Synthesis, characterisation and thermal decomposition of tin(IV) dithiocarbamate derivatives - Single source precursors for tin sulfide powders

Article abstract of DOI:10.1016/j.poly.2004.06.007

The reaction of ammonium pyrrolidinedithiocarbamate with SnPh ₂Cl₂ and SnPh₃Cl produced in good yield the compounds [Sn{S₂CN(CH₂)₄}₂{C ₆H₅}₂]??toluene (1) and Sn{S ₂CN(CH₂)₄}{C₆H₅} ₃ (2). They were fully characterised by multinuclear NMR [ ¹H,¹³C{¹H} and ¹¹⁹Sn{¹H}] and ¹¹⁹Sn M??ssbauer spectroscopies. The reaction of ammonium pyrrolidinedithiocarbamate with SnPh₂Cl₂ and SnPh₃Cl produced in good yield the compounds [Sn{S ₂CN(CH₂)₄}₂{C₆H ₅}₂]??toluene (1) and Sn{S ₂CN(CH₂)₄}{C₆H₅} ₃ (2). They were fully characterised by multinuclear NMR [ ¹H,¹³C{¹H} and ¹¹⁹Sn{¹H}] and ¹¹⁹Sn M??ssbauer spectroscopies. In addition the structure of 1 was determined, and 2 was revised by X-ray crystallographic studies. Finally, thermal decomposition experiments were carried out for both compounds in nitrogen and the residues were characterised by X-ray powder diffraction (XRD), X-ray electron probe microanalysis (EPMA), scanning electron microscopy (SEM) and ¹¹⁹Sn M??ssbauer spectroscopy. The results clearly indicate the formation of a mixture of γ-Sn ₂S₃ and SnS, both orthorhombic phases.

Full text of DOI:10.1016/j.poly.2004.06.007

Polyhedron 23 (2004) 2103–2109
www.elsevier.com/locate/poly
Synthesis, characterisation and thermal decomposition of
tin(IV) dithiocarbamate derivatives – single source precursors for
tin sulfide powders
a
a,
a,
a
b
D.C. Menezes , G.M. de Lima *, A.O. Porto *, C.L. Donnici , J.D. Ardisson ,
c
A.C. Doriguetto , J. Ellena
c
a
´ ´ ´ ´
Laboratorio de Quımica de Coordenac¸a˜o e Organometalica do Estanho, Departamento de Quımica, Universidade Federal de Minas Gerais (UFMG),
Avenida Antonio Carlos 6627, Belo Horizonte – MG, CEP 31270-901, Brazil
´
Laboratorio de Fısica Aplicada –CDTN/CNEN, Belo Horizonte – MG, Brazil
b
´
c
Grupo de Cristalografia, FFI, IFSC, USP, CP 369, Sa˜o Carlos – SP, CEP 13560-970, Brazil
Received 21 April 2004; accepted 4 June 2004
Abstract
The reaction of ammonium pyrrolidinedithiocarbamate with SnPh2Cl2 and SnPh3Cl produced in good yield the compounds
[Sn{S2CN(CH2)4}2{C6H5}2]Ætoluene (1) and Sn{S2CN(CH2)4}{C6H5}3 (2). They were fully characterised by multinuclear NMR
[1H,13C{1H} and 119Sn{1H}] and 119Sn Mo¨ssbauer spectroscopies. In addition the structure of 1 was determined, and 2 was revised
by X-ray crystallographic studies. Finally, thermal decomposition experiments were carried out for both compounds in nitrogen and
the residues were characterised by X-ray powder diffraction (XRD), X-ray electron probe microanalysis (EPMA), scanning electron
microscopy (SEM) and 119Sn Mo¨ssbauer spectroscopy. The results clearly indicate the formation of a mixture of c-Sn2S3 and SnS,
both orthorhombic phases.
ꢀ 2004 Elsevier Ltd. All rights reserved.
Keywords: Pyrolysis; Organotin derivatives; Tin sulfide
1. Introduction
centre with three short Sn–S bonds within the layer
and three long bonds to the sulfur of the next layer [3,4].
Tin sulfides might encounter applications as low-cost
green materials for photovoltaic devices either replacing
cadmium chalcogenides, which have been banned in
many countries because of their toxicity, or else as sub-
stitute to the expensive silicon-based sensors. Their
preparation methods require high temperature reactions
(more than 300 ꢁC) or special reactors [5,6]. Atmospher-
ic pressure chemical vapour deposition (APCVD) and
pyrolysis using unsymmetrical organotin dithiocarba-
mates complexes, like [(CH3)3Sn(S2CN(C4H9)CH3)]
and [(CH3CH2CH2CH2)Sn(S2CN(C4H9)CH3)]3, or hetero-
leptic thiolate/dithiocarbamate derivatives, (Et2NCS2)(RS)2-
Sn (R=Cy, CH2CF3), have already been reported [7–9].
Tin sulfides are narrow-bandgap semiconductors
with special optical and electronic properties [1]. Tin sul-
fides have three main phases: (i) SnS2, (ii) SnS that ex-
hibit layer structures and (iii) Sn2S3 which is a mixed
valence Sn(II)/Sn(IV) compound with the same local or-
der as the former sulfide, but with a ribbon-like struc-
ture [2]. Tin(II) sulfide displays a distorted rock-salt
arrangement which is isostructural to GeS (orthorhom-
bic, Pbnm group). Six sulfur atoms surround each tin
*
Correspondingauthors. Tel.:+553134997544;fax: +553134995720.
E-mail addresses: gmlima@ufmg.br (G.M. de Lima), aporto@de-
dalus.lcc.ufmg.br (A.O. Porto).
0277-5387/$ - see front matter ꢀ 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2004.06.007

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D.C. Menezes et al. / Polyhedron 23 (2004) 2103–2109
˚
However, either the decomposition temperatures are still
too high or the process goes on in complicated many step
mechanisms. Therefore the search for more appropriate sin-
gle source precursors for Sn–S based materials is still justi-
fied.
k=0.71073 A, radiation. Programs used: COLLECT
,
HKL Denzo-Scalepack, WINGX, SHELXS-97 [12], SHEL-
XL-97 and ORTEP-3 [13] and the refinements were car-
ried out on F2 using SHELXL-97 software [14]. Further
details are given in Table 1. All non-H atoms were re-
fined anisotropic. The carbonsꢀ H atoms were positioned
stereochemically and were refined with fixed individual
displacement parameters [Uiso (H)=1.2Ueq (C)] using
the SHELXL riding model.
The work reported here is part of a more general
study performed by our research team concerning pre-
cursors for tin sulfide and oxide powders, which is still
under investigation [10,11]. So far we have employed or-
ganotin derivatives such as Sn4S4R6 and Sn4O4R6
{R=methyl (Me), n-butyl or phenyl}. We found those
economically attractive not only because of the facile
preparation method but also due to their air stability,
however, the decomposition temperatures are still high.
In order to explore other promising starting materials
and check the viability as a good precursor, we have also
an interest in tin-containing dithiocarbamates complex-
es, and herein we describe the first outcomes of our
investigations.
2.2. Synthesis of [Sn{S2CN(CH2)4}2{C6H5}2]Ætoluene
(1)
[NH4][(CH2)4NCS2] (1.32 g, 8 mmol) was dissolved in
20 cm3 of ethanol and added dropwise to a solution of
(C6H5)2SnCl2 (1.38 g, 4 mmol) in the same solvent.
The mixture was stirred for two hours and then the sol-
vent was removed by filtration and a white solid,
(C6H5)2Sn[S2CN(CH2)4]2, was obtained. The ammoni-
um salt was removed by washing the product with hot
water (80 ꢁC). X-ray quality colourless crystals were ob-
tained by cooling a dichloromethane/toluene solution of
the compound. Yield: 85%. M.p. 222.5–223.1 ꢁC. IR
2. Experimental
(cmÀ1, KBr): 990 and 1050 (s, mC–S), 1560 (s, mC–N). H
1
2.1. Instrumentation and techniques:
NMR (d, CDCl3): 1.95–2.01; 3.60–3.66 (t); 7.23–7.90
IR spectra were obtained as KBr plates on a Mattson
Galaxy Model ST 3000 spectrometer in the 4000–400 cmÀ1
range. NMR spectra were record in CDCl3 at 25 ꢁC on a
Brucker Avance DRX 400. The values were referenced to
internal SiMe4 and SnMe4. C, H, N analyses were per-
formed using a Perkin–Elmer Model PE 2400 CHN.
Thermal decomposition of 1 and 2 were carried out in
a tube furnace in N2 atmospheres up to 500 ꢁC for 1 and
750 ꢁC for 2 using a heating rate of 5 ꢁC/min and a gas
flux of 100 ml/min.
Table 1
Crystal data for [(C6H5)2Sn{S2CN(CH2)4}2]Ætoluene
Empirical formula
Molecular weight
T (K)
C22H26SnN2S4
581.38
100(2)
˚
k (A)
0.71073
triclinic
Crystal system
Space group
Unit cell dimensions
ꢀ
P1
˚
a (A)
8.7355(11)
9.1326(7)
XRD patterns were collected with Rigaku Geigerflex
equipment by using Ni-filtered Cu Ka radiation
˚
b (A)
˚
c (A)
16.72.88(17)
83.704(4)
84.318(6)
˚
(k=1.5418 A) and a graphite monochromator in the dif-
a (ꢁ)
b (ꢁ)
c (ꢁ)
fracted beam. A scan rate of 4 ꢁ/min was applied to re-
cord a pattern in the 2h range of 4–80ꢁ.
88.979(5)
1320.0(2)
3
˚
119Sn Mo¨ssbauer measurements were performed on
conventional apparatus with the samples at liquid N2
temperature and a CaSnO3 source kept at room temper-
ature, for compounds 1 and 2 and both the residues in
order to identify the Sn oxidation state and number of
different sites.
V (A )
Z
2
1.463
qcalc (Mg/m3)
Absorption coefficient (mmÀ1
F(000)
Crystal size (mm3)
)
1.300
588
0.18·0.08·0.04
3.23–25.00
28756
h Range for data collection (ꢁ)
Reflections collected
The scanning electron microscopies (SEM) were tak-
en in JEOL JSM-840A equipment and the samples were
previously covered with a thin gold layer. The X-ray
electron probe microanalyses (EPMA) were carried
out in a JXA 89000 RL wavelength /energy dispersive
combined microanalyser with samples covered with a
thin film of carbon deposited by sputtering.
The intensity data for the X-ray crystallographic de-
termination of 1 were collected at 293(2) K on an En-
raf-Nonius Kappa CCD diffractometer with Mo Ka,
Independent reflections (Rint
)
4634 (0.0392)
99.7
Completeness to h=25.00ꢁ (%)
Maximum and minimum transmission
Refinement method
0.9498 and 0.7997
full-matrix least-squares
on F2
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I>2r(I)]
R indices (all data)
˚
Largest difference peak and hole (e A
CCDC reference
4634/0/282
0.999
R1 =0.0503, wR2 =0.1168
R1 =0.0555, wR2 =0.1209
2.859 and À1.520
236258
À3
)

D.C. Menezes et al. / Polyhedron 23 (2004) 2103–2109
2105
(m, 2 C6H5). 13C NMR (d, CDCl3): 26.7; 54.9; 128.1;
128.3 [1J(119Sn–13C)=811 Hz]; 134.3 [2J(119Sn–13C)
=621 Hz]; 151.6; 194.5. 119Sn NMR (d, CHCl3): À500
2
[1J(119Sn–13C)=811 Hz, J(119Sn–13C)=621 Hz]. Anal.
Calc. for C22H26SnN2S4: C, 46.75; H, 4.60; N, 4.95.
Found: C, 46.62; H, 4.54; N, 4.84%.
2.3. Synthesis of Sn{S2CN(CH2)4}{C6H5}3 (2)
Prepared accordingly using [NH4][(CH2)4NCS2]
(0.56 g, 4 mmol) and SnCl2(C6H5)2 (1.54 g, 4 mmol) dis-
solved in 20 cm3 of ethanol. Yield: 89%. M.p. 171–171.4 ꢁC.
IR (cmÀ1, KBr): 990 and 1060 (mC–S), 1460 and 1570(mC–
1
N). H NMR (d, CDCl3): 1.85–1.97 (m); 3.59–3.70 (t);
7.28–7.90 (m, 2 C6H5). 13C NMR (d, CDCl3): 26.64;
55.05; 128.45 [2J(119Sn–13C)=62 Hz]; 129.06; 136.71
[3J(119Sn–13C)=51 Hz]; 142.07 [1J(119Sn–13C) =606
Hz]; 191.57. 119Sn NMR (d, CHCl3): À174
[1J(119Sn–13C)=606
Hz,
2J(119Sn–13C)=62
Hz,
3J(119Sn–13C)=51 Hz]. Anal. Calc. for C23H23SnNS2:
C, 55.67; H, 4.64; N, 2.82. Found: C, 55.47; H, 4.73; N,
2.81%.
Fig. 1. The Molecular structure of 1 and the atom numbering scheme.
of symmetry, two Sn–C bond lengths are observed,
˚
˚
Sn–C(41) 2.166(5) A and Sn–C(41) 2.156(6) A, for the
Sn–phenyl interactions. The S–Sn–S angles, S(22)–Sn–
S(12) 89.77(5)ꢁ, S(22)–Sn–S(11) 157.20(5)ꢁ, S(12)–Sn–
S(11) 67.55(5)ꢁ are close to those found in the literature.
We have also reviewed the X-ray crystallographic struc-
ture of 2 and the data does not differ from the reported
structure [16]. The Sn(IV) displays a geometric arrange-
ment between tetrahedral and bipyramidal trigonal.
3. Results and discussion
Compounds 1 and 2 were isolated as mixture-free de-
rivatives and after re-crystallisation they showed accept-
able melting points, as well as satisfactory elemental
analyses. They were obtained as air- and moisture-stable
white crystalline solids, readily soluble in polar organic
solvents.
Compound 1 was studied by X-ray crystallography
and the results are displayed in Table 1. It is shown that
the crystalline compound possesses a very disordered
molecule of toluene in its structure (Fig. 1).
Table 2 comprises selected bond lengths and angles.
A similar derivative, [Sn{S2CN(CH2)4}2Me2], previously
published, crystallises as orthorhombic in the Pmmn
space group [15]. In this compound, the Sn atom lies
at the centre of an almost perfect octahedron with a
plane of symmetry, containing the R group and the met-
al centre, and dividing equally the two ligands. Com-
pound 1 has kept the hexacoordination and the
pseudo-octahedral geometry, but the crystals have
1
The H NMR of 1 and 2 revealed signals for the or-
ganic groups. Besides the expected resonances for the R
groups the 13C spectra revealed first and second-order
119Sn–13C couplings. Unlike other reported examples
found in the literature, which normally describe more
than one isomer in solution, detected by 119Sn NMR ex-
periments, in our case only one signal was observed, d
À500 1J(13C–19Sn)=811Hz for 1 and À174 1J(119Sn–
13C)=606 Hz for 2. The latter signal appeared upfield
compared to the former because of the higher coordina-
tion number of the Sn(IV) centre in compound 2.
ꢀ
Table 2
grown in the triclinic system with the space group P1.
Unlike the published derivative, which displays two sets
˚
Selected bond lengths (A) and angles (ꢁ) for 1
˚
of Sn–S bonds, 2.518(1) and 2.9938(1) A, all four Sn–S
distances in 1 are different. There are three slightly differ-
ent short bonds, S(22)–Sn 2.5727(13), S(12)–Sn
C(31)–Sn
C(41)–Sn
S(11)–Sn
2.156(6)
2.166(5)
2.6850(17)
S(12)–Sn
S(21)–Sn
S(22)–Sn
2.5864(14)
2.9495(16)
2.5737(13)
˚
2.5864(14) and S(11)–Sn 2.6850(17) A, and a long one
˚
S(21)–Sn 2.9495(16) A, which seems not to remain in so-
lution as will be discussed later. Apart from the longer
bond, the former bonds correlate very well with those
observed for the methyl derivative. Because of the lack
C(31)–Sn–C(41)
C(31)–Sn–S(12)
C(31)–Sn–S(22)
C(31)–Sn–S(11)
S(22)–Sn–S(12)
107.58(19)
152.82(14)
105.35(14)
94.87(14)
89.77(5)
C(41)–Sn–S(11)
C(41)–Sn–S(22)
C(41)–Sn–S(12)
S(12)–Sn–S(11)
S(22)–Sn–S(11)
92.66(14)
91.18(14)
94.29(14)
67.55(5)
157.20(5)

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D.C. Menezes et al. / Polyhedron 23 (2004) 2103–2109
Table 3
119Sn Mo¨ssbauer parametersa (isomer shift (IS), quadrupole splitting (QS), area and width) obtained at liquid nitrogen temperature for the
compounds 1 and 2 and their respective residues obtained in N2
Material
Sn site
IS (mm sÀ1
)
QS (mm sÀ1
)
Area (%)
Width (mm sÀ1
)
1
Sn(IV)
Sn(IV)
Sn(II)
Sn(IV)
Sn(II)
Sn(IV)
1.09
1.26
3.31
0.17
3.08
0.14
1.72
1.65
1.03
0.59
1.07
0.56
100
100
88
0.90
0.90
0.90
0.90
0.90
0.90
2
Residue of 1
12
77
Residue of 2
21
a
The errors associated to IS, QS and width are 0.05 mm sÀ1 and 1% for the area.
It is possible to estimate the C–Sn–C bond angle em-
ploying methods encountered in the literature, which
correlates the angle with the first-order coupling con-
stant between 119Sn and 13C, in solution [17]. The meth-
ods have provided a C–Sn–C angle for compound 1
ranging from 154.57ꢁ to 157.34ꢁ, in disagreement with
the experimental data, 107.58(19)ꢁ. Either because the
structure of 1 in solution differs drastically from that
in the solid state, or the reported methods do not apply
to this system. The latter could be justified by the disso-
ciation of the long Sn–S bond, discussed in the X-ray re-
sults, effecting a change in the coordination of the metal.
The 119Sn Mo¨ssbauer parameters, isomer shift (IS)
and quadrupolar splitting (QS) obtained for compounds
1 and 2 indicate a strong dependence upon the coordina-
tion number, hybridisation and symmetry around the
Sn(IV) nucleus. The IS for 1, 1.09 mm sÀ1 is smaller than
that for 2, 1.65 mm sÀ1, Table 3, suggesting higher coor-
dination, as attested by the X-ray and 119Sn-NMR
spectroscopic results. It is consistent with a smaller con-
tribution of s electrons to the hybridisation scheme at
the tin atom in 1 as compared to 2. The quadrupole
splitting parameters 1.30 and 1.80 mm sÀ1 points to a
lower symmetry for complex 1. These data match per-
fectly with other known values for penta and hexacoor-
dinated Sn(IV) derivatives [18].
structurally characterised. The EPMA results, Fig. 3,
clearly indicate the presence of Sn and S as major ele-
ments in the residues. However, a tiny amount of oxygen
has also been revealed, which might be due to the forma-
tion of SnO2 as a much lesser product. It has possibly
originated from the N2, which was not completely free
from moisture or oxygen, however, it is much smaller
than the quantity of carbon, employed to cover the
sample.
The diffraction patterns of the residues, Fig. 4, sug-
gested the formation of c-Sn2S3 and SnS, both ortho-
rhombic phases, in view of the diffraction lines. The
lines of SnO2, which is quite sensitive to this technique,
were not detected. A poor crystallinity of the sample has
rendered low quality XRD patterns for residue 1. Nev-
ertheless, lines at 2h/ꢁ 27.19, 31.80, 31.46 and 38,99 as-
signed to c-Sn2S3 and SnS were identified. A better
diffractogram was obtained for 2 and it was possible
to connect the lines at 2h/ꢁ 31.61 (201), 31.86 (131),
25.94 (101), 27.22 (140) and 38.94 (301) to c-Sn2S3
(JCPDS-ICCD 1996 card no. 39-0354). Likewise, those
diffractions at 2h/ꢁ 31.50 (111), 31.73 (040), 25.94
(110), 27.36 (021), 30.46 (101) and 39.24 (131)
were attributed to SnS (JCPDS-ICCD 1996 card no.
3.1. Thermal decomposition of 1 and 2 and characterisa-
tion of the residues
The thermogravimetric curves of 1 and 2, Fig. 2,
shows that the decomposition processes begin at 207
and 233 ꢁC ( 2 ꢁC), respectively, and at about 350 ꢁC
both materials have been consumed. The presence of
one more phenyl group in the structure of 2 increases
its Td (temperature of decomposition) by approximately
26 ꢁC. In both cases, the decomposition take place in a
pseudo-single step and the decomposition temperatures
are lower than those found for organotin sulfides, re-
ported by us, which have been considered a promising
single source precursor [10a].
The residue obtained after the pyrolysis of 1 and 2 car-
ried out in a tube furnace in N2 were chemically and
Fig. 2. The thermogravimetric curves of 1 (a) and 2 (b) in nitrogen.

D.C. Menezes et al. / Polyhedron 23 (2004) 2103–2109
2107
Fig. 3. The X-ray electron probe microanalysis (EPMA) of the residue of 1 (a) and 2 (b).
30-13790). The respective Miller indexes are indicated in
parenthesis.
The 119Sn Mo¨ssbauer spectra were important to con-
firm the results of XRD and EPMA, Fig. 5. The exper-
iments have clearly shown the presence of two Sn sites
corresponding to Sn(II) and Sn(IV) in the residues, in
the form of SnS and Sn2S3. Since the amount of SnO2
is not detectable, it is not absurd to assume that all
the Sn nuclei exist as tin-sulfides. For the residue of
1 there are two sets of signals, IS 3.31 mm sÀ1, QS
1.03 mm sÀ1 and IS 0.17 mm sÀ1, QS 0.59 mm sÀ1. Sim-
ilarly, for 2 IS 3.08 mm sÀ1, QS 1.07 mm sÀ1 and IS 0.14
mm sÀ1, QS 0.56 mm sÀ1 are observed. The Mo¨ssbauer
parameters for both residues are in good agreement
with similar data reported in one of our previous works
[10a]. It is important to observe that a smaller amount
of Sn(II) was produced in the decomposition of 2 (ar-
ea=77%) compared to the residue of 1 (area=88%).
In either case there is more SnS than the required
amount to match the Sn2S3 stoichiometry. It is possible
that a mixture of the two sulfides is present, which the
119Sn Mo¨ssbauer experiments cannot reveal. We have
also performed the same study on a standard of Sn2S3
and the same pattern of two set of signals with
IS=3.35 mm sÀ1, QS=0.97 mm sÀ1 for Sn(II) and
IS=0.46 mm sÀ1, QS=0.88 mm sÀ1 for Sn(IV) was en-
countered.
The scanning electron micrographs showed that lay-
ered and ribbon-like crystals basically compose the res-
idues, Fig. 6. It is a very common characteristic of SnS
and Sn2S3 systems. The SEM images have revealed the
particle size of microns and also confirmed the low crys-
tallinity of the samples, as pointed out by the XRD
diffractograms.
Fig. 4. The X-ray powder diffraction patterns of the residue 1 (a) and
2 (b).

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D.C. Menezes et al. / Polyhedron 23 (2004) 2103–2109
Fig. 5. The 119Sn Mo¨ssbauer spectra and the respective quadrupole distribution of the residue of 1 (a) and 2 (b).
5. Supplementary data
Crystallographic data for the structural analysis for
complex 1 have been deposited at the Cambridge Crys-
tallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK, and are available on request quoting
the deposition number CCDC-236258.
Acknowledgements
We thank CNPq-Brazil for granting a scholarship to
´
D.C. Menezes. We are in debit to the Laboratorio de
ˆ
´
Microscopia Eletronica e Microanalise (LMA) for per-
forming part of the analysis – financed by FAPEMIG
(Project CEX 1074/95).
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compounds 1 and 2 has been proved as single source
precursor for SnS and Sn2S3. They were obtained by a
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