Monoorganobismuth(III) dithiocarboxylates: Synthesis, structures and their utility as molecular precursors for the preparation of Bi2S3 films and nanocrystals

Article abstract of DOI:10.1016/j.ica.2009.11.002

Synthesis of a series of monoorganobismuth dithiocarboxylate complexes, [RBi(S₂CAr)₂] (R = Me, Ph, tol; Ar = Ph, tol), has been reported. They have been characterized by elemental analyses and spectroscopic methods. Molecular structures of [RBi(S₂Ctol)₂] (R = Me or Ph) have been established by single crystal X-ray diffraction studies. The bismuth atom in these complexes adopts a square pyramidal configuration with the R group at the apical position. In the solid state, these complexes show supra-molecular association devoid of Bi?S secondary interactions. Thermolysis of [RBi(S₂Ctol)₂] (R = Me or Ph) in refluxing diphenylether yielded Bi₂S₃ nanocrystals which were characterized by XRD, EDAX and SEM. The complex [PhBi(S₂Ctol)₂] has been employed for deposition of thin films of Bi₂S₃ by AACVD.

Full text of DOI:10.1016/j.ica.2009.11.002

Inorganica Chimica Acta 363 (2010) 375–380
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Monoorganobismuth(III) dithiocarboxylates: Synthesis, structures and their
utility as molecular precursors for the preparation of Bi2S3 films and nanocrystals
b
Kamal R. Chaudhari a, Neelam Yadav b, Amey Wadawale a, Vimal K. Jain a, , Rakesh Bohra
*
a Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
b Department of Chemistry, Rajasthan University, Jaipur 302004, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Synthesis of a series of monoorganobismuth dithiocarboxylate complexes, [RBi(S2CAr)2] (R = Me, Ph, tol;
Ar = Ph, tol), has been reported. They have been characterized by elemental analyses and spectroscopic
methods. Molecular structures of [RBi(S2Ctol)2] (R = Me or Ph) have been established by single crystal
X-ray diffraction studies. The bismuth atom in these complexes adopts a square pyramidal configuration
with the R group at the apical position. In the solid state, these complexes show supra-molecular asso-
ciation devoid of Biꢀ ꢀ ꢀS secondary interactions. Thermolysis of [RBi(S2Ctol)2] (R = Me or Ph) in refluxing
diphenylether yielded Bi2S3 nanocrystals which were characterized by XRD, EDAX and SEM. The complex
[PhBi(S2Ctol)2] has been employed for deposition of thin films of Bi2S3 by AACVD.
Received 16 April 2009
Received in revised form 17 September
2009
Accepted 3 November 2009
Available online 10 November 2009
Keywords:
Bismuth
X-ray structure
Bi2S3 nanocrystals
Thin films
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
2. Results and discussion
The chemistry of 1,1-dithiolate complexes of arsenic, antimony
and bismuth has been an active area of research for more than four
decades and has been dominated by complexes derived from xan-
thate, dithiocarbamate and phosphorus based dithio acid ligands
[1]. In contrast to this, the dithiocarboxylate complexes of these
elements have received some attention only recently [2–4], and
their utility as molecular precursors for metal sulfide has been
demonstrated by us [4].
Both classical and organometallic complexes of bismuth with
xanthates [5–10], dithiocarbamates [11–19] and dithiophos-
phates/phosphinates [20–28] have been isolated and characterized
by several workers. Although these complexes in general adopt an
associated structure formed through secondary intermolecular
Biꢀ ꢀ ꢀS interactions, discrete monomeric structures also exist. At-
tempts to correlate structural motif based on either ligand type or
R group on bismuth lead to little success. For instance, [MeBi(S2-
COMe)2] exists in a supramolecular chain form [10], while [PhBi(S2-
COMe)2] is a monomer [7], whereas [PhBi(S2CNEt2)2] adopts a
dimeric structure [17]. Thus it is of interest to examine structural
features of methyl and phenyl bismuth complexes containing
dithiocarboxylate groups and evaluate their suitability as molecular
precursors for the preparation of Bi2S3 thin films and nanocrystals.
2.1. Synthesis and spectroscopy
Reactions of MeBiCl2 with dithiocarboxylic acids in the presence
of triethylamine as HCl scavenger afforded [MeBi(S2CAr)2]. The
corresponding aryl bismuth derivatives were conveniently synthe-
sized either by treatment of triarylbismuth with two equivalents of
dithiocarboxylic acid or by disproportionation between R3Bi and
Bi(S2CAr)3 (Scheme 1). These complexes are orange–red to
brown–red crystalline solids. NMR (1H and 13C) spectra displayed
expected resonances attributable to RBi and ArCS2 fragments.
2.2. Molecular structures of [RBi(S2Ctol)2] (R = Me or Ph)
The structures of [RBi(S2Ctol)2] (R = Me or Ph) have been estab-
lished unambiguously by X-ray crystallography (Figs. 1 and 2).
Structures of these compounds are isomorphous. The coordination
around bismuth is defined by the carbon atom of Me or Ph and four
sulfur atoms of anisobidentate dithiocarboxylate groups. The bis-
muth acquires a distorted square pyramidal configuration with
Me/Ph occupying the apical position and four sulfurs at the corners
of the square. There is a void opposite to the R group and appears
to be filled by a stereochemically active lone pair of electrons while
the gap in the square plane defined by four sulfur atoms may be
occupied by the electron pairs on sulfur.
* Corresponding author.
E-mail addresses: jainvk@barc.gov.in, jainvk@apsara.barc.ernet.in (V.K. Jain),
rkbohra@sifymail.com (R. Bohra).
Each dithiocarboxylate ligand forms one shorter (ꢁ2.68 Å) and
onelonger(ꢁ2.96 Å)Bi–Sbondswhicharewithintherangereported
0020-1693/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2009.11.002

376
K.R. Chaudhari et al. / Inorganica Chimica Acta 363 (2010) 375–380
Table 1
[MeBi(S2CAr)2] + 2 Et3N.HCl
MeBiCl2 + 2 ArCS2H + 2 Et3N
Selected bond lengths (Å) and angles (°) for [RBi(S2Ctol)2] (R = Me, Ph).
[RBi(S2CAr)2] + 2 RH
3 [RBi(S2CAr)2]
R3Bi + 2 ArCS2H
MeBi(S2Ctol)2
PhBi(S2Ctol)2
Bi1–C17
Bi1–S1
Bi1–S2
Bi1–S3
Bi1–S4
S1–C1
S2–C1
S3–C9
S4–C9
2.245(12)
2.673(4)
2.945(4)
2.678(3)
2.961(4)
1.717(13)
1.687(14)
1.715(12)
1.656(12)
2.301(15)
2.686(4)
2.960(5)
2.688(6)
2.957(4)
1.698(18)
1.69(2)
R3Bi + 2 Bi(S2CAr)3
Scheme 1.
for 1,1-dithiolate complexes of bismuth [7,10,14]. The Bi–C distance
in [MeBi(S2Ctol)2] (2.245 (12) Å) is similar to the length reported for
[MeBi(S2COMe)2] [10] and [MeBi(S2CNEt2)2] [14], whereas this dis-
tance for [PhBi(S2Ctol)2] (2.301(7) Å) is slightly longer than the one
reported for [PhBi(S2CC6H4OMe-p)2] (2.254(7) Å) [3], [PhBi(S2-
COMe)2] (2.25(1) Å) [7], and [PhBi(S2CNEt2)2] (2.241(10) Å) [17].
Although various angles involving bismuth in two compounds are
similar, the C(17)–Bi-(1)–S(4) in [MeBi(S2Ctol)2] (84.0(4) °) is smal-
ler than that for the corresponding phenyl derivative and also from
the one reported for [MeBi(S2COMe)2] (86.8(2) °) [10]. Selected bond
lengths and angles are summarized in Table 1. Some salient struc-
tural features of these complexes with other organobismuth dithiol-
ate complexes are compared in Table 2.
Unlike other organobismuth supramolecular chains which are
stabilized through secondary weak Biꢀ ꢀ ꢀS interactions [6,10,14,17],
such interactions are, however, absent in the crystal structures of
[RBi(S2Ctol)2] (R = Me or Ph) described here. In [MeBi(S2Ctol)2],
weak Hꢀ ꢀ ꢀS contacts are responsible for polymeric chain. The dis-
tances between S-2 and H-16B and S-4 and C-10 of the adjacent mol-
ecule and S-2 and H-16C of the next molecule are 2.862, 3.488 and
2.968 Å, respectively. In [PhBi(S2Ctol)2], the void of two molecules
face each other with a Biꢀ ꢀ ꢀBi distance of ꢁ4.0 Å which is the sum
of van der Waals radii of two bismuth atoms (4.0 Å).
1.711(15)
1.648(18)
C17–Bi1–S1
C17–Bi1–S2
C17–Bi1–S3
C17–Bi1–S4
S1–Bi1–S2
S1–Bi1–S3
S1–Bi1–S4
S2–Bi1–S4
S3–Bi1–S2
S3–Bi1–S4
S2–C1–S1
S4–C9–S3
C1–S1–Bi1
C1–S2–Bi1
C9–S3–Bi1
C9–S4–Bi1
94.2(5)
86.1(4)
91.9(4)
84.0(4)
62.85(11)
81.66(11)
143.79(10)
152.19(11)
144.16(11)
62.30(10)
119.4(8)
120.5(8)
92.9(5)
92.0(5)
90.9(4)
92.5(5)
90.2(4)
62.84(14)
80.31(13)
142.72(15)
154.34(15)
143.08(13)
62.42(14)
121.5(8)
121.7(9)
92.2(6)
84.5(5)
92.8(4)
84.4(5)
83.3(5)
91.7(6)
83.9(5)
18.7%. Found Bi, 83.0; S, 17.0% (for Bi2S3 obtained from [MeBi(S2C-
tol)2]); Bi, 79.9; S, 20.1% (for Bi2S3 obtained from [PhBi(S2Ctol)2])}.
The average size of the particles estimated by employing Scherrer
equation was ꢁ16 nm. The SEM images of as synthesized nano-
crystals (Figs. 4 and 5) showed the formation of nanorods and
nanoparticles for samples obtained from [PhBi(S2Ctol)2] and [Me-
Bi(S2Ctol)2], respectively.
2.3. Bi2S3 nanocrystals and thin film
Thermolysis of [RBi(S2Ctol)2] (R = Me or Ph) in diphenyl ether at
260 °C gave a blackish powder which was separated by centrifuga-
tion. The powder X-ray diffraction pattern of as prepared materials
(Fig. 3) was consistent with the formation of Bi2S3 (JCPDS file No.
17-0320). The EDAX analysis of these samples were in agreement
with the composition of Bi2S3 {Anal. Calc. for Bi2S3: Bi, 81.3; S,
TG analysis of [PhBi(S2CPh)2] showed a two-step decomposi-
tion with the formation of Bi2S3 at 470 °C (weight loss found:
55.2%; calculated weight loss for Bi2S3: 56.6%). To assess the
suitability of these complexes as molecular precursors for depo-
sition of Bi2S3 films, one representative complex [PhBi(S2Ctol)2]
was chosen as precursor for deposition of Bi2S3 films by AACVD
Fig. 1. Molecular structure of [MeBi(S2Ctol)2] (ellipsoids drawn with at 50% probability).

K.R. Chaudhari et al. / Inorganica Chimica Acta 363 (2010) 375–380
377
Table 2
Salient structural features of organobismuth 1,10-dithiolate complexes.
Compound
Nuclearity
Bi–S distance in Å
Bi–S(short)
\S–Bi–S in (°)
Reference
Bi–S(long)
D Bi–S
[MeBi(S2Ctol)2]
[MeBi(S2COMe)2]
Monomer
Polymer
Supramolecular chain motif through
Bi–S secondary interactions
2.676(av)
2.71–2.78
2.956(av)
2.84–2.99
0.28
0.06–0.28
This work
10
S1BiS2
ꢁ62
S3BiS4
ꢁ64
[MeBi(S2CNEt2)2]
Dimer
2.67–2.70
2.93–2.98
0.23–0.31
S1BiS2
63.4
14
S3BiS4
62.9
[PhBi(S2Ctol)2]
PhBi(S2COMe)2
Monomer
Monomer
2.687(av)
2.649–2.67
2.958(av)
2.961–3.0793
0.27
0.351–0.4303
This work
7
S1BiS2
63.7
S3BiS4
61.8
[PhBi(S2CNEt2)2]
Dimer
2.71–2.676
2.92–2.94
0.244–0.269
S1BiS2
63.9
17
S3BiS4
63.5
MesBi(S2PPh2)2
Monomer
Supramolecular chain
Monomer
2.662
2.66
ꢁ2.67
3.123
3.23
ꢁ2.98
0.461
0.57
0.31
26
6
3
[Ph2Bi(S2COPri)]
–
[PhBi(S2CC6H4OMe-p)2]
ꢁ62.36
Fig. 2. Molecular structure of [PhBi(S2Ctol)2] (ellipsoids drawn with 50% probability).

378
K.R. Chaudhari et al. / Inorganica Chimica Acta 363 (2010) 375–380
160
140
120
100
80
60
40
20
0
10
20
30
40
50
60
70
2θ
Fig. 3. XRD pattern of Bi2S3 prepared from PhBi(S2Ctol)2 in refluxing diphenylether at 260 °C.
Fig. 4. SEM images of Bi2S3 prepared from PhBi(S2Ctol)2 in diphenylether at 260 °C.
Fig. 5. SEM images of Bi2S3 prepared from MeBi(S2Ctol)2 in diphenylether at 260 °C.
(aerosol assisted chemical vapor deposition). Macroscopically
homogeneous, black Bi2S3 films on glass and silicon wafers were
deposited at 450 °C. The composition of these films was analyzed
by EDAX (Found: Bi, 79.9; S, 20.1% (on glass substrate); Bi, 81.7;
S, 18.3% (on Si wafer). There was hardly any noticeable differ-
ence between the films grown on glass and Si wafers. The mor-
phologies of the films were studied by SEM and representative
images are given in Fig. 6. The SEM image showed that the
deposited films are uniform (Fig. 6a) comprising of micron-sized
(Fig. 6b) fibers of Bi2S3. Similar fibrous films have been deposited
earlier by MOCVD using classical tris-chelates, [Bi(S2CNR2)3] and
[Bi(S2COR)3] [29,30].
by standard procedures. Bismuth trichloride was sublimed under
vacuum before use. Dithiocarboxylic acids (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))
[31], MeBiCl2 [32], Ph3Bi [33], (tol)3Bi [33] and [Bi(S2CAr)3] (1H
NMR in CDCl3 [Bi(S2CPh)3] 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). [Bi(S2Ctol)3] d: 2.38 (s, Me);
7.20 (d, 8 Hz, H-3, 5); 8.14 (d, 8 Hz, H-2, 6)) [4] were prepared
according to literature methods.
Infrared spectra were recorded as Nujol mulls between CsI
plates on a Bomem MB-102 FT IR spectrometer. 1H and 13C{1H}
NMR spectra were recorded on a Bruker Avance-II 300 MHz spec-
trometer in CDCl3 and DMSO-d6 solution. Chemical shifts are rela-
tive to internal chloroform peak (7.26 ppm and 77.0 ppm for 1H
and 13C{1H}NMR, respectively) or DMSO peak (2.49 ppm and
39.5 ppm for 1H and 13C{1H}NMR, respectively). Electronic spectra
were recorded in dichloromethane on a Chemito Spectrascan UV
3. Experimental
All experiments involving bismuth compounds were carried out
under anhydrous conditions in Schlenk flasks. Solvents were dried

K.R. Chaudhari et al. / Inorganica Chimica Acta 363 (2010) 375–380
379
Fig. 6. SEM images of Bi2S3 thin films deposited on glass substrate from [PhBi(S2Ctol)2] using aerosol assisted chemical vapor deposition at 450 °C.
double beam UV–Vis spectrophotometer. Powder X-ray diffraction
data were collected on a Philips PW 1820.
in CDCl3: 127.9, 128.2, 133.6, 133.9 (BiPh), 21.8, 126.4,
128.6; 138.8, 149.0 (C6H4, dithio), 240.9 (C@S).
(b) To
benzene solution (60 cm3) of triphenyl bismuth
(173 mg, 0.39 mmol), solution of tolCS2H (132 mg,
a
3.1. Preparation of [MeBi(S2Ctol)2]
a
0.78 mmol) in the same solvent was added with stirring.
The whole mixture was refluxed for 5 h. The solvent was
evaporated under vacuum to afford a dark brown crystalline
solid (242 mg, 99% yield) m.p. 140 °C (decomp.)
To a benzene solution (60 cm3) of methylbismuth dichloride
(300 mg, 1.02 mmol), a solution of tolCS2H (336 mg, 2.0 mmol)
and triethylamine (202 mg, 2.0 mmol) in the same solvent were
added with stirring. The whole reaction mixture was stirred at
room temperature for 5 h. The precipitate was filtered through a
G-3 filtration unit. The filtrate was dried in vacuum to give a brown
solid (443 mg, 78%); m. p. 175 °C (decomp.). Anal. Calc. for
C17H17BiS4: C, 36.5; H, 3.0; S, 22.9%. Found: C, 37.0; H, 2.8; S,
3.4. Preparation of [PhBi(S2CPh)2]
Prepared similar to [PhBi(S2Ctol)2] (a and b) as an orange solid
in 98% yield; m.p. 135 °C (decomp.) Anal. Calc. for C20H15BiS4: C,
40.5; H, 2.5%. Found: C, 40.7; H, 2.4%. UV–Vis kmax: 253, 320 nm.
22.3%. UV–Vis kmax: 254, 319 nm. IR:
m , m(C@S)
(C–S) 722 cmꢂ1
1170 cmꢂ1 1H NMR in DMSO-d6 d: 1.69 (s, BiMe), 2.31(s, tol–
.
Me), 7.28 (d, 8.0 Hz, H-3, 5); 8.10 (d, 8.0 Hz, H-2, 6). 13C{1H}NMR
in DMSO-d6: 21.6 (s, Me–tol); 31.1(s, BiMe), 126.4, 129.0, 144.8,
147.2 (C6H4), 243.0 (C@S).
IR:
(t, H-3, 4, 5 (CS2Ph)); 7.62–7.73 (br, H-3, 4, 5 (Ph)); 8.25 (d,
m , m .
(C–S) 723 cmꢂ1 (C@S) 1216 cmꢂ1 1H NMR in CDCl3 d: 7.41
6.0 Hz, Ph H-2,
6 (CS2Ph)); 8.80 (d, 9.0 Hz, H-2, 6 (PhBi)).
13C{1H}NMR in CDCl3: 127.9, 130.5, 133.8, 137.6 (PhBi), 126.4,
3.2. Preparation of [MeBi(S2CPh)2]
128.7, 130.5, 139.4, (C6H5, dithio), 241.5 (C@S).
Prepared similar to [MeBi(S2Ctol)2] as an orange crystalline
solid in 75% yield; m.p. 190 °C (decomp.). Anal. Calc. for
C15H13Bi S4: C, 34.0; H, 2.5; S, 24.2%. Found: C, 33.5; H, 2.2; S,
3.5. Preparation of [tolBi(S2Ctol)2]
Prepared similar to [PhBi(S2Ctol)] (b) as brown solid in 98% yield,
m.p. 95 °C (decomp.)Anal. Calc. forC23H21BiS4: C, 43.5; H, 3.3%. Found:
24.5%. UV–Vis kmax: 251, 320 nm. IR:
m , m(C@S)
(C–S) 723 cmꢂ1
1218 cmꢂ1 1H NMR in DMSO-d6 d: 1.69 (s, BiMe); 7.44 (t,
.
C, 43.1; H, 3.0%. UV–Vis kmax: 252, 340 nm. IR:
m ,
(C–S) 725 cmꢂ1
m
(C@S) 1177 cmꢂ1 1H NMR in CDCl3 d: 2.27 (s, Me, Bitol); 2.37 (s,
.
8 Hz, H-3, 5); 7.67 (t, 7.5 Hz, H-4); 8.16 (d, 6.0 Hz, H-2, 6).
13C{1H}NMR in DMSO-d6: 43.2(s, Me), 126.2, 128.5, 133.8,
149.7 (C6H5), 244.2 (C@S).
S2Ctol3); 7.21 (d, 9.0 Hz, CS2tol H-3, 5); 7.48 (d, 9.0 Hz, Bitol H-3, 5);
8.15 (d, 8.4 Hz, CS2tol H-2, 6); 8.69 (d, 8.1 Hz, Bitol H-2, 6). 13C{1H}
NMR in CDCl3: 21.5 (s, Me, Bitol) 21.8 (C6H4CH3); 126.6, 128.5,
131.3, 133.7, 137.5, 139.4, 145.2, 146.8 (C6H4 + C6H4), 240.8 (C@S).
3.3. Preparation of [PhBi(S2Ctol)2]
(a) To
a
benzene solution (60 cm3) of triphenyl bismuth
3.6. Preparation of [tolBi(S2CPh)2]
(142 mg, 0.32 mmol), a solution of [Bi(S2Ctol)3] (461 mg,
0.65 mmol) in the same solvent was added with stirring.
The whole mixture was refluxed for 5 h. The solvent was
evaporated under vacuum to afford a dark brown residue
(555 mg, 92% yield) m.p. 140 °C (decomp.). Anal. Calc. for
C22H19BiS4: C, 42.6; H, 3.1%. Found: C, 42.1; H, 2.9%. UV–
Prepared similar to [PhBi(S2Ctol)] (b) as brown solid in 98%
yield, m.p. 130 °C (decomp.) Anal. Calc. for C21H17BiS4: C, 41.6; H,
2.8%. Found: C, 41.7; H, 2.2%. UV–Vis kmax: 252, 320 nm. IR:
m(C–
S) 720 cmꢂ1 (C@S) 1173 cmꢂ1. 1H NMR in CDCl3 d: 2.38 (s, Me, Bi-
,
m
tol); 7.21 (d, 7.5 ditho); 7.39 (t, BiPh), 7.71 (t, BiPh); 8.16 (d, 7.5 Hz,
dithio), 8.83 (d, BiPh). 13C{1H}NMR in CDCl3: 21.8 (s, Me, Bitol)
126.7, 128.6, 130.5, 132.8, 137.6, 139.4, 145.3, 146.8 (C6H4 + Ph),
240.9 (C@S).
Vis kmax
1222 cmꢂ1
7.52 (7.5 Hz, tol); 8.24 (d 8 Hz, Ph), 8.67 (d, tol). 13C{1H}NMR
:
253, 320 nm. IR:
m , m(C@S)
(C–S) 729 cmꢂ1
.
1H NMR in CDCl3 d: 2.30 (s, CH3); 7.41(t, Ph);

380
K.R. Chaudhari et al. / Inorganica Chimica Acta 363 (2010) 375–380
Table 3
Acknowledgement
Crystallographic and structural determination data for [RBi(S2Ctol)2] (R = Me, Ph).
Complex
[MeBi(S2Ctol)2]
[PhBi(S2Ctol)2]
We express our sincere gratitude to Drs. T. Mukherjee and D.
Das for the encouragement of this work. We are thankful to
Department of Chemistry, IIT Bombay for providing micro-analysis
of the compounds. Authors NY and RB thank CSIR and DST for
financial support.
Chemical formula
Formula wt.
Color
C17H17S4Bi
558.53
Brown
0.30 ꢃ 0.2 ꢃ 0.1
Monoclinic
C2/c
C22H19S4Bi
620.59
Red
Crystal size (mm3)
Crystal system
Space group
Unit cell dimensions
a (Å)
0.20 ꢃ 0.10 ꢃ 0.05
Triclinic
ꢀ
P1
Appendix A. Supplementary material
18.740(5)
8.146(2)
25.112(9)
90.000
100.41(3)
90.000
3770.3(19)
1.968
8
9.789/2128
2.51 to 27.51
ꢂ13 6 h 6 24
0 6 k 6 10
ꢂ32 6 l 6 32
psi-scan
11.550(5)
11.720(4)
8.940(4)
107.35(3)
96.62(3)
105.15(3)
1090.2(7)
1.890
b (Å)
c (Å)
CCDC 717119 and 717120 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-
ated with this article can be found, in the online version, at
doi:10.1016/j.ica.2009.11.002.
a
(°)
b (°)
c
(°)
Volume (Å3)
Density Calc. (g cmꢂ3
)
Z
l
2
(mmꢂ1)/F(000)
8.474/596
2.54 to 27.49
ꢂ14 6 h 6 14
ꢂ15 6 k 6 14
ꢂ16 6 l 6 11
psi-scan
References
h for data collection/°
Limiting indices
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Absorption correction
Refinement method
Full matrix least squares Full matrix least squares
on F2 > 0
on F2 > 0
6073/4995
Reflections collected/
unique
Data/restraints/
parameters
5172/4335
4335/0/199
4995/0/244
Final R1,
x
R2 indices
0.0654/0.1026
0.2905/0.1506
0.897
1.531 and ꢂ2.153
0.063/0.133
0.193/0.173
1.001
1.538 and ꢂ2.608
R1,
xR2 (all data)
Goodness of fit on F2
Largest diff. peak and
hole (e.Åꢂ3
)
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3.7. Preparation of Bi2S3 nanocrystals
In a typical experiment diphenylether (25 cm3) in a three-necked
flask was degassed at refluxing temperature under a nitrogen atmo-
sphere for 30 min. To this a weighed quantity of [MeBi(S2Ctol)3]
(21 mg; 0.04 mmol)/[PhBi(S2Ctol)2] (42 mg, 0.07 mmol) was added
and the mixture was refluxed for 3 h, gradually cooled and centri-
fuged to give nanocrystals of Bi2S3 which were thoroughly washed
with methanol and dried under vacuum.
3.8. Preparation of Bi2S3 films
In a typical deposition experiment, [PhBi(S2Ctol)2] (24 mg) dis-
solved in 100 ml toluene was employed. An aerosol of this precur-
sor solution was generated using an ultrasonic humidifier. The
aerosol so generated was transported through argon as a carrier
gas with a flow of 1.5 cfm to a preheated reactor holding two
glass/silicon wafers as substrate. Decomposition of precursor on
preheated substrate led to deposition of Bi2S3 films.
4. Crystallography
Intensity data for [RBi(S2Ctol)2] (R = Me or Ph) were measured on
a Rigaku AFC 7S diffractometer fitted with Mo-Ka(k 0.71069 Å) radi-
ation so that hmax = 27.5°. The structures were solved by direct meth-
odsand refinementwas on F2 [34]usingdata thathadbeen corrected
for an absorption effects with an empirical procedure [35,36] with
non-hydrogen atoms modeled with anisotropic displacement
parameters with hydrogen atoms in their calculated positions.
Molecular structures were drawn using ORTEP [37]. Molecular and
structural determination data are listed in Table 3.
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(1968) 351.