Synthesis, structural, Continuous Shape Measure and bond valence sum characterization of bismuth(III) complexes of substituted dithiocarbamates and their solvothermal decomposition

Article abstract of DOI:10.1016/j.ica.2014.04.042

Bismuth(III) complexes, [Bi(chmdtc)₃] (1) [Bi(chedtc) ₃] (2) and [Bi(dchdtc)₃] (3) (where chmdtc = cyclohexylmethyldithiocarbamate, chedtc = cyclohexylethyldithiocarbamate and dchdtc = dicyclohexyldithiocarbamate) have bee

Full text of DOI:10.1016/j.ica.2014.04.042

Accepted Manuscript
Synthesis, Structural, Continuous shape measure and Bond valence sum char-
acterization of bismuth(III) complexes of substituted dithiocarbamates and their
solvothermal decomposition
Subbarayan Sivasekar, Kuppukkannu Ramalingam, Corrado Rizzoli, Nagarajan
Alexander
PII:
S0020-1693(14)00283-7
http://dx.doi.org/10.1016/j.ica.2014.04.042
ICA 15990
DOI:
Reference:
Inorganica Chimica Acta
To appear in:
Received Date:
Revised Date:
Accepted Date:
11 January 2014
23 April 2014
28 April 2014
Please cite this article as: S. Sivasekar, K. Ramalingam, C. Rizzoli, N. Alexander, Synthesis, Structural, Continuous
shape measure and Bond valence sum characterization of bismuth(III) complexes of substituted dithiocarbamates
and their solvothermal decomposition, Inorganica Chimica Acta (2014), doi: http://dx.doi.org/10.1016/j.ica.
2014.04.042
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Synthesis, Structural, Continuous shape measure and Bond valence sum
characterization of bismuth(III) complexes of substituted dithiocarbamates and their
solvothermal decomposition
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Subbarayan Sivasekar,a Kuppukkannu Ramalingam,∗ a Corrado Rizzolib and
Nagarajan Alexandera
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aDepartment of Chemistry, Annamalai University, Annamalainagar 608 002, India
bDepartment of General and Inorganic Chemistry, University of Parma, Parma-43100, Italy
Bismuth(III) complexes, [Bi(chmdtc)3] (1) [Bi(chedtc)3] (2) and [Bi(dchdtc)3] (3), (where
chmdtc = cyclohexylmethyldithiocarbamate, chedtc = cyclohexylethyldithiocarbamate and dchdtc =
dicyclohexyldithiocarbamate ) have been prepared and characterized by electronic, IR, NMR (1H
and 13C) spectra, and single crystal X-ray diffraction. Electronic spectra of the complexes show
signature bands in the range: 418-423 nm due to charge transfer transitions. The characteristic
thioureide bands occur at 1474, 1467 and 1443 cm-1 for (1), (2) and (3) respectively. Single crystal
X-ray structures of [Bi(chmdtc)3] (1), [Bi(chedtc)3] (2) and [Bi(dchdtc)3] (3) indicate that the short
Bi---S interactions between the molecules lead to dimeric structures. CShM calculations on the
chromophores clearly quantify the extent of deviation from the ideal geometry. BiS6 chromophore
in (1) is a distorted octahedron. The coordination geometry for both [Bi(chedtc)3] (2) and
[Bi(dchdtc)3] (3) should be better described as distorted pentagonal pyramidal. The higher BVS
values observed in the present set of compounds support the fact that the Bi-S bonds are more
covalent.
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∗ Corresponding author, Tel.:+91 413 2202834; fax: +91 414 422265.
E-mail address: krauchem@yahoo.com (K. Ramalingam)

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Keywords: Bismuth(III); dithiocarbamate; non-covalent interactions; pentagonal pyramid; crystal
structures; nanosulfide.
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1. Introduction
Bismuth is a group 15 element with the most common formal oxidation state of +3. Bismuth
compounds have long been used as therapeutic agents. The chalcogenides of bismuth(III) find
increasing applications in solar cells, photolithography, optical memory devices and as photo- and
thermo-electric conductors [1,2]. Trivalent bismuth xanthates, dithiocarbamates and alkyl- as well
as alkylenedithiophosphates have been prepared and some of the dithio derivatives show interesting
catalytic and biocidal applications [3,4]. The antimicrobial and anti-tumor activity of binary
bismuth(III) dithiocarbamates of the general formula, Bi(S2CNR2)3 has been reported [5].
Dithiocarbamates are known to show a variety of coordination modes such as isobidentate,
anisobidentate, monodentate and triconnective [6]. Bismuth dithiocarbamates serve as useful
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precursors for the preparation of Bi2S3 and offer a facile transformation at low temperature
compared to the traditional high sintering temperature methods [7-11]. In continuation of our efforts
to identify new precursors for the preparation of Bi2S3, we report the synthesis and characterization
of [Bi(chmdtc)3] (1), [Bi(chedtc)3] (2) and [Bi(dchdtc)3] (3) . On heating the trisdithiocarbamates in
diethylenetriamine, in a non-conventional solvothermal process, nano Bi2S3 separated which was
characterized by SEM, EDS and HRTEM techniques.

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R1
R2
S
S
N
C
Cyclohexylmethyldithiocarbamate Cyclohexylethyldithiocarbamate Dicyclohexyldithiocarbamate
(dchdtc)
(chedtc)
(chmdtc)
R1: -CH3, R2: -C6H11
R1: -C2H5, R2: -C6H11
R1, R2: -C6H11
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2. Experimental
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Bismuth nitrate (SD fine chemicals, India), the parent amines (Fisher Scientific, India) and
the solvents (SD fine chemicals, India) were commercially available analytical grade materials and
were used as supplied without further purification. Melting points of solid products were
determined with digital melting / boiling point apparatus, Jains, India. Elemental analyses were
carried out with Elementar, Vario Micro Cube instrument. IR spectra were recorded on an Avatar
Nicolet FT-IR spectrometer (range 4000–400 cm-1) as KBr pellets of the compounds. Electronic
spectra were recorded in CCl4 on a Hitachi U-2001 double beam spectrometer. Thermal analysis
was carried out with NETZSCH STA 449F3 instrument under nitrogen atmosphere with a heating
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rate of 10 K / minute. 1H and C NMR spectra were recorded on a Bruker AMX-400 spectrometer
at room temperature using CDCl3 as solvent. NMR spectra were recorded at room temperature with
TMS as an internal reference and CDCl3 as the solvent. The powder diffraction data were collected
in the 2θ range = 2-80o using Bruker-D8 X-ray diffractometer equipped with Cu-Kα radiation at
o
fixed current and potential. The scan speed and step sizes were 0.05 min-1 and 0.00657
respectively. Scanning electron micrographs of the samples were recorded with JEOL JSM-
5610Lv microscope. HRTEM measurements were carried out on JEOL 2100 (Field emission)
with an accelerating voltage of 200kV. Some important infra red spectral bands and the

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electronic spectral data are listed in Table 1. NMR spectral data of bismuth complexes are listed in
Table 2.
2.1
X-ray crystallography
Intensity data were collected at ambient temperature (295 K) on a Bruker APEX-II CCD
diffractometer with graphite monochromated MoKα radiation (λ = 0.71073 Å) and were corrected
for absorptions with a multi-scan technique [12-14]. The structures were solved by direct methods
using SIR97 and were refined by SHELX97 [15]. The non-hydrogen atoms were refined
anisotropically and all the hydrogen atoms were fixed geometrically. Molecular plots were obtained
using the ORTEP-3 program [16]. In (2), the CCl4 solvent molecule and one cyclohexyl group are
disordered over two sets of orientations with site occupancy of 0.5. One ethyl group is also
disordered over two orientations with site occupancies of 0.65 and 0.35 for the major and minor
components of disorder respectively. Crystal data, data collection and refinement parameters are
given in Table 3. Selected bond parameters are given in Table 4. ORTEP diagrams of (1), (2) and
(3) are shown in Figures 1, 2 and 3 respectively.
2.2
Preparation of the complexes
2.2.1 Preparation of tris(cylochexylmethyldithiocarbamato)bismuth(III);[Bi(chmdtc)3](1)
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N-cyclohexyl-N-methylamine (6 mmol; 0.78 mL) and carbon disulfide (6 mmol; 0.36 mL)
in ethanol were mixed under ice-cold condition (5°C) to obtain yellow dithiocarbamic acid solution.
To the freshly prepared dithiocarbamic acid solution, acidified solution of Bi(NO3)3 pentahydrate (2
mmol; 0.96 g) was added with constant stirring. A yellow solid separated from the solution, which
was filtered, washed with alcohol and was dried in air. (Yield: 73%, dec., 124°C. Anal. calc. for
C24H42BiN3S6 (774.0): C, 37.24; H, 5.47; N, 5.42.Found: C, 37.19; H, 5.42; N, 5.38 %)
2.2.2 Preparation of tris(cylochexylethyldithiocarbamato)bismuth(III); [Bi(chedtc)3](2)

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N-cyclohexyl-N-ethylamine (0.03 mol, 4.49 mL), carbon disulfide (0.03 mol, 5 mL) in
methanol (20 mL) and a weakly acidified solution of bismuth(III) nitrate pentahydrate (0.01 mol,
4.85g) were used for the preparation. A similar procedure as described in 2.2.1 was used for the
preparation. (Yield: 78%, m.p., 188°C. Anal. calc. for C55H96Bi2Cl4N6S12 (1785.9): C, 36.99; H,
5.42; N, 4.70. Found: C, 36.95; H, 5.38; N, 4.66 %)
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2.2.3 Preparation of tris(dicylochexyldithiocarbamato)bismuth(III); [Bi(dchdtc)3](3)
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A similar procedure as described in 2.2.1 was employed for the preparation of the
dicyclohexylamine analogue. N,N-dicyclohexylamine (0.03 mol, 4.49 mL), carbon disulfide (0.03
mol, 5 mL in 20 mL methanol) and bismuth(III) nitrate pentahydrate (0.01 mol, 4.85g) were used
for the preparation. (Yield: 67%, m.p., 145°C. Anal. calc. for C41H69BiN4S6 (1019.3): C, 48.31; H,
6.82; N, 5.49. Found: C, 48.26; H, 6.78; N, 5.45 %)
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2.2.4 Preparation of nano Bi2S3 by non-conventional solvothermal decomposition of
Tris(disubstituteddithiocarbamato)bismuth(III)
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1mM of tris(disubstituteddithiocarbamato)bismuth(III) complexes (1), (2) and (3) as clear
solutions in chloroform (100 mL) were heated with diethylenetriamine (2 mL) at 60oC for 45
minutes. Solid yellow bismuth sulfide obtained was separated from chloroform, washed with ether,
chloroform and dried in air.
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3.
Results and discussion
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3.1
Infrared spectral studies
For complexes (1), (2) and (3) the νC−N (thioureide) bands are observed at 1474, 1467 and
1443 cm-1 respectively. The ν(C−S) stretching bands are observed around 1000 cm-1 supporting [17]
the bidentate coordination mode of the dithiocarbamate to the metal center, and the νC−H bands are
observed in the range: 2850-2929 cm-1.

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3.2
Electronic spectra
Electronic spectra of the compounds show bands between 364 and 376 nm for the three
compounds which are due to intraligand π- π* transitions, mainly associated with the N−C=S and
S−C=S groups [18, 19]. The electronic spectra of the complexes show charge transfer transitions in
the range: 410-423 nm.
3.3
NMR spectral studies
Chemical shifts reported in Spectral Data Base for Organic compounds (SDBS) for the
parent amines are shown in brackets in the Table 2 [20]. 1H NMR of complex (1) shows an intense
signal at 5.08 ppm (2.303 ppm) corresponding to single proton integration due to α-CH of the
cyclohexyl ring. CH3 protons (α’-CH3) attached to the nitrogen appear at 3.28(s) ppm (2.421 ppm)
with proton integration corresponding to three. The α-CH and α’-CH3 protons are affected to a
maximum extent on complexation. In the cyclohexyl ring all the equatorial protons are deshielded
to a large extent compared to the axial protons. The equatorial protons appear in the range: 1.80-
1.88 ppm. The axial protons appear between 1.69-1.71ppm. 13C NMR spectrum of (1) shows a
weak signal at 200.7 ppm due to the thiouriede carbon [21]. The α-carbon of cyclohexyl ring
appears at 62.8 ppm (58.63 ppm) and α’-CH3 appears at 35.2 ppm (33.60 ppm). The β,γ- and δ-
carbon signals were the least affected and appeared at 25.40, 25.50 and 29.80 ppm respectively.
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In complex (2), H NMR of α-CH proton of the cyclohexyl ring appeared at 5.04 ppm and
α’-CH2 appeared at 3.74-3.80 ppm corresponding to two protons. β´-CH3 protons of the ethyl group
appeared as a well resolved triplet 1.50-1.95 ppm. 13C NMR spectrum of (2) showed the
characteristic thiouriede signal at 200.6 ppm. β’-CH3 appeared at 14.40 ppm as a much shielded
signal and α’- CH2 appears to be highly deshielded at 43.60 ppm. α- CH signal of the cyclohexyl

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ring appears at 63.20 ppm. The β,γ- and δ- carbon signals which were the least affected on
complexation appeared at 30.46 and between 24.60 to 25.70 ppm.
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In the case of complex (3), α-CH proton of the cyclohexyl ring was observed at 5.31 ppm (2.546
ppm). β, γ- and δ-CH2 signals appeared in the region of 1.82-2.09(e) ppm (collapsed) (1.606 - 1.856
ppm). The axial proton signals appeared between 1.35-1.53 ppm(1.021 - 1.246 ppm). 13C NMR
exhibited a weak characteristic signal due to thiouriede carbon at 200.8 ppm. 13C NMR signal
corresponding to the α-C(H) carbon of the cyclohexyl ring was found to be significantly shielded
and appeared at 65.21 ppm (53.17 ppm) . β-C(H2), and γ -C(H2) carbons appeared in the region of
25.03 - 29.78 ppm (26.32 – 34.51ppm). Signals observed at ~ 7.20 and 2.35 ppm in the 1H NMR
spectra of the three compounds are due to the aromatic and methyl protons of toluene which is the
solvent used for crystallization. NMR spectra of the complexes clearly indicated that the immediate
environment around thiouriede nitrogen was largely affected by complex formation.
3.4
Thermogravimetric analysis
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Thermal analyses of the compounds were carried out under nitrogen atmosphere. A toluene
recrystallized sample of (1) was used for the thermal analysis and hence a loss of solvent was
observed. [Bi(chmdtc)3](1) showed initial loss of the solvent of crystallization, toluene around
198oC. A large mass loss (63.9%) was observed in the range of 260-320 oC. At temperatures above
500 oC, the mass loss was insignificant and the residue agreed well for Bi2S3 as the residue (Exptl.:
30.3%; Calcd.: 29.7%). [Bi(chedtc)3](2) showed a minor loss due to the solvent of crystallization,
CCl4 at160oC. A large chunk of mass (60.1%) was lost in the temperature range: 220-280 oC. Above
500 oC, the mass remained constant and the final residue confirmed the formation of Bi2S3 (Exptl.:
28.5%; Calcd.: 28.8%). [Bi(dchdtc)3] (3) followed a similar pattern of decomposition. Loss of
solvent of crystallization, CH3CN was observed at 240 oC. Largest mass loss (62.0%) was observed
in the temperature range: 250-290 oC. The final residue formed above 500 oC was Bi2S3 (Exptl.:
26.2%; Calcd.: 25.2%). Thermal analysis confirmed the proposed formulae of the compounds. The

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most important observation is that in all the three compounds the final residue was found to be
Bi2S3. Among the three compounds the dicyclo- analogue, [Bi(dchdtc)3] (3) showed the highest
thermal stability.
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3.5
Structural analysis
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[Bi(chmdtc)3](1) crystallizes in monoclinic lattice with four molecules per unit cell. The
asymmetric unit of (2) contains two crystallographically independent [Bi(chedtc)3] complex
molecules of similar conformation and one disordered CCl4 solvent molecule of crystallization.
Complex (3) crystallizes with acetonitrile solvent molecules in a stoichiometric complex/solvent
molar ratio of 1:1. The dithiocarbamate group in all complexes acts in the usual asymmetric
bidentate mode, each ligand chelating Bi through a shorter (mean value 2.72(3) Å) and a
longer (mean value 2.88(2) Å) Bi–S bond. It is noticeable that in the ligands the C–S bonds
associated with the shorter Bi–S bonds are significantly longer (mean value 1.734(4) Å) than
those associated with the longer Bi–S bonds (mean value 1.717(4) Å). The thioureide C–N
distances (mean value 1.332(3) Å for all complexes) indicate a delocalization of the electron
density over the S2CN fragment and suggest a partial double bond character of these bonds. The
observed values of the Bi–S, C–S and C–N bonds are in good agreement with those calculated
for 13 related bismuth dithiocarbamate complexes reported in the literature recently [22, 23],
where the mean shorter and longer Bi–S distances are 2.719(14) and 2.889(6) Å, respectively,
the corresponding mean longer and shorter C–S distances are 1.728(3) and 1.709(3) Å,
respectively, and the mean value of the C–N bonds is 1.330(3) Å. The BiS6 chromophore in
[Bi(mchdtc)3] (1) assumes a remarkably distorted octahedral geometry, similar to that observed in
tris(N-(n-hexyl)-N-methyldithiocarbamato-S,S')bismuth(iii) [24]. The best equatorial plane is
defined by the S1/S3/S4/S6 set of donor atoms (r.m.s. 0.0501; maximum deviation 0.0767(10) Å

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for atom S4) and the apical positions occupied by atoms S2 and S5. The bismuth cation is displaced
from the equatorial plane by 0.58752(10) Å toward S5. The S–Bi–S bond angles fall in the range
61.55(3)–153.34(3)°. The coordination geometry for both [Bi(chedtc)3] (2) and [Bi(dchdtc)3] (3)
should be better described as distorted pentagonal pyramidal instead, as usually observed in most
related bismuth dithiocarbamate complexes. The basal plane is defined by atoms S1/S2/S3/S5/S6
(r.m.s 0.4141; maximum displacement 0.605(2) Å for atom S2) and S7/S8/S9/S10/S11 (r.m.s.
0.2883; maximum displacement 0.466(3) Å for atom S9) in (2), and by atoms S1/S2/S3/S4/S6
(r.m.s. 0.1891; maximum displacement 0.3072(9) Å for atom S4) in (3). Atoms S4 and S12 in (2)
and S5 in (3) occupy the vertices and are displaced by 2.2479(1), 2.2610(16) and 2.0983(7) Å,
respectively, from the least square mean basal plane. The bismuth centres protrude from the
respective mean basal plane in opposite direction to the apical position by 0.3024(2) and
0.2789(2) Å in (2) and 0.43876(11) Å in (3). The S–Bi–S bond angles are not dissimilar to
those found in (1) ranging from 62.25(5) to 158.22(5)° in (2) and from 61.89(6) to 159.97(6)° in
(3). The different coordination geometry observed in [Bi(chmdtc)3] (1) may be attributed to the
steric demand of the methyl substituent of the carbamate groups which is comparatively less
demanding than that of the ethyl and cyclohexyl analogues and hence the six coordinated
bismuth distorts to a lesser extent from the preferred octahedral geometry.
All complexes form dimeric units through non-covalent Bi⋅⋅⋅S interactions involving
symmetry related molecules as depicted in Figure 4, with Bi⋅⋅⋅S distances (3.2375(10) Å in (1);
3.3587(17) and 3.1449(15) Å in (2); 3.3260(6) Å in (3) notably shorter than the sum of the van
der Waals radii (1.80 for S [25] and 2.07 for Bi [26]). The Bi⋅⋅⋅Bi separations within the dimers
are 4.9110(5), 4.4655(4)-4.8894(4) and 4.5058(3) Å in (1), (2) and (3), respectively. The
molecular conformation of the complexes is stabilized by intramolecular C–H⋅⋅⋅S hydrogen
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bonds involving methine and methylene hydrogen atoms of the ligands with H⋅⋅⋅S distances
varying in the range 2.44–2.46 Å in (1), 2.44–2.46 Å in (2) and 2.39–2.76 Å in (3).
3.6
Continuous shape measure
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Continuous Shape measure (CShM) effectively quantifies the distance of a given structure
from the desired ideal symmetry or from a reference shape [27-30]. In practice, idealizations of
molecular structures is achieved by associating the position of a set of atoms with the vertices of a
reference polyhedron and qualitative descriptions such as ‘slightly distorted’ or ‘severely distorted’
relative to the reference polyhedron are often required. To quantify the degree of distortion of a
particular molecular structure from an ideal polyhedron one can use symmetry measures.
Continuous shape measure (CShM) methodology has been successfully applied to transition metal
complexes and metal oxides. For six coordination, the ideal geometries are ideal octahedron (iOh)
or ideal trigonal prism (itp). In the present investigation, the coordination around bismuth in (2) and
(3) is distorted pentagonal pyramid whereas in (1) it’s a distorted octahedron. It is natural to
consider the transformation of ppy to iOh or itp. In the present case, the Continuous Shape measure
calculations on the three complexes for the BiS6 core yielded 10.237607, 27.662944 and 29. 921790
for (1), (2) and (3) respectively. The observed CShM values follow the order for (3) > (2) > (1).
Complex (3) deviates to the largest extent from the octahedral geometry than the other two because
of the largest steric demand of the two cyclohexyl rings. Between the two, the methyl analogue (1)
is closer to the octahedral geometry than its ethyl analogue (2). The observed CShM value clearly
indicate the closeness of (1) to octahedral geometry. The other two BiS6 cores associated with (2)
and (3) are not close to octahedral geometry but to pentagonal pyramid (ppy) geometry as evident
from S-Bi-S angles. Between the two, compound (2), shows four of the five S-Bi-S angles in the
range of 87.34(5) to 93.63(6)o indicating a distorted pentagonal pyramid. The axial Bi-S bonds are

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shorter than the equatorial bonds in compounds (2) and (3). All the three complexes show little
tendency to distort towards trigonal prismatic geometry. Distortion from the octahedral geometry to
pentagonal pyramid is minimal in the methyl analogue and is a maximum in the dicyclohexyl
analogue due to steric demands which is quantified by the reported values.
3.7
BVS calculations
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Bond valence sum (BVS) calculations offer a reliable method of assigning formal oxidation
states of an atom in a compound from the bond parameters. The method depends on the Rij value
for an i-j bond in a compound which is predominantly ionic [31]. In a compound, the oxidation
state of a central atom ‘i' bonded to ‘j’ corresponds to the bond valence, Sij, and the total valence of
the central atom which is its oxidation state, ΣSij = exp[(Ro - Rij)/b] and Ro is used as
reported[32,33] and Rij is the experimentally determined bond distance. The constant b can be
assumed to be 0.37[34, 35]. Bond valence sums calculated for the complexes from the structural
data reported for the compounds in this study are 3.2618, 3.2811 and 3.3833 for (1), (2) and (3)
respectively. The calculated values have been found to be higher than the expected formal oxidation
state of +3. The higher values observed in the present set of compounds support the fact that the Bi-
S bonds are more covalent.
3.8
Characterization of Bi2S3
3.8.1 Powder XRD
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Powder XRD of the solvothermally prepared bismuth sulfide is shown in Figure 5 along
with SEM and EDX. The broadened PXRD indicates the nano sized nature of the sample and
matched well with the JCPDS pattern reported for Bi2S3, PDF # 75-1306 and two strong signals
corresponding to 26.76o (130), 29.93o (211) are observed[36,37]. On heating the three compounds
under identical conditions in diethylenetriamine at 60oC, Bi2S3 appeared as a precipitate very early

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in the case of (3) compared to other two compounds within the shortest period compared to the
other two. Hence qualitatively, the ease of formation of the nanosulfide from the dithiocarbamates
based on its first appearance from (3) was slightly better than from the compounds (1) and (2).
Based on the observation, the ease of formation of nanosulfide from the bismuth dthiocarbamates
follows the order: (3) > (1) > (2). However, the mean Bi-S bond distances for the three compounds
are almost similar (2.8125(10), 2.8129(17) 2.7977(9) Å in (1), (2) and (3) respectively).
3.8.2 SEM-EDX
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SE micrographs of the prepared bismuth sulfide are shown in Figures 5. The morphology of
surface shows crystalline grains with large size distribution. The energy dispersive spectrum
confirmed the presence of bismuth and sulfur in 2:3 ratio.
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3.8.3 HRTEM and SAED
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HRTEM and SAED (inset) are shown in Figure 6. HRTEM showed the Bi2S3 to be nano
wires < 10 nm size. SAED pattern confirmed the crystalline nature of the sample. Fringe spacing of
the Bi2S3 wires is ~ 0.5nm. The SAED pattern showed strong diffractions due to (001) and (120)
oriented single crystals.
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4.
Conclusions
[Bi(chmdtc)3] (1), [Bi(chedtc)3] (2) and [Bi(dchdtc)3] (3) show interesting variations
in the geometry around bismuth. The single crystal X-ray structures showed the Bi-S bonds to vary
largely due to variations in the steric effects. NMR spectra of the complexes clearly indicated that
the immediate environment around thiouriede nitrogen was largely affected by complex formation.
CShM calculations on the chromophores clearly quantify the extent of deviation from the ideal
octahedral geometry. BiS6 chromophore in (1) is a distorted octahedron whereas in the other two,

13
268
269
270
271
272
273
274
distorted pentagonal pyramidal geometry prevails. Stabilization of the dimer in (2) is favoured to a
large extent than the other two because of the pentagonal pyramid geometry assumed by the BiS6
core. In the three compounds, the steric effect is active in controlling the geometry around bismuth.
The bond valence sums indicate the highly covalent nature of the Bi-S bonds. Non conventional
solvothermal decomposition of the compounds yield nano Bi2S3. The ease of formation of the
nanosulfide followed the order: (3) > (1) > (2). The nano wires of Bi2S3 have been characterized by
a host of techniques.
275
Appendix A
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
Supplementary material
CCDC 967477, 954122 and 954123 contain the supplementary crystallographic data for (1), (2) and
(3). These data can be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

14
291
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17
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Captions for figures
379
380
381
382
383
384
385
386
387
388
389
390
391
392
Figure 1.
Figure 2.
ORTEP of [Bi(chmdtc)3] (1). Hydrogen atoms are omitted for clarity
ORTEP of one complex molecule in [Bi(chedtc)3] (2). Only the major component
of the disordered ethyl chain is shown. Hydrogen atoms are omitted for clarity
Figure 3.
Figure 4.
ORTEP of [Bi(dchdtc)3] (3). Hydrogens atoms are omitted for clarity
ORTEP plot of the dimers
Figure 5
Figure 6
PXRD, SEM and EDX of nano Bi2S3
HRTEM and SAED of nano Bi2S3
393
394
395
396
397
398
399
400
401
402
403
404
405
406
407
408
409

18
410
411
412
413
414
415
416
417
Table 1 Electronic and IR spectral data
† Free
Compound
Uv-Vis (nm)
Intraligand νC-N
IR (cm-1)
418
†νC-S
CT
νC-H
418
420
423
364
367
376
1474
1467
1443
2850-2925*
2852-2929*
2851-2927*
1004
(1010)
1009
(1017)
1010
[Bi(chmdtc)3] (1)
[Bi(chedtc)3] (2)
[Bi(dchdtc)3] (3)
(1018)
419
dithiocarbamate νC-S wave numbers are given in parentheses
*
420
421
422
423
424
425
426
427
428
429
νC-H wave numbers for the free dithiocarbamates are in the range of 2850-2930 cm-1

19
430
431
†
Table 2 NMR spectral data (ppm)
β-CH2/
α’-CH3/ CH2
Complex
NMR
1H
α-CH
N13CS2
γ- CH2 & δ- CH2
5.08
1.80-1.88(e)
1.69-1.71
3.28
-
200.7
-
(2.303)
(2.421)
[Bi(chmdtc)3] (1)
62.8
29.80
35.2
13C
(58.63)
25.40,25.50
(33.60)
1.83-1.93(e)
1.56-1.69
3.74-3.80
1.31-1.37
1H
5.04
63.2
[Bi(chedtc)3] (2)
30.46
43.60
14.40
13C
200.6
24.60-25.70
1.82-2.09(e)
(1.606 - 1.856)
1.35-1.53
5.31
1H
-
-
-
(2.546)
(1.021 - 1.246)
(Collapsed)
[Bi(dchdtc)3] (3)
29.66
65.21
200.8
13C
25.03 - 29.78
(26.32 – 34.51)
(53.17)
432
†
433
434
435
Chemical shifts reported in Spectral Data Base for Organic compounds (SDBS) for the parent amines are
shown in brackets
436

20
437
438
Table 3. Crystal data, data collection and refinement parameters for
[Bi(chmdtc)3], [Bi(chedtc)3] and [Bi(dchdtc)3]
Complex
Empirical formula
Formula weight
Colour
[Bi(chmdtc)3]
C24H42BiN3S6
[Bi(chedtc)3]
2(C27 H48 Bi N3 S6)·CCl4
3571.96
[Bi(dchdtc)3]
C39 H66 Bi N3 S6·C2 H3 N
1019.34
774.0
Yellow
Yellow
Yellow
Habit
Block
Block
Prism
Crystal system
Space group
Monoclinic
P 21/c
Monoclinic
Monoclinic
C 2/c
P 21/c
Crystal dimension(mm3)
0.28 x 0.27 x 0.24
0.27 x 0.23x 0.18
0.32 × 0.24 × 0.18
12.6224(17)
20.526(3)
13.1879(17)
90.00
a (Å)
b(Å)
30.3139(17)
14.9828(8)
34.549(3)
90.00
10.5705(8)
16.1324(12)
27.975(2)
90.00
Å)
α (°)
β (°)
109.137(2)
90.00
108.3958(12)
90.00
97.9920(12)
90.00
γ(°)
3228.0(8)
4
U (A3)
Z
14889.8(17)
4
4724.2(6)
4
Dc(g cm-3)
F(000)
1.593
1.433
1.593
3228.0(8)
7152
2088
MoKα (0.71073)
1.42-25.25
ω scan
MoKα (0.71073)
1.42-25.25
ω scan
MoKα (0.71073)
1.46-25.50
ω scan
λ(Å)
θ range (°)
Scan type
–15 ≤ h ≤ 15;
–25 ≤ k ≤ 25;
–16 ≤ l ≤ 16
-36 ≤h≤ 36;
-17≤k ≤ 17;
-41≤l≤ 41
-12 ≤ h≤ 12;
-19≤k ≤ 19;
-33≤ l≤ 33
Index range
6350
4885
Reflections collected
13477
9374
8789
7644
Reflections [Fo> 2 σ (Fo)]
w=1/[s2(Fo2)+(0.0218P)2
+2.2017P] where
P=(Fo2+2Fc2)/3
w = 1/[\S2(Fo2) +
(0.0212p)2 ] where
P = (Fo2 + 2Fc2)/3
w=1/[s2(Fo2)+(0.0405P)2+46
.8561P] where
Weighting scheme
P=(Fo2+2Fc2)/3
Number of parameters
refined
307
743
470
Final R, Rw (obs, data)
GOOF
0.0206, 0.0432
0.995
0.0391, 0.0872
1.011
0.0210, 0.0485
1.029
439
440
441

21
442
443
Table 4 Selected bond distances (Å) and bond angles (˚)
[Bi(chedtc)3]
[Bi(chmdtc)3]
[Bi(dchdtc)3]
Bi1–S1
2.7770(9)
2.6884(8)
2.9974(10)
2.7876(10)
2.9326(9)
2.6921(11)
1.721(3)
1.729(3)
1.706(3)
1.739(4)
1.702(3)
1.742(3)
1.329(3)
1.337(4)
1.331(4)
112.39(3)
Bi1–S1
Bi1–S2
Bi1–S3
Bi1–S4
Bi1–S5
Bi1–S6
C1–S1
2.7554(17) Bi2–S7
2.8545(18) Bi2–S8
2.9428(18) Bi2–S9
2.6060(18) Bi2–S10
2.9560(18) Bi2–S11
2.7669(17) Bi2–S12
2.951(2)
2.8167(19)
2.776(2)
2.816(2)
2.8396(19)
2.6400(16)
1.731(6)
1.714(7)
1.719(9)
1.719(8)
1.703(6)
1.743(6)
1.330(9)
1.334(11)
1.327(8)
61.89(6)
Bi1–S1
Bi1–S2
Bi1–S3
Bi1–S4
Bi1–S5
Bi1–S6
C1–S1
2.9201(6)
2.8288(10)
2.8359(8)
2.8057(9)
2.5841(8)
2.8121(8)
1.736(3)
1.717(3)
1.730(3)
1.711(3)
1.751(2)
1.709(3)
1.333(4)
1.484(4)
1.330(3)
61.46(2)
Bi1–S2
Bi1–S3
Bi1–S4
Bi1–S5
Bi1–S6
C1–S1
1.733(6)
1.709(6)
1.705(6)
1.743(6)
1.717(6)
1.728(6)
1.329(8)
1.323(8)
1.335(8)
63.45(6)
C28–S7
C1–S2
C1–S2
C28–S8
C1–S2
C9–S3
C10–S3
C10–S4
C19–S5
C19–S6
N1–C1
N2–C10
N3–C19
S1–Bi1–S2
C37–S9
C14–S3
C14–S4
C27–S5
C27–S6
N1–C1
N2–C15
N3–C27
S1–Bi1–S2
C9–S4
C37–S10
C46–S11
C46–S12
N4–C28
N5–C37
N6–C46
S7–Bi2–S8
C17–S5
C17–S6
N1–C1
N2–C9
N3–C17
S1–Bi1–S3
S1–Bi1–S4
S1–Bi1–S6
S3–Bi1–S4
S3–Bi1–S6
S4–Bi1–S6
S2–Bi1–S5
153.34(3)
94.00(3)
61.55(3)
140.36(3)
81.44(3)
136.50(3)
S1–Bi1–S4
S1–Bi1–S6
S2–Bi1–S3
S2–Bi1–S4
S3–Bi1–S4
S3–Bi1–S5
S4–Bi1–S5
S4–Bi1–S6
S5–Bi1–S6
90.52(5)
75.84(5)
77.28(5)
91.31(7)
64.24(5)
85.82(5)
93.63(6)
87.35(5)
62.25(5)
S7–Bi2–S11
S7–Bi2–S12
S8–Bi2–S9
S8–Bi2–S12
S9–Bi2–S10
S9–Bi2–S12
78.20(5)
82.49(5)
75.35(6)
97.79(5)
63.94(7)
87.56(7)
S1–Bi1–S5
S1–Bi1–S6
S2–Bi1–S3
S2–Bi1–S5
S3–Bi1–S4
S3–Bi1–S5
S4–Bi1–S5
S4–Bi1–S6
S5–Bi1–S6
84.99(2)
82.11(2)
73.62(2)
91.49(2)
62.71(2)
83.53(2)
81.95(2)
76.42(3)
66.09(2)
S10–Bi2–S11 81.83(6)
S10–Bi2–S12 90.66(6)
S11–Bi2–S12 65.56(5)

22
444
445
446
447
448
449
450
451
452

23
453
454
455
456
457
458
459
460
461
462
463
464
465
466

24
467
468
469
470
471
472
473
474
475
476
477
478
479
480

25
481
482
483
484
485
486
487
488
489
490
491
492
493
494

26
495
496
497
498
499
500
501
502
503
504
505
506
507
508
509
510
511
512
513
514
515
516
517

27
518
519
520
521
522
523
524
525
526
527
528
529
530

28
531
532
533
Synthesis, Structural, Continuous shape measure and Bond valence sum characterization of
bismuth(III) complexes of substituted dithiocarbamates and their solvothermal decomposition
Subbarayan Sivasekar, Kuppukkannu Ramalingam,* Corrado Rizzoli and Nagarajan Alexander
534
535
536
537
Geometrical distortions from iOh in tris(dithiocarbamato)bismuth(III) have been quantified by Continuous
Shape Measure (CShM) analysis. BiS6 chromophore in [Bi(chmdtc)3] (1) is a distorted octahedron. The coordination
geometry in [Bi(chedtc)3] (2) and [Bi(dchdtc)3] (3) should be described as distorted pentagonal pyramid. The higher
BVS values observed in the present set of compounds support the fact that the Bi-S bonds are more covalent.
538

29
539
540
541
Synthesis, structural, Continuous shape measure and Bond valence sum characterization of
bismuth(III) complexes of substituted dithiocarbamates and their solvothermal decomposition
542
Subbarayan Sivasekar, Kuppukkannu Ramalingam,* Corrado Rizzoli and Nagarajan Alexander
543
544