3
80
J Chem Crystallogr (2011) 41:379–385
M
N
Cl
Cl
Cl
Cl
S
C
H
C
S
C
H
C
H
H
N
H
N
N
N
N
HL
Potential biding modelof HL
M
S
S
S
NH
C
NH NH
C
NH
NH
C
N
N
C
S
NH
M
H Q
Potential biding modelof H2 Q
2
2
Fig. 1 The potential binding model of the ligands HL and H Q
Experimental
solution was filtered, and the filtrate was evaporated by
heating until about 30 mL solution was left and then, the
left solution was cooled to room temperature. Four days
later, two kinds of crystals suitable for an X-ray structure
determination were obtained by slowly evaporating an
acetonitrile solution in air, one kind of crystals was green
and anther kind was dark-green. For the green one (yield
87%), Anal. Calcd. for C H Cl N NiS : C, 48.82; H,
Materials and Instrument
Elemental analyses for carbon, hydrogen and nitrogen were
performed by a Perkin-Elmer 240C elemental instrument.
The melting points were determined on a Yanaco MP-500
-
1
melting point apparatus. IR spectra (4000–400 cm ), as
3
2
26
4
8
2
KBr pellets, were recorded on a Nicolet FT-IR spectro-
1
photometer. H NMR spectroscopy (DMSO-d6) were
3.33; N, 14.24. Found: C, 48.68; H, 3.39; N, 14.41. IR
(KBr): t 3430, 1596, 1507, 1432, 1314, 1249, 1191, 1044,
-
1
recorded on Avance Mercury plus-400 instrument with
TMS as an internal standard.
775, 689 cm . For the dark-green one (yield 4%), Anal.
Calcd. for C H Cl N Ni S : C, 47.87; H, 3.35; N, 14.89.
6
0
50
4
16
3 6
Found: C, 47.71; H, 3.24; N, 14.62. IR (KBr): t 3430,
1
596, 1536, 1505, 1433, 1385, 1314, 1249, 1081, 1047,
-
996, 762, 689, 485 cm .
1
Synthesis of the HL and Two Complexes
All chemicals were obtained from a commercial source and
used without further purification.
Structure Determination
The HL was synthesized as follows: 4-phenylthiosemi-
carbazide (8.35 g, 0.05 mol) and 2,6-dichlorobenzaldehyde
The crystal structures of the HL and the complexes 1 and 2
were determined based on data collected on a Bruker Smart
APEX2 CCD diffractometer with graphite-monchromated
(
(
8.75 g, 0.05 mol) were mixed in acetonitrile solution
200 mL) and stirred with refluxing. Eight hour later, light-
˚
Mo-Ka radiation [k = 0.71073 A, T = 296(2) K]. The
yellow solids were observed and then, the reaction was
stopped and the mixture was cooled to room temperature.
The yellow solids were obtained by filtration and dried at
room temperature. Yield: 88%. Mp. 192.0–193.2 °C. Anal.
Calcd. for C H Cl N S: C, 51.86; H, 3.42; N, 12.96.
empirical absorption correction was based on equivalent
reflections, and other possible effects, such as absorption
by the glass fiber, were simultaneously corrected. The
structures of the three compounds were solved by direct
2
1
4
11
2
3
methods and refined by least squares on F . The hydrogen
1
Found: C, 51.68; H, 3.39; N, 12.81. H NMR (400 MHz,
atom positions were fixed geometrically at calculated dis-
tances and allowed to ride on the parent carbon or nitrogen
atoms. All non-hydrogen atoms were anisotropically
refined. The SMART software was used for collecting
frames of data, indexing reflections, and determination of
lattice constants; SAINT-PLUS for integration of intensity
of reflections and scaling; SADABS for absorption cor-
rection; and SHELXTL for space groups and structure
determinations, refinements, graphics, and structure
reporting [17–19].
DMSO): d 2.51 (s, H, -NH), 3.34 (s, H, -NH), 7.17–7.65
(
m, 8H, ArH–), 8.42(s, H, -CH). IR (KBr): t 3450, 3337,
3
124, 2981, 1536, 1505, 1448, 1426, 1268, 1203, 1076,
-
76, 695, 528 cm ; Crystals suitable for an X-ray struc-
1
7
ture determination were obtained by slowly evaporating an
ethanol solution of the compound in air.
The mononuclear Ni(II) complex (1) and trinulclear
Ni(II) complex (2) were then obtained: to a warm solution
of HL (3.24 g, 10.0 mmol) in acetonitrile (40 mL) was
added with stirring NiAc Á4H O (1.25 g, 5.0 mmol) and
2
2
The crystallographic collection and refinement parame-
ters for the three compounds are listed in Table 1.
the mixture was refluxed for 2 h. The yellow–brown
1
23
Wang, Hong Yan
