2N], 3.76 [t,
4H, (–CH2)2O].

P.C. Srivastava et al. / Polyhedron 29 (2010) 2202–2212
2205
Table 2
Bond lengths and bond angles for complexes C5H10TeI[S2CN(C2H5)2] (1), C5H10TeI[S2CNC4H8O] (2), C5H10TeBr[S2CN(C2H5)2] (4), C5H10TeCl[S2CN(C2H5)2] (7),
C5H10TeCl[S2CNC4H8O] (8) and C5H10TeCl[S2CNC5H10] (9).
Bond lengths and angles
Te–C
1
2
4
7
8
9
2.182(5)
2.169(5)
2.522(1)
3.094(5)
2.144(4)
2.151(4)
2.520(10)
3.0418(4)
2.152(7)
2.170(7)
2.5057(17)
2.151(2)
2.142(2)
2.5329(7)
2.118(6)
2.158(8)
2.541(2)
2.154(2)
2.158(4)
2.5037(6)
Te–S
Te–I
Te–Br
Te–Cl
2.9324(8)
175.34(5)
2.6031(4)
2.662(2)
2.6863(5)
\I–Te–S
175.48(3)
171.92(2)
\Br–Te–S
\Cl–Te–S
169.58(2)
97.58
171.24(2)
99.40
171.475(19)
95.28
\C–Te–C
93.10
97.82
93.40
\Te–C(1)–C(2)/\Te–C(11)–C(12)*
115.4(3)
116.8(4)
113.5(4)
113.6(4)
115.5(3)
1.788(5)
1.644(5)
1.343(6)
121.9(3)
114.4(4)
123.7(4)
116.5(3)*
119.1(5)*
116.8(5)*
118.5(4)*
115.6(3)*
1.751(3)
1.685(3)
1.316(4)
120.7(2)
115.5(2)
123.7(3)
115.5(5)
117.2(6)
114.2(7)
115.7(6)
114.6(5)
1.776(7)
1.699(7)
1.306(9)
120.4(4)
116.0(5)
123.7(6)
115.17(17)
116.1(2)
114.6(2)
115.1(2)
114.96(16)
1.765(3)
1.688(3)
1.318(3)
120.18(16)
115.2(2)
124.6(2)
115.17(17)*
116.1(2)*
114.6(2)*
115.1(2)*
114.96(16)*
1.765(3)
1.688(3)
1.318(3)
120.18(16)
115.2(2)
124.6(2)
115.97(15)*
115.89(19)*
114.09(18)*
114.7(2)*
\C(1)–C(2)–C(3)/\C(11)–C(12)–C(13)*
\C(2)–C(3)–C(4)/\C(12)–C(13)–C(14)*
\C(3)–C(4)–C(5)/\C(13)–C(14)–C(15)*
\C(4)–C(5)–Te/\C(14)–C(15)–Te*
114.84(15)*
1.773(2)
1.694(2)
C–S
C@S
C–N
S–C–S
S–C–N
N–C–S
1.329(3)
120.56(12)
115.59(16)
123.84(16)
1,1,2,3,4,5,6-Heptahydro-1-chloro-1-(piperidine dithiocarbamato)
tellurane C5H10TeCl(S2CNC5H10 (9 ): yield: 1.40 g (43%), m.p.
2.2. X-ray measurements
)
120 °C (dec.). Anal. Calc. for C11H20ClNS2Te: C, 33.58; H, 5.09; N,
A summary of the crystal data and refinement parameters for
C5H10TeI{S2CN(C2H5)2} (1), C5H10TeI(S2CNC4H8O) (2), C5H10TeBr-
{S2CN(C2H5)2} (4), C5H10TeCl{S2CN(C2H5)2} (7), C5H10TeCl(S2CN-
C4H8O) (8), C5H10TeCl(S2CNC5H10) (9) and SC(NHC6H5)2 (11) are
given in Table 1. The crystals of 1, 2 were mounted on a Bruker
P4S and of 4, 7, 8, 9 and 11 on an Oxford Diffraction Gemini diffrac-
3.56; Te, 32.0. Found: C, 33.55; H, 5.08; N, 3.54; Te, 32.0%. FT-IR
(KBr, cmÀ1): 1475 m, 1433 s; (
m
CN); 1006 s, 971 s (
mCS); 507 m
(m
TeCH2). 1H NMR (CDCl3) d ppm: 3.18 [t, 4H, –(CH2)2Te], 2.38
[m, 4H and 2H, TeCCH2 and TeCCH2CH2], 1.94 [m, 4H and 2H,
NCCH2 and NCCCH2], 4.10 [s, 4H, (–CH2)2N].
1,1,2,3,4,5,6-Heptahydro-1-chloro-1-(aniline dithiocarbamato) tel-
lurane C5H10TeCl(S2CNHC6H5) (10): yield: 1.00 g (67%), m.p. 115 °C.
Anal. Calc. for C12H16ClNS2Te: C, 35.90; H, 3.99; N, 3.49; Te, 31.8.
Found: C, 35.88; H, 3.95; N, 3.46; Te, 31.7%. FT-IR (KBr, cmÀ1):
tometer using graphite-monochromatic Mo
K
a
radiation
(k = 0.71073 Å). The structures of 1 and 4 were solved in space
group P212121, 2 in space group P2(1)/n, 7 in space group Pbca,
8 in space group P1, 9 in space group P121/c1 and 11 in space
group Pnma. The data were corrected for Lorentz, polarization
and absorption effects. The structures were solved by routine hea-
vy atom and Fourier methods (SHELXS-97 [27]). Non-hydrogen
atoms were refined anisotropically by full-matrix least squares
1525 m, 1454 m; (mCN); 1031 m, 1000 w (mCS); 527 m (mTeCH2).
1H NMR (CDCl3) d ppm: 3.54 [t, 4H, –(CH2)2Te], 2.14 [m, 4H, TeC-
CH2], 1.88 [m, 2H, TeCCH2CH2], 7.25–7.47 [m, 5H, –C6H5].
1,1,2,3,4,5,6-Heptahydro-1,1-(diethyldithiocarbamato) tellurane
C5H10Te{S2CN(C2H5)2}2 (12): yield: 0.59 g (27%), m.p. 118 °C. Anal.
Calc. for C15H30N2S4Te: C, 36.46; H, 6.08; N, 5.67; Te, 25.8. Found:
C, 36.43; H, 6.05; N, 5.66; Te, 25.8%. FT-IR (KBr, cmÀ1): 1483 s.,
1445 s (mCN); 976 s (mCS); 563 s (m
TeCH2). 1H NMR (CDCl3) d
ppm: 3.20 [t, 4H, –(CH2)2Te], 2.13 [m, 4H, TeCCH2], 1.75 [m, 2H,
TeCCH2CH2], 3.94 [q, 8H, (–CH2)2N], 1.28 [t, 12H, (–CH3)C].
13C{1H} NMR (CDCl3) d ppm: 40.25 (TeCH2), 27.17 (TeCCH2),
30.55 (TeCCH2CH2), 48.39 (NCH2), 23.25 (NCCH3), 198.73 (S2CN).
125Te NMR (CDCl3, 25 °C) d ppm: 526.0.
1,1,2,3,4,5,6-Heptahydro-1,1-bis(morpholine dithiocarbamato)tel-
lurane C5H10Te(S2CNC4H8O)2 (13): yield: 1.22 g (56%), m.p. 170 °C.
Anal. Calc. for C15H26N2O2S4Te: C, 34.50; H, 4.98; N, 5.37; Te,
24.5. Found: C, 34.48; H, 4.94; N, 5.36; Te, 24.4%. FT-IR (KBr,
cmÀ1): 1465 s, 1427 s ( TeCH2); 1H
mCN); 984 m (mCS); 539 s (m
NMR (CDCl3) d ppm: 3.77 [t, 4H, (CH2)2Te], 2.17 [m, 4H, TeCCH2],
4.13 [t, 4H, (–CH2)2N], 3.84 [t, 8H, (–CH2)2O].
1,1,2,3,4,5,6-Heptahydro-1,1-(piperidine dithiocarbamato) tellu-
rane C5H10Te(S2CNC5H10)2 (14): yield: 0.50 g (22%), m.p. 120 °C.
Anal. Calc. for C17H30N2S4Te: C, 39.41; H, 5.79; N, 5.40; Te, 24.6.
Found: C, 39.40; H, 5.77; N, 5.37; Te, 24.6%. FT-IR (KBr, cmÀ1):
1475 vs 1431 vs; (mCN); 967 s (mCS); 510 m (m
TeCH2). 1H NMR
(CDCl3) d ppm: 3.33 [t, 4H, –(CH2)2Te], 2.07 [m, 4H, TeCCH2],
4.04 [s, 8H, (–CH2)2N], 1.96,1.59 [m, 8H, (–CH2)2C] 13C{1H} NMR
(CDCl3) d ppm: 40.42 (TeCH2), 25.90 (TeCCH2), 29.74 (TeCCH2CH2),
53.38 (NCH2), 20.54 (NCCH2), 145.31 (S2CN).
Fig. 1. Crystal structure of C5H10TeI{S2CN(C2H5)2} (1).

2206
P.C. Srivastava et al. / Polyhedron 29 (2010) 2202–2212
Fig. 2. Stair type supramolecular association of C5H10TeI{S2CN(C2H5)2 (1).
using the SHELXL-97 program [27] with hydrogen atoms in idealized
positions (Table 1). Selected bond lengths and bond angles for 1, 2,
4, 7, 8, and 9 are listed in Table 2.
(3.574, 3.915 Å) resulting in the formation of a dimer. The sulfur
atoms involved in the formation of TeÁÁÁS secondary bonds are
those of >CS2 group (a) free sulfur (b) sulfur covalently bonded to
tellurium.
The former sulfur atom of >CS2 group also enters into the for-
mation of intramolecular TeÁÁÁS secondary bonds (3.253 Å)
[28,29]. These dimers are further connected through C–HÁÁÁI hydro-
gen bonds (Table 3) in which hydrogen of >CH2 of diethyl dithio-
carbamate group forms hydrogen bond with free iodine atom of
(1). The binding of dimers through C–HÁÁÁI interactions results in
the formation of stair like supramolecular association (Fig. 2).
3. Results and discussion
3.1. X-ray structures of complexes 1, 2, 4, 7, 8 and 9
The X-ray structures of complexes 1, 2, 4, 7, 8 and 9 show that
these complexes contain the monomeric unit of C5H10TeX(S2CNR)
(X = Cl, Br, or I; R = (C2H5)2, C4H8O, C5H10, C6H5NH). In complexes
(1, 2, 4, 7, 8 and 9), there is telluracyclohexane ring and the ring
has chair conformation due to staggered situation of C–H bonds
on neighbouring carbon atoms. The tellurium atom is bonded
through one of the sulfur of alkyl/aryl dithiocarbamate group
(S2CNR) and one halogen atom (X) by two axial bonds approxi-
mately perpendicular to the C–Te–C plane (Table 2) which deviates
from linearity with a sulfur and halogen atom pushed away from
the equatorial electron lone pair in agreement with the earlier
observations [5,6]. Tellurium atom forms two normal bonds with
the two neighbouring carbon atoms (average \C–Te–C = 96.25
3.15) (Table 2). The four closest atoms S,C,C,X and steriochemically
active electron lone pair provide a distorted trigonal bipyramidal
geometry around tellurium atom. The other three atoms makes
an angle (average \C(2)–C(3)–C(4)/C(12)–C(13)–C(14) = 115.15
1.65) (Table 2). The ring has chair confirmation in which part of
the ring is flattened and a part is considerably puckered.
3.3. Supramolecular association of C5H10TeI(S2CNC4H8O) (2)
In the same way as discussed above for the supramolecular
association of (1), the two molecules of C5H10TeI(S2CNC4H8O) (2)
are interconnected through intermolecular TeÁÁÁS secondary bonds
(3.618 Å) (sulfur atom involved is free sulfur atom of CS2 group)
resulting in the formation of dimer. This sulfur atom also enter into
the formation of intramolecular TeÁÁÁS secondary bond (3.196 Å).
Another dimer is formed through C(sp3)HÁÁÁO hydrogen bonds
The S2CNR group is bonded to tellurium through one of the sul-
fur which is connected to carbon through single bond and the other
sulfur of C@S (CS2 group) is attached to tellurium through intramo-
lecular TeÁÁÁS secondary bonds in complexes 1, 2, 4, 7, 8 and 9 (Figs.
1, 3, 5, 7, 9 and 11 and Table 3). In complexes 1, 2, 4, 7 and 9 this
sulfur atom also enters into the formation of intermolecular TeÁÁÁS
secondary bonds (Table 3).
In complexes 1, 2 and 4, the supramolecular association is
formed only through Te–S secondary bonds whereas in the case
of complexes 7, 8 and 9, the supramolecular association is achieved
through TeÁÁÁS secondary bonds, C–HÁÁÁO/C–HÁÁÁCl hydrogen bonds
(Table 3). These supramolecular associations have been discussed
as follows.
3.2. Supramolecular association of C5H10TeI{S2CN(C2H5)2} (1)
In the unit cell, molecules of C5H10TeI{S2CN(C2H5)2} (1) are
interconnected through intermolecular TeÁÁÁS secondary bonds
Fig. 3. Crystal structure of C5H10TeI(S2CNC4H8O) (2).

P.C. Srivastava et al. / Polyhedron 29 (2010) 2202–2212
2207
Fig. 4. Hexameric supramolecular association of C5H10TeI(S2CNC4H8O) (2).
C(sp3)HÁÁÁO hydrogen bonds [hydrogen is of >CH2 group of
C5H10Te heterocycle and O is of the ligand C4H8O] resulting in
the formation of hexameric supramolecular association for (2)
(Fig. 4).
3.4. Supramolecular association of C5H10TeBr{S2CN(C2H5)2} (4)
In the unit cell, molecules of C5H10TeBr[S2CN(C2H5)2] (4) are
interconnected through intermolecular TeÁÁÁS secondary bonds
[30] resulting in the formation of dimers. In the dimers sulfur of
first monomeric unit (sulfur covalently bonded to Te atom) is
bonded to Te of second monomeric unit through intermolecular
TeÁÁÁS secondary bonds while the sulfur of second monomeric unit
(free sulfur of CS2 group) is bound to Te atom of first monomeric
unit.
The free sulfur of CS2 group also forms intramolecular TeÁÁÁS sec-
ondary bonds [3.228 Å]. These dimers are interconnected through
intermolecular TeÁÁÁS secondary bonds (TeÁÁÁS(2)#1 = 3.5789(18) Å,
TeÁÁÁS(1)#2 = 3.8876(18) Å) resulting in hexameric supramolecular
association (zig-zag ribbon) (Fig. 6).
The hexameric supramolecular association formed in complex
(4) is different from the hexameric supramolecular association
present in (1) and (2) in the respect that in complex (4) the dimers
are interconnected through TeÁÁÁS secondary bonds. Whereas in
complex (4) the dimers are interconnected through C–H–I hydro-
gen bonds and in complex (2) the dimers are interconnected
through C(sp3)HÁÁÁO hydrogen bonds.
Fig. 5. Crystal structure of C5H10TeBr{S2CN(C2H5)2} (4).
3.5. Supramolecular association of C5H10TeCl{S2CN(C2H5)2} (7)
(hydrogen is of >CH2 group of the ligand C4H8O group and oxygen
is of C4H8O group of another molecule).
These two different type of dimers (one formed through inter-
molecular TeÁÁÁS secondary bonds and the other formed through
C–HÁÁÁO hydrogen bonds) are further connected through
As discussed above for the complexes (1) and (4) in the unit cell
of complex (7), in the unit cell, molecules of C5H10TeCl[S2-
CN(C2H5)2] are connected through intermolecular TeÁÁÁS secondary
bonds [3.5760(7) Å] [2] resulting in the formation of dimers.

2208
P.C. Srivastava et al. / Polyhedron 29 (2010) 2202–2212
Fig. 6. Hexameric supramolecular association (zig-zag ribbon) of C5H10TeBr{S2CN(C2H5)2} (4).
Cl the nuclearity of the supramolecular association is reduced from
hexameric to tetrameric supramolecular association.
3.7. Supramolecular association of C5H10TeCl(S2CNC5H10) (9)
In the unit cell, molecules of C5H10TeCl(S2CNC5H10) form dimers
through cooperative participation of intermolecular TeÁÁÁS second-
ary bonds (3.557 Å) [2] and C–HÁÁÁCl hydrogen bonds. The C(sp3)–
HÁÁÁCl hydrogen bonds (Table 3) involve C–H group of piperidine
ring and Cl of the same molecule. These dimers are joined through
C(sp3)–HÁÁÁCl hydrogen bond resulting in the formation of deca-
meric supramolecular association (Fig. 12), having the highest
nuclearity in the supramolecular associations in the present inves-
tigation. The C(sp3)–HÁÁÁCl hydrogen bonds involve C–H groups of
telluracyclohexane ring and Cl of other molecules (Table 3).
Fig. 7. Crystal structure of C5H10TeCl{S2CN(C2H5)2} (7).
3.8. The X-ray structure and supramolecular association of the cleaved
S
C
These dimers are further interconnected through C(sp3)–HÁÁÁCl
hydrogen bonds (Table 3) to form stair type supramolecular asso-
ciation (Fig. 8) as is present in complex (1). Apart from these inter-
molecular TeÁÁÁS secondary bonds, intramolecular TeÁÁÁS secondary
bonds [3.2468(7) Å] is also present.
A comparative account of supramolecular association present in
the complexes C5H10TeI{S2CN(C2H5)2} (1), C5H10TeBr{S2CN(C2H5)2}
(4) and C5H10TeCl{S2CN-(C2H5)2} (7) reveals that complexes (1)
and (7) possess stair type supramolecular associations whereas
the complex (4) possess different (zig-zag ribbon) type supramo-
lecular association.
product SC(NHC6H5)2
(11)
NHC6H5
H5C6HN
The X-ray structure analysis data at 200(2) K of the cleaved
product [obtained in the substitution reaction of C5H10TeCl2 and
NH4S2CNHC6H5 in 1:1 M ratio] reveals that the carbon atom of
C@S of CS2 group is bonded to two C6H5NH groups (Fig. 13) with
the bond distances and bond angles S–C(1) = 1.6930(18) Å, C(1)–
N = 1.3462(13) Å, N–C(2) = 1.4295(14) Å, \S–C(1)–N = 122.73(8)°,
\C(1)–N–C(2) = 124.71(10)°, \N–C(2)–C(3) = 120.31(12)°. The C–
C bond lengths and \C–C–C bond angles of C6H5 rings are in the
usual range 1.3795–1.3925 Å and 119.31–120.53°, respectively.
S
In the unit cell, the molecules of
(11) are
3.6. Supramolecular association of C5H10TeCl(S2CNC4H8O) (8)
C
NHC6H5
H5C6HN
In the unit cell, molecules of C5H10TeCl(S2CNC4H8O) are
connected through C(sp3)–HÁÁÁO hydrogen bonds to form dimers.
These dimers are interconnected through C(sp3)–HÁÁÁCl hydrogen
bonds to form tetrameric supramolecular association (Fig. 10 and
Table 3).
interconnected through N–HÁÁÁS hydrogen bonds resulting in the
formation of trimeric supramolecular associations having distorted
hexagonal cavities (Fig. 14). Such type of supramolecular associa-
tions with cavities might be, probably, suitable for the binding of
guest molecules [31]. The parameters related to N–H(0A)ÁÁÁS hydro-
gen bonds are: NÁÁÁS#2 = 3.4917(11) Å, H(0A)ÁÁÁS#2 = 2.65 Å and
\N–H(0A)ÁÁÁS#2 = 160.2°.
A comparative account of supramolecular association present in
complexes (2) and (8) reveals that with the change of I atom with

P.C. Srivastava et al. / Polyhedron 29 (2010) 2202–2212
2209
Fig. 8. Hexameric supramolecular association of C5H10TeCl{S2CN(C2H5)2} (7).
pared to our earlier report [6] on the cleaved product
Te(S2CNC5H10 2 (15) obtained in the substitution reaction of
C8H8TeI2 (heterocyclic organotellurium complex) with
)
NH4S2CNC5H10 (Reaction 2) (supported by QC calculations) indi-
cates that in the former reaction, from the product obtained after
substitution(exchange) reaction with dithiocarbamate ligand, all
the bonds associated with Te viz. Te–C, Te–Cl, Te–S are cleaved
and, probably, some rearrangement takes place whereas in the lat-
ter reaction after substitution (exchange) reaction with dithiocar-
bamate ligand the cleavage of only Te–C bonds takes place
(Table 4).
Such type of cleavage reactions are also comparable with our
next report on dialkyltellurium dithiocarbamates viz. the reaction
of (C2H5)2TeI2 with NH4S2CNC5H10 (Reaction 3) and
NH4S2CNC4H8O (Reaction 4) resulting in the formation of the
H
Fig. 9. Crystal structure of C5H10TeCl(S2CNC4H8O) (8).
S
C
cleaved products Te(S2CNC5H10 2
)
(15) and
(16),
TeOC4H8N
H
The above cleaved product
(11) obtained
NHC6H5
H5C6HN
respectively. Here, in the former case after substitution (exchange)
reaction of dithiocarbamate group Te–C bonds are broken as was in
the above sited case with C8H8TeI2 as precursor [6] while in the
in the substitution reaction of C5H10TeCl2 (heterocyclic organotel-
lurium complex) with NH4S2CNHC6H5 (Reaction 1) is when com-
Table 3
Secondary bonds (TeÁÁÁS) and C–HÁÁÁX (X = O, Cl) hydrogen bond parameters for complexes 1, 2, 4, 7, 8 and 9.
Bond lengths and angles
1
2
4
7
8
9
TeÁÁÁS (intramolecular)
TeÁÁÁS (intermolecular)
3.253
3.574
3.915
4.149
3.196
3.618
3.228
3.5789(18)
3.8876(18)
3.2468(7)
3.5760(7)
3.218
3.226
3.557
CÁÁÁI (d)
CÁÁÁCl (d)
3.866(10)
2.89
3.860
3.465
2.89
3.527(2)
3.668(2)
CÁÁÁO (d)
HÁÁÁI (d)
HÁÁÁCl (d)
3.169
2.81
2.74
HÁÁÁO (d)
2.49
C–HÁÁÁI (h)
C–HÁÁÁCl (h)
134.88
177.2
162.9
147.8
129.4
155.4
C–HÁÁÁO (h)

2210
P.C. Srivastava et al. / Polyhedron 29 (2010) 2202–2212
Fig. 10. Tetrameric supramolecular association of C5H10TeCl(S2CNC4H8O) (8).
Fig. 11. Crystal structure of C5H10TeCl(S2CNC5H10) (9).
H
H
latter case the cleaved product
is, probably, due to
TeOC4H8N
(a) the evolution of CS2 and (b) breaking of Te–C bonds and then
some sort of rearrangement (Table 4).
Thus in nut-shell in the first place, in the present investigation;
in the absence of QC calculations on the cleaved product
S
C
(11) it is actually difficult to define the path-
Fig. 12. Decameric supramolecular association of C5H10TeCl(S2CNC5H10) (9).
NHC6H5
H5C6HN
way through which the cleaved product has been obtained. On
the basis of our earlier QC calculations on the cleaved product
Te(S2CNC5H10)2 [6], the postulated pathways involve (a) first li-
fuming nitric acid is not able to break Te–C (alkyl) bonds instead
it results in the formation of (Me2TeNO3)2O whereas in contrast
to this, in all the above discussed cleavage reactions carried out
in our research group, Te–C (alkyl) bonds have been scissioned
(Table 4).
gand (dtc) substitution/exchange reaction occurs which is followed
by (b) cleavage reaction. In the second place, the Te–C (alkyl) bonds
are, in general, very stable for example we [32] have observed that
even the reaction of Me2TeI2 [containing Te–C (alkyl) bond] with

P.C. Srivastava et al. / Polyhedron 29 (2010) 2202–2212
2211
4. Conclusions
Among organo (heterocyclic) tellurium(IV) dialky/aryl dithio-
carbamates there is no report on supramolecular assemblies of
C5H10Te dialky/aryl dithiocarbamates where dithiocarbamate
groups behave as unidentate ligands. The supramolecular associa-
tions, reported in the present investigation, have been built up
through intermolecular TeÁÁÁS secondary bonds and/or C–HÁÁÁX
(X = O, Cl, I) hydrogen bonds. The postulated pathway for obtaining
Fig. 13. Crystal structure of SC(NHC6H5)2 (11).
Fig. 14. Trimeric supramolecular association of SC(NHC6H5)2 (11).
Table 4
Description of the cleavage reactions.
Reaction
Molar ratio
Postulated intermediate product obtained by
substitution/exchange of the ligand
(dithiocarbamate group)
Cleaved product
Characterization mode
of the cleaved product
Reference
1. C5H10TeCl2
+ NH4S2CNHC6H5
1:1
single crystal X-ray
diffraction data
[present Investigation]
Cl
C5H10Te
S
SCNHC6H5
C
NHC6H5
H5C6HN
S
2. C8H8TeI2
+ NH4S2CNC5H10
1:2
H10C5NCS2TeS2CNC5H10
single crystal X-ray
diffraction data
[6]
S
SCNC5H10
C8H8Te
SCNC5H10
S
3. (C2H5)2TeI2
+ NH4S2CNC5H10
1:2
1:2
H10C5NCS2TeS2CNC5H10
single crystal X-ray
diffraction data
[to be published]
[to be published]
S
C2H5
SCNC5H10
Te
C2H5
SCNC5H10
S
S
4. (C2H5)2TeI2
+ NH4S2CNC4H8O
single crystal X-ray
diffraction data
H
TeOC4H8N
H
C2H5
SCNC4H8O
Te
C2H5
SCNC4H8O
S

2212
P.C. Srivastava et al. / Polyhedron 29 (2010) 2202–2212
(b) O.D. Fox, M.G.B. Drew, E.J.S. Wilkinson, P.D. Beer, Chem. Commun. (2000)
391;
the cleaved product is based on the comparative account with
other similar type of cleavage reactions.
(c) O.D. Fox, M.G.B. Drew, P.D. Beer, Angew. Chem., Int. Ed. 39 (2000) 136.
[8] J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry: Principles of Structure
and Reactivity, Pearson Education, Inc., 2000. pp. 929, 958.
[9] E.L.M. Lempers, J. Reedjik, Adv. Inorg. Chem. 37 (1991) 175.
[10] R.C. Vallari, R. Pietruszko, Science 216 (1982) 637.
[11] M.S. Wysor, L.A. Zwelling, J.E. Sanders, M.M. Grenan, Science 217 (1982)
454.
5. Supplementary data
CCDC 660999, 654231, 763397, 763398, 763399, 763400 and
763401 contain the supplementary crystallographic data for 1, 2,
4, 7, 8, 9 and 11. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
[12] (a) I. Haiduc, F.T. Edelmann, Supramolecular Chemistry, Wiley VCH,
Weinheim, NY, 1999;
(b) I. Haiduc, J. Zukerman-Schpector, Phosphorus, Sulfur Silicon 171 (2001)
171.
[13] (a) J.-M. Lehn, Angew. Chem., Int. Ed. Engl. 27 (1988) 89;
(b) J.-M. Lehn, Supramolecular Chemistry, VCH, Weinheim, 1995.
[14] E. Weber, J. Mol. Graphics 7 (1989) 12.
[15] F. Vögtle, Supramolecular Chemistry, Wiley, Chichester, 1991.
[16] (a) G.R. Desiraju, Angew. Chem., Int. Ed. Engl. 34 (1995) 2311;
(b) P.J.M.W.L. Birker, H.C. Freeman, Chem. Commun. (1976) 312.
[17] G.M. Whitesides, E.C. Simanek, J.P. Mathias, C.T. Seto, D.N. Chin, M. Mammen,
D.M. Gordon, Acc. Chem. Res. 28 (1995) 37.
Acknowledgements
P.C.S. is thankful to Department of Science and Technology
(DST), Government of India and Council of Scientific and Industrial
Research (CSIR), New Delhi for financial support.
[18] J. Bernstein, M.C. Etter, L. Leiserowitz, in: H.B. Burgi, J.D. Dunitz (Eds.),
Structure Correlation, vol. 2, VCH, Weinheim, 1994, pp. 431–507.
[19] G.R. Desiraju, in: Crystal Engineering: The Design of Organic Solids, Elsevier,
New York, 1989.
[20] (a) M.C. Etter, Acc. Chem. Res. 23 (1990) 120;
(b) M.C. Etter, J. Phys. Chem. 95 (1991) 4601.
[21] P.C. Srivastava, S. Bajpai, R. Lath, C. Ram, Sm. Bajpai, R.J. Butcher, M. Zimmer,
M. Veith, J. Organomet. Chem. 649 (2002) 70.
References
[1] O. Foss, Acta Chem. Scand. 7 (1953) 227.
[2] I. Haiduc, R.B. King, M.G. Newton, Chem. Rev. 94 (1994) 301. and references
therein.
[3] (a) J.E. Drake, L.N. Khasrou, A.G. Mislankar, R. Ratnani, Inorg. Chem. 38 (1999)
3994;
(b) J.E. Drake, J. Yang, Inorg. Chem. 36 (1997) 1890;
(c) J.E. Drake, R.J. Drake, L.N. Khasrou, R. Ratnani, Inorg. Chem. 35 (1996) 2831;
(d) J.H.E. Bailey, J.E. Drake, Can. J. Chem. 71 (1993) 42.
[4] V.G. Montalvo, R.A. Toscano, A.B. Delgado, R. Cea-Olivares, Polyhedron 20
(2001) 203.
[5] V.G. Montalvo, A.M. Polo, R. Montoya, R.A. Toscano, S.H. Ortega, R. Cea-
Olivares, J. Organomet. Chem. 623 (2001) 74.
[6] P.C. Srivastava, S. Bajpai, R. Lath, R. Kumar, V. Singh, S. Dwivedi, R.J. Butcher, S.
Hayashi, W. Nakanishi, Polyhedron 27 (2008) 835. and references therein.
[7] (a) P.D. Beer, N. Berry, M.G.B. Drew, O.D. Fox, M.E.P. Tosta, S. Patell, Chem.
Commun. (2001) 199;
[22] W.V. Farrar, J.M. Gulland, J. Chem. Soc. (1945) 11.
[23] F. Einstein, J. Trotter, C. Williston, J. Chem. Soc. A (1967) 2018.
[24] P.C. Srivastava, S. Bajpai, R. Lath, Sm. Bajpai, R. Kumar, R.J. Butcher, Polyhedron
23 (2004) 1629.
[25] P.C. Srivastava, Sm. Bajpai, S. Bajpai, R. Kumar, R.J. Butcher, Indian J. Chem. 43A
(2004) 2558.
[26] A.I. Vogel, Quantitative Inorganic Analysis, Longman, London, 1975. p. 267.
[27] G.M. Sheldrick, SHELXS 86, SHELXS 97 and SHELXL 97, University of Göttingen, 1987
and 1997.
[28] A. Panda, G. Mugaesh, H.B. Singh, R.J. Butcher, Organometallics 18 (1999)
1986.
[29] N. Sudha, H.B. Singh, Coord. Chem. Rev. 135/136 (1994) 469.
[30] N.W. Alcock, Adv. Inorg. Chem. RadioChem. 15 (1972) 1.
[31] D.M. Roundhill, Prog. Inorg. Chem. 43 (1995) 533.
[32] P.C. Srivastava, S. Bajpai, C. Ram, R. Kumar, R.J. Butcher, J. Organomet. Chem.
692 (2007) 2482.