7
0
R. Chauhan et al. / Inorganica Chimica Acta 415 (2014) 69–74
+
À
to the best of our knowledge and findings, [Ni(dppe)dtc] X spe-
cies have never been explored as possible single-source precursor
for the nickel sulfides.
With these viewpoints and in the quest for new precursors for
the nickel sulfides having different morphologies herein we wish
to report the synthesis, characterization and thermal decomposi-
(C–S). Anal. Calc. for C33
2 6 3 2
H37Cl F NNiOP S : C, 45.32; H, 4.31; N,
1.62; S, 7.42. Found: C, 45.92; H, 4.34; N, 1.69; S, 7.52%.
113 cm S mol in 10 M dichloromethane solution.
K
M
2
À1
À3
+
[Ni{S
81%); m.p. 231 °C. H NMR (CDCl
5.32 (s, 1H, –OH), 3.84 (s, 2H, –CHax), 3.65 (s, 2H, –CHeq), 2.12
(br. s, 4H, –CH –CH –), 2.06 (s, 2H, –CHax) 1.92 (s, 2H, –CHeq.),
1.79 (s, 1H, –CHax). C NMR (CDCl
138.2, 134.2, 132.4, 129.8, 129.5 (C
2
CN(CH
2
)
4
CHOH)}(dppe)] BPh
4
ÁCH
2
Cl
2
(2) (0.840 g, yield
1
3
, d): 7.76–7.16 (m, 40H, C
6 5
H
),
tion products of the heteroleptic complex cation [Ni{S
2
CN(CH
2
)
4
2
2
+
À
À
13
CHOH)}(dppe)] with different counter anions viz. PF
6
, BPh
4
3
, d): 199.5 (–NCS
), 64.8, 47.9, 33.8 (piper-
P NMR (CDCl , d): 62.04 (dppe).
2
), 140.1,
À
and BF
4
.
6 5
H
3
1
dine), 25.6 (–CH
2 2
–CH –).
3
À1
m
max(KBr)/cm 3435 (–OH), 1435 (C@N), 1103 (C–S). Anal. Calc.
2
. Experimental
2 2 2
for C57H57BCl NNiOP S : C, 65.92; H, 5.53; N, 1.35; S, 6.18. Found:
2
À1
À3
C, 66.01; H, 5.58; N, 1.46; S, 6.48%.
K
M
110 cm S mol in 10
M
2.1. Materials and physical measurements
dichloromethane solution.
+
[
Ni{S
2
CN(CH
2
)
4
CHOH)}(dppe)] BF
4
.CH
, d): 7.55–7.23 (m, 20H, C
.28 (s, 1H, –OH), 3.84 (s, 2H, –CHax), 3.63 (s, 2H, –CHeq), 2.02
–CH –), 1.99 (s, 2H, –CHax) 1.83 (s, 2H, –CHeq.),
2
Cl
2
(3) (0.563 g, yield
All the synthetic manipulations were performed under ambient
atmosphere. The solvents were dried and distilled before use by
1
7
5
(
1
1
0%); m.p. 241 °C. H NMR (CDCl
3
6 5
H
),
1
13
31
following standard procedures. H, C and P NMR spectra were
recorded on JEOL AL300 FTNMR spectrophotometers. Chemical
shifts were reported in parts per million using TMS as internal
br. s, 4H, –CH
2
2
13
3 2
.73 (s, 1H, –CHax). C NMR (CDCl , d): 199.8 (–NCS ), 138.2,
32.4, 129.5 (P–C
6
5
H ), 64.8, 47.9, 33.8 (piperdine), 25.6
standard for H and C NMR and phosphoric acid for 31P NMR.
Elemental analysis was performed on Exeter analytical Inc. ‘‘Model
CE-440 CHN analyser’’. The structural characterization of the nickel
sulfide were done using X-ray diffraction (XRD) measurements
using Bruker AXS D8 Discover X-ray diffractometer, with Ni-
1
13
31
À1
(
–CH
2
–CH
2
–). P NMR (CDCl
3
, d): 63.67.
m
max(KBr)/cm
3403
(
–OH), 1434 (C@N), 1081 (C–S). Anal. Calc. for C33
H37BCl
2
F
4
NNiOP2-
2
S : C, 49.17; H, 4.63; N, 1.74; S, 7.96. Found: C, 49.83; H, 4.68; N,
2
À1
À3
1
.86; S, 8.10%.
M
K = 115 cm S mol in 10 M dichloromethane
solution.
1
filtered Cu Ka radiation (k = 1.5405 Å). Small quantities of the
decomposed products were dispersed in ethanol by sonicating
for about 3 min. 5 mL of the suspension was placed on copper grids
using a microliter pipette for SEM measurements that was carried
out using a Hitachi S-4800 scanning electron microscope. For
UV–Vis and photoluminescence measurements the nickel sulfides
were dispersed in ethanol by sonicating for about 3 min. The
UV–Vis and photoluminescence spectra for the complex precursors
in dichloromethane solution and the obtained nickel sulfides by
thermal decomposition of precursors were obtained using
Shimadzu UV–Vis–NIR spectrophotometer (Model UV-3600) and
Shimadzu (RF-5301 PC) spectrophotometer, respectively. The
2
.3. Preparation of nickel sulfides
The decomposition of precursor complex salts 1, 2 and 3 were
performed at 500 °C for 5 h in argon gas atmosphere in tubular
furnace (with heating rate of 10 °C min ). The obtained nickel
sulfides were washed thrice with de-ionised water (15 mL) and
air-dried.
À1
2.4. X-ray crystallography
precursor [Ni(dppe)Cl
2
] was prepared in accordance with the
Intensity data for 2 was collected at 150(2) K on a Nonius Kappa
literature procedure [29].
CCD diffractometer system equipped with graphite monochromat-
ed Mo Ka radiation k = 0.71073 Å. The final unit cell determination,
+
À
À
scaling of the data, and corrections for Lorentz and polarization
effects were performed with Denzo-SMN [30]. The structures were
solved by direct methods (SIR97) [31] and refined by a full-matrix
2
.2. Syntheses of [Ni{S
2 2 4 6 4
CN(CH ) CHOH)}(dppe)] X (X = PF (1), BPh
(2), BF (3))
4
2
least-squares procedure based on F [32]. All non-hydrogen atoms
4
-Hydroxypiperidine (0.102 g, 1.01 mmol) was dissolved in
anhydrous THF (10 mL) and to it was added NaOH (0.040 g,
.00 mmol) dissolved in water (0.5 mL). The mixture was stirred
for 10 min and then CS (0.091 g, 1.20 mmol) was added. The
mixture was stirred for additional 30 min until the color of the
solution became yellow. To the yellow-coloured dithiocarbamate
were refined anisotropically; hydrogen atoms were located at cal-
culated positions and refined using a riding model with isotropic
thermal parameters fixed at 1.2 times the Ueq value of the appro-
priate carrier atom.
1
2
Crystal data: C113
a = 9.3157(3) Å, b = 14.5509(5) Å, c = 19.4084(7) Å,
b = 90.936(2),
H
110
B
2
Cl
2
N
2
Ni
2
O
2
P
4
S
4
, M = 1990.09, triclinic, P 1ꢀ ,
= 101.346(2),
c = 91.9370(10) V = 2577.25(15) Å , Z = 1, Dcalc = 1.282
a
solution was added NH
0.684 g, 2.00 mmol)/NH BF
methanol (10 mL) with vigorous stirring. To the resulting mixture
Ni(dppe)Cl (0.528 g, 1.03 mmol) dissolved in dichloromethane
35 mL) was added dropwise and the solution was additionally
4
PF
6
(0.326 g, 2.00 mmol)/NaBPh
4
3
(
4
4
(0.208 g, 1.98 mmol) dissolved in
À3
mg m
,
F(000) = 1042, crystal size 0.30 Â 0.10 Â 0.05 mm,
reflections collected 25741, independent reflections 9291
R(int) = 0.0724], Final indices [I > 2 (I)] R = 0.0704 wR = 0.1585,
R indices (all data) R = 0.1014, wR
on F 1.099, Largest difference peak and hole 1.263 and À0.476 e Å
2
[
r
1
2
(
1
2
= 0.1739, Goodness-of-fit (GOF)
stirred for another 1 h and then vacuum evaporated to dryness.
The residual mass was dissolved in dichloromethane (5 mL) and
filtered through Celite and petroleum ether (50 mL) was added to
precipitate the orange yellow-coloured residue.
2
À3
.
3. Results and discussion
[
Ni{S
4%); m.p. 237 °C. H NMR (CDCl
.30 (s, 1H, –OH), 3.87 (s, 2H, –CHax), 3.68 (s, 2H, –CHeq), 2.09
–CH –), 2.03 (s, 2H, –CHax) 1.87 (s, 2H, –CHeq.),
2
CN(CH
2
)
4
CHOH)}(dppe)]PF
6
ÁCH
2
Cl
2
(1) (0.639 g, yield
1
7
5
(
1
1
3
, d): 7.56–7.26 (m, 20H, C
H
6 5
),
3.1. Synthesis
+
À
À
br. s, 4H, –CH
.73 (s, 1H, –CHax). C NMR (CDCl
32.4, 129.5 (P–C
–CH
2
2
All the three [Ni{S
2
CN(CH
2
)
4
CHOH)}(dppe)] X (X = PF
6
(1),
1
3
3
, d): 199.8 (–NCS
2
), 138.2,
BPh (2), BF (3)) compounds were obtained by addition of stoichi-
4
4
6
H
5
), 64.8, 47.9, 33.8 (piperdine), 25.6
ometric amounts of Ni(dppe)Cl
2
, 4-piperidinoldithiocarbamate and
3
1
À
À
À
À
4
(
2
–CH
2
–). P NMR (CDCl
3
, d): 62.06 (dppe), À142.77 (PF
6
)
the counter anions PF
6
,
BPh
4
,
BF
in THF, methanol and
1
À1
J(PF) 708.71 Hz.
m
max(KBr)/cm 3437 (–OH), 1435 (C@N), 1103
dichloromethane mixture (Scheme 1). All the three compounds