Antimony and bismuth dithiocarboxylates: Synthesis, characterization, crystal structures of [Sb(S2Ctol)3] and [Bi(S2CPh)3] and their transformation to polycrystalline M2S3 (M = Sb, Bi)

Article abstract of DOI:10.1016/j.ica.2008.08.022

Antimony and bismuth dithiocarboxylates of the type [M(S₂CAr)₃] (M = Sb, Bi; Ar = C₆H₅ (Ph), 4-MeC₆H₄ (tol)) have been synthesized. These complexes were characterized by elemental analysis,

Full text of DOI:10.1016/j.ica.2008.08.022

Inorganica Chimica Acta 362 (2009) 1819–1824
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Antimony and bismuth dithiocarboxylates: Synthesis, characterization,
crystal structures of [Sb(S2Ctol)3] and [Bi(S2CPh)3] and their transformation
to polycrystalline M2S3 (M = Sb, Bi)
*
Kamal R. Chaudhari, Amey P. Wadawale, Shamik Ghoshal, Suresh M. Chopade, V.S. Sagoria, Vimal K. Jain
Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Antimony and bismuth dithiocarboxylates of the type [M(S2CAr)3] (M = Sb, Bi; Ar = C6H5 (Ph), 4-MeC6H4
(tol)) have been synthesized. These complexes were characterized by elemental analysis, IR, UV–Vis, and
1H NMR spectroscopy. X-ray crystal structural analyses of [Sb(S2Ctol)3] and [Bi(S2CPh)3] showed that the
dithiocarboxylates are asymmetrically chelated to metal atom. The latter acquires a distorted pentagonal
pyramidal geometry as a consequence of the presence of a stereochemically active lone pair of electrons.
Pyrolysis of these complexes either in a furnace or in refluxing diphenylether gave M2S3 as characterized
by their XRD pattern and EDAX analysis.
Received 28 March 2008
Received in revised form 21 July 2008
Accepted 24 August 2008
Available online 29 August 2008
Keywords:
Antimony
Bismuth
Ó 2008 Elsevier B.V. All rights reserved.
Dithiocarboxylic acid
X-ray structure
Metal sulfide
1. Introduction
with little attention on dithiocarboxylates (D) [17]. The sustained
interest in these complexes has been associated due to their
Group V-chalcogenide materials are of special importance ow-
ing to their good photovoltaic properties and high thermo-electric
power which allow potential applications in various opto-elec-
tronic and thermo-electric cooling devices [1,2]. The compounds,
Sb2S3 (band gap 1.78–2.5 eV) and Bi2S3 (band gap 1.3–1.7 eV), di-
rect band semiconductors, have received considerable attention re-
cently [3,4]. Polymer coated Bi2S3 nanoparticles have been used as
imaging agent in X-ray computed tomography [5]. Several syn-
thetic strategies have been adopted to prepare M2S3 [4,6,7],
although use of single source precursors for their preparation ap-
pears to be quite promising. The potential of 1,1-dithiolate com-
plexes of antimony and bismuth for the preparation of thin films
and nanoparticles of M2S3 (M = Sb or Bi) has been realized only re-
cently. Thus complexes, [Sb(S2CNRR0)3] [8], [Bi(S2CNRR0)3] [9],
[Bi(S2COR)3] (R = Me or Et) [10], [MeBi(S2COR)2] [11] and [Bi{S2-
P(OC8H17)2}3] [12], have been used as molecular precursors for
the synthesis of M2S3. The 1,1-dithiolate complexes have a niche
over other precursors like [M(SR)3] [13,14] and ½BifðSPPri Þ Ng ꢀ
numerous applications (catalysts, lubricants, biocides and materi-
als science) and diverse structural features ranging from mono-
meric to polymeric supramolecular assemblies. Subtle variations
in the nature of the organic substituents on the dithiolate group
usually result in different structural motifs [16].
S
S
S
S
Y
Y
R2 N
RO
R
C
C
C
P
-
-
-
-
S
S
S
S
(Y = R or OR)
(A )
(B )
(D )
(C )
In the above prospective it was considered worthwhile to examine
dithiocarboxylates of antimony and bismuth with the following
objectives: (a) to identify the kind of structural motifs adopted by
this family of 1,1-dithiolate ligands, and (b) to assess their suitabil-
ity as molecular precursors for the preparation of M2S3. The results
of this work are described herein.
2
2
3
[15] due to their ease of synthesis and cleaner decomposition.
The chemistry of 1,1-dithiolate complexes of arsenic, antimony
and bismuth has been an active area of research for nearly half a
century [16] and has been dominated by ligands of the type A–C
2. Experimental
All experiments involving antimony and bismuth trichlorides
were carried out under anhydrous conditions in Schlenk flasks.
* Corresponding author.
E-mail address: jainvk@barc.gov.in (V.K. Jain).
0020-1693/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2008.08.022

1820
K.R. Chaudhari et al. / Inorganica Chimica Acta 362 (2009) 1819–1824
Fig. 1. Molecular structure of [Sb(S2Ctol)3] (ORTEP diagram with 50% probability). Inset shows the line diagram of the molecule.
Solvents were dried by standard procedures. Antimony and bis-
muth trichlorides were sublimed before use. Dithiocarboxylic acids
were prepared by the reported methods [18]. (1H NMR in CDCl3,
PhCS2H d: 6.40 (s, br, SH); 7.39 (br, 2H, H-3, 5); 7.57 (br, 1H, H-
4); 8.07 (br, 8.2 Hz, H-2,6). tolCS2H, d: 2.38 (s, Me); 4.71 (s, SH);
7.19 (d, 8.3 Hz, 2H, H-3,5); 7.98 (d, 8.2 Hz, 2H, H-2,6) (C6H4)). Infra-
red spectra were recorded as Nujol mulls between CsI plates on a
Bomem MB-102 FT IR spectrometer. 1H NMR spectra were re-
corded on a Bruker Avance 200 spectrometer as a CDCl3 solution.
Chemical shifts are relative to the internal chloroform peak (d
7.26 ppm). Electronic spectra were recorded in dichloromethane
on a Chemito Spectrascan UV double beam UV–Vis spectropho-
Fig. 2. Molecular structure of [Bi(S2CPh)3] (ORTEP diagram with 50% probability). Inset shows the line diagram of the molecule.

K.R. Chaudhari et al. / Inorganica Chimica Acta 362 (2009) 1819–1824
1821
tometer. The TG analyses were performed on a Netzsch STA Luxx
2.2. X-ray crystallography
instrument which was calibrated with CaC2O4 ꢁ H2O. Powder X-
ray diffraction data were collected on a Philips PW 1820.
Red crystals of [Sb(S2Ctol3] and [Bi(S2CPh)3] were grown from
dichloromethane/hexane mixture and dichloromethane containing
few drops of pyridine, respectively. Addition of pyridine facilitates
dissolution of sparingly soluble complexes, possibly by the forma-
2.1. Synthesis
2.1.1. Preparation of [Sb(S2CPh)3]
tion of a labile pyridine adduct. Intensity data were measured on
Rigaku AFC7S diffractometer fitted with Mo Ka ((k-0.71069 ÅA)
0
To
a
benzene solution (60 cm3) of antimony trichloride
(619 mg, 2.71 mmol), a solution of PhCS2H (1.258 g, 8.15 mmol)
and triethylamine (825 mg, 8.15 mmol) in the same solvent was
added with stirring. The whole was stirred at room temperature
for 4 h. The precipitate was filtered through a G-3 filtration unit
and thoroughly washed with methanol to remove Et3N ꢁ HCl, and
the orange residue was dried in vacuo (835 mg, 53%). M.p. 175 °C
(decomp.). Anal. Calc. for C21H15S6Sb: C, 43.4; H, 2.6; S, 33.1. Found:
radiation so that hmax = 27.5°. The structure was solved by direct
methods [19] and refinement was on F2 [20] using data corrected
for absorption correction effects with an empirical procedure
[21,22]. The non-hydrogen atoms were refined with anisotropic
displacement parameters and fitted with hydrogen atoms in their
calculated positions. Molecular structure was drawn using ORTEP
[23]. Crystallographic and structural determination data are listed
in Table 1.
C, 42.9; H, 2.1; S, 33.5%. UV–Vis kmax: 244, 315 nm.
m(C–S)
722 cmꢂ1 (C@S) 1220 cmꢂ1 1H NMR in CDCl3 d: 7.41 (t, 7.4 Hz,
,
m
.
H-3, 5), 7.63 (t, 7.2 Hz, H-4); 8.24 (d, 8 Hz, H-2, 6).
2.3. Preparation of M2S3
2.1.2. Preparation of [Sb(S2Ctol)3]
(a) Pyrolysis in a furnace: A weighed quantity of the complex in a
quartz boat was heated in a pre-heated furnace at 300 °C
under a flowing nitrogen atmosphere for 4 h. After cooling,
the residue was analyzed by XRD pattern and EDAX.
(b) Solvothermal decomposition of complexes: Thermolysis of
both antimony and bismuth complexes was carried out in
a similar manner. In a typical experiment, diphenylether
(25 cm3) in a three-necked flask was degassed at refluxing
temperature under nitrogen for 30 min. To this a weighed
quantity of [Bi(S2Ctol)3] (42 mg, 0.06 mmol) was added
and the mixture was refluxed for 3 h and gradually cooled.
Thorough washing with methanol (5 ꢃ 3 cm3) followed by
centrifuging and drying under vaccum gave a black residue
(10 mg, 65%), which was characterized as Bi2S3 by XRD and
EDAX analysis.
[Sb(S2Ctol)3] was prepared similar to [Sb(S2CPh)3] as an orange
crystalline solid in 75% yield; m.p. 190 °C (decomp.). Anal. Calc. for
C24H21S6Sb: C, 46.2; H, 3.4; S, 30.8. Found: C, 46.0; H, 2.9; S, 30.5%.
UV–Vis kmax: 242, 337 nm. m , m
(C–S) 721 cmꢂ1 (C@S) 1222 cmꢂ1. 1H
NMR in CDCl3 d: 2.37 (s, Me); 7.17 (d, 7.5 Hz, H-3, 5); 8.16 (d,
7.6 Hz, H-2, 6).
2.1.3. Preparation of [Bi(S2CPh)3]
[Bi(S2CPh)3] was prepared similar to antimony complex as an
orange-red solid (pyridine instead of triethylamine was used in
the reaction) in 69% yield; m.p. 135 °C (decomp.). Anal. Calc. for
C21H15BiS6: C, 37.7; H, 2.3; S, 28.8. Found: C, 38.1; H, 2.3; S,
29.2%. UV–Vis kmax
: 242, 324 nm. m , m(C@S)
(C–S) 723 cmꢂ1
1210 cmꢂ1 1H NMR in CDCl3 d: 7.40 (t, 7.6 Hz, H-3,5); 7.63 (t,
.
7.6 Hz, H-4); 8.21 (d, 7.8 Hz, H-2,6).
3. Results and discussion
2.1.4. Preparation of [Bi(S2Ctol)3]
[Bi(S2Ctol)3] was prepared similar to antimony complex as an
orange-red solid in 79% yield; m.p. 185 °C (decomp.). Anal. Calc.
for C24H21BiS6: C, 40.5; H, 3.0; S, 27.0. Found: C, 40.2; H, 2.7; S,
3.1. Synthesis and spectroscopy
Treatment of antimony and bismuth trichlorides with dithio-
carboxylic acid in 1:3 stoichiometry in the presence of triethyl-
amine in benzene afforded orange-red tris dithiocarboxylate
complexes of the general formula [M(S2CAr)3] (M = Sb or Bi;
Ar = Ph or tol) (Scheme 1). The electronic spectra of these com-
plexes exhibited two strong absorptions at ꢄ245 and ꢄ330 nm
26.8%. UV–Vis kmax
: 235, 345 nm. m , m(C@S)
(C–S) 720 cmꢂ1
1224 cmꢂ1 1H NMR in CDCl3 d: 2.38 (s, Me); 7.20 (d, 8 Hz, H-3,
.
5); 8.14 (d, 8 Hz, H-2, 6).
Table 1
attributable to p–p p
* and n– * transitions in the thiocarbonyl group
Crystallographic data and structural refinement details for [Sb(S2Ctol3] and
[Bi(S2CPh)3]
[24]. The band at ꢄ330 was accompanied by an ill-defined shoul-
der ꢄ350 nm. The IR spectra displayed absorptions due to
m(C@S)
and
m
(C–S) stretchings at ꢄ1220 and ꢄ720 cmꢂ1, respectively
[Sb(S2Ctol)3]
[Bi(S2CPh)3]
[25]. 1H NMR spectra showed characteristic peaks due to aryl pro-
tons of the dithiocarboxylate groups. The 2,6-protons of the aryl
group are deshielded with respect to the corresponding resonances
for the free ligand.
Chemical formula
Formula weight
Crystal size (mm)
Crystal System
Space group
a (Å)
C24H21S6Sb
623.52
0.40 ꢃ 0.20 ꢃ 0.05
monoclinic
C2/c
C21H15BiS6
668.67
0.30 ꢃ 0.05 ꢃ 0.05
monoclinic
C2/c
35.00(3)
31.800(8)
b (Å)
c (Å)
6.388(5)
27.250(12)
120.10(5)
6.4700(13)
24.874(7)
119.30(2)
3.2. Crystal structures of [Sb(S2Ctol)3] and [Bi(S2CPh)3]
b (Å)
Volume (Å3)/Z
5271(7)/8
1.533/2496
2.67–27.50
ꢂ25 6 h 6 45
0 6 k 6 8
ꢂ35 6 l 6 30
7111/6022
6022/0/283
0.0686, 0.0920
0.3056, 0.1352
0.906
4463.1 (18)/8
8.468/2560
2.60–27.51
ꢂ23 6 h 6 41
0 6 k 6 8
ꢂ32 6 l 6 28
6071/5137
5173/0/253
0.0470, 0.0657
0.1643, 0.0858
0.936
The complexes [Sb(S2Ctol)3] and [Bi(S2CPh)3] are discrete
monomers having isomorphous structures (Figs. 1 and 2). Overall
molecular geometry can be described as pentagonal pyramidal.
All the three dithiocarboxylates are asymmetrically chelated to
the central metal atom. The two dithiocarboxylate ligands are
nearly coplanar (164.73° for Sb, 163.65° for Bi) while the third li-
gand is approximately orthogonal to these ligands with S1 at the
apex of the pyramid. There is a void opposite to this apical ligand
which can be thought of being occupied by stereochemically active
lone pair of electrons. This void in associated structures (e.g.,
l
(mmꢂ1)/F(000)
h Range (°)
Limiting indices
Number of reflections/unique
Number of data/restraints/parameters
Final R1 [I > 2r(I)]
R1, wR2 (all data)
Goodness of fit on F2

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K.R. Chaudhari et al. / Inorganica Chimica Acta 362 (2009) 1819–1824
plexes, respectively, as a consequence of a small bite of dithiocar-
boxylate ligand.
S
S
3 Et3N
S
MCl3 + 3 ArCS2H
A variety of tris complexes of antimony and bismuth containing
1,1-dithiolates such as xanthates, dithiocarbamates and dithio-
phosphates have been characterized by X-ray crystallography.
The metal atom in these complexes adopts either a regular octahe-
dral geometry or a distorted variance of this configuration (e.g.,
pentagonal pyramid) depending on whether the lone pair of elec-
tron is subdued or is stereochemically active. Both discrete mono-
mers and associated structures formed by a weak secondary Mꢁ ꢁ ꢁS
interaction have been identified (Table 3) [27–35]. Attempts to
rationalize the observed stereochemistry based on factors, such
as ligand acidity, ligand bite, nature of the substituents on the li-
gand or the size of the metal ion, have met with little success.
Nonetheless the crystal packing factors, which are difficult to eval-
uate, seem to play a significant role in determining the stereo-
chemistry of the molecule.
M
S
-3 Et3N.HCl
S
S
(M = Sb, Bi; S∩S = ArCS2 ; Ar = phenyl (Ph), p-tolyl (tol))
-
Scheme 1.
Bi(S2PMe2)3 [26]) is filled by sulfur atom of a chelating ligand of
another molecule giving secondary Mꢁ ꢁ ꢁS linkages.
The asymmetry in the M–S bonds of the apical ligand is higher
than for the remaining two ligands. The difference in the M–S dis-
tances between long and short M–S bonds of a chelating dithiocar-
boxylate group is greater for antimony complex than the
corresponding values for the bismuth derivative. Owing to the
anisobidentate chelating ligands, an inverse relationship between
M–S and C–S bond distances is evident from Table 2. Thus the
shorter M–S distances are associated with longer C–S distances
and vice-versa for a four-membered ‘MS2C’ chelate ring. The C–S
distances (short 1.66 (av.) and long 1.71 (av.) Å) are essentially
similar to those reported for dithiocarboxylate complexes [24].
The M–S distances (short and long) are within the range reported
for tris dithiolates of antimony and bismuth. The S–M–S angles
in the chelate are 64° and 63° (av.) for antimony and bismuth com-
3.3. Thermal studies
The TG curve of [Sb(S2CPh)3] showed a single step decomposi-
tion at 275 °C with weight loss of 69.4%, suggesting the formation
a
100
80
60
40
20
0
Table 2
Selected bond distances (Å) and angles (°) for [Sb(S2Ctol)3] and [Bi(S2CPh)3]
[Sb(S2Ctol)3]
[Bi(S2CPh)3]
M–S(1)
M–S(2)
M–S(3)
M–S(4)
M–S(5)
M–S(6)
C(1)–S(1)
C(1)–S(2)
C(8)–S(3)
C(8)–S(4)
C(15)–S(5)
C(15)–S(6)
C(1)–C(2)
C(8)–C(9)
C(15)–C(16)
2.481(3)
2.935(3)
2.654(3)
2.866(4)
2.636(3)
2.808(3)
1.728(9)
1.652(9)
1.700(10)
1.666(11)
1.714(10)
1.667(11)
1.461(12)
1.492(13)
1.496(14)
2.581(2)
2.938(3)
2.764(3)
2.903(3)
2.742(3)
2.860(3)
1.746(9)
1.651(8)
1.710(10)
1.672(11)
1.698(9)
1.679(10)
1.472(10)
1.488(12)
1.470(12)
10
20
30
40
50
60
70
2θ degree
S(1)–M–S(2)
S(1)–M–S(3)
S(1)–M–S(4)
S(1)–M–S(5)
S(1)–M–S(6)
S(2)–M–S(3)
S(2)–M–S(4)
S(2)–M–S(5)
S(2)–M–S(6)
S(3)–M–S(4)
S(3)–M–S(5)
S(3)–M–S(6)
S(4)–M–S(5)
S(4)–M–S(6)
S(5)–M–S(6)
M–S(1)–C(1)
M–S(2)–C(1)
S(1)–C(1)–S(2)
M–S(3)–C(8)
M–S(4)–C(8)
S(3)–C(8)–S(4)
M–S(5)–C(15)
M–S(6)–C(15)
S(5)–C(15)–S(16)
64.70(10)
84.35(10)
79.65(11)
88.32(10)
84.31(11)
132.71(10)
75.66(10)
132.00(10)
73.36(10)
63.73(9)
77.73(10)
140.91(9)
140.41(9)
148.85(9)
64.66(9)
94.6(3)
63.84(8)
86.07(8)
80.30(8)
87.45(8)
82.79(8)
132.18(7)
76.09(8)
134.10(7)
77.84(8)
62.17(8)
75.33(8)
137.06(8)
136.29(8)
153.21(7)
62.89(7)
93.3(3)
b
100
80
60
40
20
0
81.0(3)
119.7(5)
91.2(4)
84.8(4)
120.3(7)
90.4(4)
83.3(3)
119.5(5)
90.8(4)
86.9(4)
120.0(6)
90.3(3)
10
20
30
40
50
60
70
2θ degree
85.6(4)
119.1(7)
86.7(3)
120.0(6)
Fig. 3. XRD pattern of Sb2S3 prepared from [Sb(S2CPh)3]. (a) Heated in a furnace at
300 °C, (b) in diphenylether at 230 °C.

K.R. Chaudhari et al. / Inorganica Chimica Acta 362 (2009) 1819–1824
1823
Table 3
Salient structural features of some 1,1-dithiolate complexes of antimony and bismuth
Compound
Nuclearity
M–S distance in Å
M–S(short)
\S–M–S in (°)
\S–X–S in (°) (X = C or P)
Reference
M–S(long)
DM–S
a
a
[Sb(S2Ctol)3]
[Bi(S2CPh)3]
[Sb(S2COEt)3]
monomer
monomer
monomer
dimer
dimer
monomer
dimer
2.48–2.64
2.58–2.74
2.511(2)
2.477–2.591
2.596–2.747
2.463–2.673
2.487–2.631
2.595–2.775
2.53
2.81–2.93
2.86–2.94
3.002(3)
2.930–3.079
2.933–2.998
2.763–2.878
2.886–2.965
2.908–2.964
3.00
0.17–0.45
0.12–0.36
0.49
0.36–0.60
0.21–0.40
0.12–0.41
0.26–0.48
0.18–0.36
0.47
ꢄ64
119.7
120
ꢄ63
64.65(6)
64.4 (av.)
63.5 (av.)
64.6–66.9
64.8 (av.)
63.5 (av.)
72.6
72.0
71.0–74.4
73.1
123.8(5)
123.7 (av.)
123.8 (av.)
117.5–118.9
118.5
27
28
28
29
30
30
31
32
33
34
35
[Sb(S2COMe)3]2
[Bi(S2COMe)3]2
[Sb{S2CN(CH2CH2OH)2}3]
[Sb(S2CNEt2)3]2
[Bi(S2CNEt2)3]2
[Sb{S2P(OMe)2}3]
[Bi{S2P(OEt)2}3]
[Sb(S2PEt2)3]
dimer
116.6–120.4
112.5
monomer
monomer
monomer
monomer
dimer
2.758
2.799
0.04
2.503–2.583
2.753–2.813
2.456–2.598
2.907–3.137
2.787–2.858
2.923–3.187
0.39–0.63
0.02–0.07
0.16–0.40
110.0–112.8
111.8
110.4–113.3
[Bi(S2PEt2)3]
[Bi(S2PPh2)3]2
ꢄ73
a
This work.
a
100
80
60
40
20
0
10
20
30
40
50
60
70
Fig. 5. SEM of Bi2S3 prepared from [Bi(S2Ctol)3] by solvothermal decomposition in
diphenylether at 230 °C.
2θ degree
100
b
gave M2S3 (M = Sb or Bi) as revealed by their XRD patterns1,2 [14]
.
Thermolysis of [Sb(S2CPh)3] and [Bi(S2Ctol)3] in diphenylether at
230 °C gave a brownish powder which was characterized as M2S3
from their EDAX analyses (Calc. for Sb2S3: Sb, 71.7; S, 28.3. Found:
Sb, 72.5; S, 27.5%. Calc. for Bi2S3: Bi, 81.3; S, 18.7. Found: Bi, 78.4; S,
21.6%) XRD patterns (Figs. 3 and 4).1,2 The SEM image (Fig. 5) of
these materials showed star like growth pattern of M2S3.
80
60
40
20
Acknowledgements
The authors thank Drs. T. Mukherjee and D. Das for encourage-
ment of this work. We are grateful to Dr. S. K. Gupta for providing
EDAX and SEM data.
Appendix A. Supplementary material
0
10
20
30
40
50
60
70
CCDC 678137 and 678138 contain the supplementary crystallo-
graphic data for [Sb(S2Ctol)3] and Bi(S2CPh)3]. These data can be
obtained free of charge from The Cambridge Crystallographic Data
2θ degree
Fig. 4. XRD pattern of Bi2S3 prepared from [Bi(S2Ctol)3] (a) heated in a furnace at
300 °C, (b) in diphenylether at 230°.
1
of Sb2S3 (calc. wt loss = 70.8%). The complexes [Sb(S2CAr)3] (Ar = Ph
or tol) and [Bi(S2Ctol)3] when heated in a furnace at 300 °C for 4 h
JCPDS File No. 42-1393 (for Sb2S3).
JCPDS File No 17-0320 (for Bi2S3).
2

1824
K.R. Chaudhari et al. / Inorganica Chimica Acta 362 (2009) 1819–1824
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