J Chem Crystallogr (2011) 41:980–985
981
used as received without further purification. Infrared
spectra were recorded on Perkin-Elmer 2000 FT-IR spec-
ligand (2) (0.274 g, 1.25 mmol), was added 0.338 g
(1.25 mmol) HgCl in 20 mL of the same solvent to obtain
2
-
1
trometer in the range 370–3600 cm as KBr disc. NMR
spectra were obtained on a Bruker NMR spectrometer.
Proton chemical shifts are reported in parts per million
an immediate precipitation. The reaction mixture was then
stirred for 1 h at room temperature. The pale green product
was filtered, washed with water and dried in vacuo. Sin-
gle crystals suitable for X-ray analysis were obtained by
recrystallizing the product in chloroform/methanol solvent
mixture. Yield: 0.520 g, (yield = 72%), mp = 218 °C.
(
ppm) relative to Me Si. Elemental analyses were performed
4
by using a Fisons elemental analyzer. The ligands were
prepared by modification of a literature procedure [14].
1
H NMR (CDCl ) d = 7.42–7.33 (m, C H –N(C H )),
3
6
5
2
5
Synthesis of Sodium N-methyl-
N-phenyldithiocarbamate (1)
7.28–7.24 (m, C H –N(CH )), 4.16 (q, CH –N(C H )),
6 5 3 2 2 5
1
1.53 (s, CH –N(CH )), 1.26 (t, CH –N(C H )). C NMR
3
3
3
3
2
5
(
CDCl ) d 206.43, 205.84 (CS ), 147.47, 145.26 (C H –N
3
2
6 5
Sodium hydroxide (2 g, 0.05 mol) dissolved in minimum
amount of distilled water was allowed to attain an ice
temperature; to this cold carbon disulphide (3, 0.05 mL)
was added. This was then followed by the addition of
N-methyl aniline (5.44 mL, 0.05 mol). The mixture was
stirred for 2 h while keeping the temperature below 4 °C.
A yellowish-white solid product, which hinders the stirring
process, separated out which was filtered, washed with
ether and finally recrystallized from warm acetone. The
(C H )), 129.66, 128.80, 126.43, 125.34 (C H –N (CH )),
2 5 6 5 3
55.86 (CH -(C H )), 48.93 (CH –N (CH )), 12.26 (CH -
3
2
2
5
3
3
(C H )).
2
5
-
1
Selected IR (KBr), t(cm ): 1459 (C=N), 1280 (C –N),
2
966 (C=S).
Anal. Calc. for C H N S Hg (579.17): C, 35.25; H,
1
7 18 2 4
3.13; N, 4.84; S, 22.14. Found: C, 30.49; H, 2.75; N, 3.97;
S, 20.38.
white solid product was dried under vacuum over CaCl at
2
room temperature giving 8.4 g (yield = 82%) (sodium
N-methyl-N-phenyldithiocarbamate); mp [ 300 °C.
Crystallographic Experimental Section
Data Collection
-
1
Selected IR (KBr), t(cm ): 3444 and 1630 (water),
455 (C=N), 1262 (C –N), 962 (C=S)
1
2
Synthesis of Sodium N-ethyl-N-phenyldithiocarbamate
2)
A yellow crystal with approximate dimensions 0.46 9
3
0.45 9 0.30 mm was selected under oil under ambient
(
conditions and attached to the tip of a MiTeGen Micro-
MountÓ. The crystal was mounted in a stream of cold
nitrogen at 100(2) K and centered in the X-ray beam by
using a video camera. The crystal evaluation and data
collection were performed on a Bruker CCD-1000 dif-
Sodium N-ethyl-N-phenyldithiocarbamate was prepared
using similar procedure for (1) above. A round bottom flask
was cooled in a freezing mixture of common salt and ice.
To this, sodium hydroxide (2 g, 0.05 mol) dissolved in
minimum quantity of distilled water was added followed
by the addition of carbon disulphide (3, 0.05 mL). To this
mixture, N-ethyl aniline (6.44 mL, 0.05 mol) cooled in ice
was added and stirred for 4 h keeping the temperature
below 4 °C. A yellowish-white crystalline product sepa-
rated out and was filtered. The residue was dispersed in
˚
fractometer with Mo-Ka (k = 0.71073 A) radiation and
the diffractometer to crystal distance of 4.9 cm. The initial
cell constants were obtained from three series of scans at
different starting angles. Each series consisted of 20 frames
collected at intervals of 0.3° in a 6° range about with the
exposure time of 10 s per frame. A total of 181 reflections
were obtained. The reflections were successfully indexed
by an automated indexing routine built in the SMART
program. The final cell constants were calculated from a set
of 9907 strong reflections from the actual data collection.
The data were collected by using the full sphere data col-
lection routine to survey the reciprocal space to a resolution
4
0 mL of ether and the white sodium N-ethyl-N-phen-
yldithiocarbamate was isolated from the colourless crys-
talline impurity. The product was rinsed with ether and
dried under vacuum over CaCl at room temperature giving
2
6
.1 g (yield = 56%) white solid, mp = 98–100 °C.
-1
Selected IR (KBr), t(cm ): 3435 and 1637 (water),
453 (C=N), 1261 (C –N), 960 (C=S)
˚
of 0.71 A. A total of 25094 data were harvested by col-
1
2
lecting three sets of frames with 0.25° scans in u with an
exposure time 12 s per frame. These highly redundant
datasets were corrected for Lorentz and polarization
effects. The absorption correction was based on fitting a
function to the empirical transmission surface as sampled
by multiple equivalent measurements [15].
Synthesis of Complex [Hg(S CN(C H )C H ) ]Á
2
2
5
6 5 2
[
Hg(SCN(CH )C H )(SCN(C H )C H )] (3)
3 6 5 2 5 6 5
To a well stirred 20 mL aqueous solution of ligand (1)
0.256 g, 1.25 mmol) and 20 mL aqueous solution of
(
123