666
KHAN et al.
Organotin chlorides were purchased from Aldrich.
Synthesis of PhSnCl2L
The preparation of compound (
(1)
The organic solvents like methanol, chloroform,
DMSO, acetone and diethyl ether were purchased
from Merck and dried by standard methods [12].
1) was carried out
at room temperature. 4ꢀmethylꢀ1ꢀpiperidine dithiocarꢀ
boxylic acid (3.0 g, 17.1 mmol) and phenyltintrichloride
(2.82 mL, 17.1 mmol) were added to 100 cm3 of dry
chloroform and stirred for 6 hours. The resulting soluꢀ
tion was kept in open air at temperature for 4–5 days.
After the evaporation of solvent the solid complex was
well air dried and was recrystallized from acetone
petroleum ether 4 : 1 (v/v) mixture. Yield: 72%. m.p.
Xꢀray Crystallography
Xꢀray crystallographic data with graphiteꢀmonoꢀ
chromated Mo
K
radiation ( = 0.71073 Å) were colꢀ
λ
α
lected on a Bruker Smart APEX CCD diffractometer,
with cryocooling to 100 K using an Oxford Cryosysꢀ
tems 700 Series Cryostream Cooler. A semiꢀempirical
absorption correction using equivalents was applied
with SADABS (Bruker (2001). SADABS (Version
2.03a) and SHELXTL (Version 6.12). Bruker AXS
Inc., Madison, Wisconsin, USA) and the structure was
solved by direct methods and refined by a fullꢀmatrix
least squares procedure based on F2 using the
SHELX97 [13]. All other calculations and graphics
were performed with the SHELXTL package (Bruker
(2001). SADABS (Version 2.03a) and SHELXTL
(Version 6.12). Bruker AXS Inc., Madison, Wisconsin,
USA) Program System.
194–196
°
C. Solubility: Acetone, methanol, THF and
DMSO. Elemental analysis data for C13H17NS2Cl2Sn
:
Calcd., %C, 35.40; %H, 3.89; %N, 3.18; %S, 14.54.
(Found) %C, 35.44; %H, 3.92; %N, 3.21; %S, 14.58.
IR (KBr, cm–1): 1218 (
ν
C=S), 427 (
Sn–Cl), 1452 ( C–N), 2875 (
CH3). H NMR (CDCl3, ppm), nJ(1H, H),
ν
Sn–S), 315
(ν
2961 (
Sn–C), 237 (
ν
ν
ν
CH2),
1
1
ν
2.79 (t, 4H, (10.5)), 1.55–1.64 (m, 4H), 1.20–1.34
(m, H), 0.90 (d, 3H, CH3, (6.3)), [7.22–7.33 (m, 5H),
SnPh].13C NMR (CDCl3, ppm), 193.57 (CSS), 54.12
(Cꢀ2,2'), 33.75 (Cꢀ3,3'), 28.78 (Cꢀ4), 21.22 (Cꢀ5,
CH3), [136.91, 133.72, 128.33, 129.76, SnPh].
Synthesis of PhSnClL2
Compound ( ) was synthesized in the same way as
compound ( ). For complexation, (3.0 g, 17.1 mmol)
(2)
Synthesis of 4ꢀMethylꢀ1ꢀpiperidine
2
Dithiocarboxylic Acid (HL
)
1
of 4ꢀmethylꢀ1ꢀpiperidine dithiocarboxylic acid and
(1.41 mL, 8.5 mmol) of phenyltintrichloride were
mixed. It was recrystallized from acetone: petroleum
The ligand was synthesized by the reported method
[11]. 4ꢀMethylꢀ1ꢀpiperdine dithiocarboxylic acid was
prepared by the reaction of 4ꢀmethylpiperdine and
carbon disulfide as given below:
ether 4 : 1 (v/v) mixture. Yield: 69%. m.p. 148 C. Solꢀ
°
ubility: acetone, methanol, THF and DMSO. Eleꢀ
mental analysis data for C20H29N2S4ClSn: Calcd.,
%C, 41.42; %H, 5.04; %N, 4.83; %S, 22.12. (Found)
%C, 41.46; %H, 5.08; %N, 4.87; %S, 22.08. IR (KBr,
S
NH
dry MeOH
6 h stirring
N
C
SH
+ CS2
(KBr, cm–1): 1237 (
C), 232 ( Sn–Cl), 1453 (
2965 (
CH3). H NMR (CDCl3, ppm), nJ(1H, H),
ν
C=S), 432 (
ν
Sn–S), 323 (
ν
Sn–
CH3
ν
ν
C–N), 2868 (
ν
CH2),
CH3
1
1
ν
2.78 (t, 8H, (10.8)), 1.56–1.64 (m, 8H), 1.21–1.35
(m, 2H), 0.90 (d, 6H, CH3, (6.3)), [7.34–7.38 (m,
5H), SnPh].13C NMR (CDCl3, ppm), 196.04 (CSS),
53.36 (Cꢀ2,2'), 33.45 (Cꢀ3,3’), 29.08 (Cꢀ4), 21.84 (Cꢀ
25.0 mL (1.0 mmol) of 4ꢀmethyl piperidine was added
into 100 mL dried methanol, kept in 250 mL two necked
round bottom flask equipped with condenser and magꢀ
netic stirrer. After stirring for 15 min, 15.2 mL (1.0 mmol)
of carbon disulphide was added drop wise. This mixꢀ
ture was stirred at room temperature for 6 hours. The
shining white precipitates formed were filtered
through a whatman filter paper, washed with dried
diethyl ether and were recrystallized from chloroform.
5, CH3), [136.23, 133.45, 128.2, 129.49 4
J[14], SnPh],
Synthesis of (tBu)2SnClL
Compound ( ) was synthesized by the same proceꢀ
. Solubility: acetone, dure used for synthesis of compound ( ). Here (3.0 g,
(3)
3
Yield: 74%. m.p. 163–165
°
C
1
chloroform, methanol and DMSO. Elemental analyꢀ 17.1 mmol) of 4ꢀmethylꢀ1ꢀpiperidine dithiocarboxyꢀ
sis data for C7H13NS2: Calcd., %C, 47.96; %H, 7.47; lic acid and (5.20 g, 17.1 mmol) of ditertiarybutyltin
%N, 7.99; %S, 36.58. (Found) %C, 47.92; %H, 7.51; dichloride as starting materials. It was recrystallized
%N, 8.03; %S, 36.54. IR (KBr, cm–1): 1282 (
2754 ( S–H), 1410 ( C–N), 2856 (
CH3). H NMR (CDCl3, ppm), nJ(1H, H), 2.78 nol, THF and DMSO. Elemental analysis data for
ν
C=S), from acetone: petroleum ether 4 : 1 (v/v) mixture.
ν
ν
ν
CH2), 2949 Yield: 65%. m.p. 123 . Solubility: Acetone, methaꢀ
°
C
1
1
(
ν
(t, 2,2', (12.0)), 1.56–1.81 (m, 3,3'), 1.16–1.28 (m, C15H30NS2ClSn: Calcd., %C, 40.70; %H, 6.83; %N,
4), 0.90 (d, CH3, (6.6)), 1.58 (s, SH). 13C NMR 3.16; %S, 14.49. (Found) %C, 40.74; %H, 6.79; %N,
(
CDCl3, ppm), 178.6 (CSS), 44.74 (Cꢀ2,2'), 30.01 (Cꢀ 3.12; %S, 14.45. IR (KBr, cm–1): 1228 (
ν
C=S), 428 (ν
Sn–Cl), 1452 (ν C–N),
3,3'), 28.28 (Cꢀ4), 21.61 (Cꢀ5, CH3).
Sn–S), 529 (
ν
Sn–C), 262 (
ν
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 5 2012