R. Chauhan et al. / Inorganica Chimica Acta 430 (2015) 168–175
169
1
[
Bi(dtc)
3
] (1) (dtc = 4-hydroxypiperdine dithiocarbamate) complex
[Bi(HOCH(CH
NMR (CDCl
–
1
2
)
4
NCS
2
)
3
] (1) (0.582 g, yield 79%); m.p. 241 °C. H
as single-source precursor for Bi–Bi
S
2 3
.
3
, d): 5.28 (s, 1H, –OH), 5.24 (s, 2H, –CH), 3.84 (s, 2H,
CHax), 3.63 (s, 2H, –CHeq), 1.99 (s, 2H, –CHax) 1.83 (s, 2H, –CHeq.),
.73 (s, 2H, –CHax). C NMR (CDCl , d): 199.8 (–NCS ), 64.8, 47.9,
3 2
33.8 (piperidine). mmax (KBr)/cm 3403 (–OH), 1434 (C@N), 1081
C–S). Anal. Calc. for C18 Bi: C, 29.30; H, 4.10; N, 5.60; S,
26.08. Found: C, 30.10; H, 4.28; N, 5.74; S, 27.23%.
1
3
ꢀ1
2
. Experimental
(
30 3 3 6
H N O S
2
.1. Materials and physical measurements
All the synthetic manipulations were performed under ambient
2
.3. X-ray crystallography
atmosphere. The solvents were dried and distilled before use by
following the standard procedures. 1H and C NMR spectra were
recorded on JEOL AL300 FTNMR spectrometer. Chemical shifts
were reported in parts per million using TMS as internal standard.
The electronic absorption spectra in DMSO solution were recorded
13
Intensity data for 1 was collected at 150(2) K on a Nonius Kappa
CCD diffractometer using graphite monochromated Mo Karadiation
k = 0.71073 Å. Unit cell determination, scaling of the data, and cor-
rections for Lorentz and polarization effects were performed with
Denzo-SMN [36]. The structure was solved by direct methods
using
Elemental analysis was performed on an Exeter analytical Inc.
‘Model CE-440 CHN analyser’’. Structural characterization of Bi
and Bi was done using X-ray diffraction (XRD) measurements
on a Bruker D8 Advance X-ray diffractometer equipped with gra-
phite monochromator using Cu K (k = 1.54 Å) radiation, at a scan-
a SPECORD 200 PLUS BU UV–Vis spectrophotometer.
(SIR97) [37] and refined by a full-matrix least-squares procedure
‘
2
based on F [38]. All non-hydrogen atoms were refined anisotropi-
cally; hydrogen atoms were located at calculated positions and
refined using a riding model. The asymmetric unit of 1 consists of
half a dimeric Bi complex and one solvent molecule of MeOH. One
OH-group (O2/O2A) is disordered over two sites in the ratio 60:40.
All hetero hydrogen atoms have been located in the difference
Fourier map and were refined with bond lengths restraints.
2 3
S
a
ꢀ1
ning rate of 0.21° min . The SEM–EDS analyses were carried out
using a SIRION FESEM instrument. FESEM images for the samples
were carried out by Hitachi S-4800 scanning electron microscopy.
TEM analysis were carried out by TEM Techni.
Crystal data:
38
C H
66Bi
2
N
6
O
8
S
12
,
M = 1537.64, triclinic, P 1ꢀ ,
= 102.3288
a = 8.82520(10) Å, b = 11.5573(2) Å, c = 15.2345(2) Å,
a
3
(
9), b = 101.2230(10),
c
= 107.6689(7), V = 1389.09(3) Å , Z = 1,
2
2 4 2 3
.2. Synthesis of [Bi(HOCH(CH ) NCS ) ] (1)
ꢀ3
D
0
6
wR
calc = 1.838 mg m
,
F(000) = 758, crystal size 0.25 ꢁ 0.20 ꢁ
.05 mm, reflections collected 19089, independent reflections
319 [Rint = 0.0903], final indices [I > 2 (I)] = 0.0453
= 0.1118, R indices (all data) R = 0.0484, wR = 0.1134, GOF
.051, largest difference peak and hole 3.004 and ꢀ4.330 e Å
4
-hydroxypiperidine (0.303 g, 3 mmol) was dissolved in 15 mL
r
R
1
of anhydrous THF and to it was added NaOH (0.120 g, 3 mmol) dis-
solved in 0.5 mL of water. The mixture was stirred for 10 min and
then CS (0.273 g, 3.6 mmol) was added. The mixture was stirred
2
for an additional 30 min until the color of the solution became
yellow. To the resulting mixture bismuth nitrate pentahydrate
2
1
2
ꢀ3
1
.
2.4. Syntheses of Bi2S3
(
0.485 g, 1 mmol) dissolved in methanol (10 mL) was added drop-
wise and the solution was additionally stirred for another 1 h. The
resulting solution was filtered and evaporated at room tempera-
ture to obtain yellow colored crystals of [Bi(HOCH(CH ) NCS ) ].
2 4 2 3
2
.4.1. Synthesis of 1
Decomposition of the precursor complex was performed at
5
50 °C for 6 h in an argon gas atmosphere in a tubular furnace
ꢀ1
(
with a heating rate of 10 °C min ). The obtained product 1 was
S Na
S
washed thrice with de-ionised water (15 mL) and air-dried.
CS2 + NaOH
HO
N
HO
NH
THF + H O
2
2.4.2. Synthesis of 1a
In solvothermal decomposition the precursor complex was dis-
solved in ethylene glycol (15 mL) and heated to 250 °C under argon
atmosphere to obtain bismuth sulfide 1a.
1
/3 Bi(NO ) .5H O in MeOH
3 3 2
2.4.3. Synthesis of 1b
OH
In a capping agent mediated synthesis the precursor (0.200 g)
was added to ODA (n-octadecylamine, 2.330 g) at 75 °C under
nitrogen atmosphere. The reaction mixture was heated up to
2
00 °C with mild stirring for 3 h. After 3 h, it was cooled to 90 °C
N
N
and then ethanol (50 mL) and toluene (15 mL) solvent mixture
was added. The solid powder 1b was isolated after centrifugation
followed by drying under vacuum.
S
Bi
S
S
S
S
S
N
2.4.4. Synthesis of 1c
The precursor (0.200 g) was added to DDT (dodecanethiol,
.14 mL) at room temperature under nitrogen atmosphere. Then
HO
2
the reaction mixture was heated at 160–170 °C with gentle stirring
for 3 h. The precursor started decomposing at lower temperature in
presence of the capping agent as compared to solid state. At the
end of decomposition the solid product was washed with ethanol
OH
1
(
4 ꢁ 25 mL) followed by washing with diethyl ether (30 mL) and
Scheme 1. Synthesis of the complex 1.
finally centrifuged to collect 1c which was dried under vacuum.