J Chem Crystallogr (2011) 41:528–532
529
–CH3); 2.89 (d, 6H, J 45.0 Hz; –N(CH3)2); 5.81 (s, 1H,
–CH). 13C NMR (75.46 MHz, CDCl3): d 26.5 (1C); 162.5
(2C); 94.7 (3C); 162.5 (4C); 137.8 (5C); 169.9 (11C); 135.7
(12C). IR (KBr), m(cm-1): m(N–H): 3281 m; m(C=O, DMF):
1653 s; m(C=N): 1561 s, 1519 s; m(C=C): 1487 s, 1452 s,
1429 m; m(N–N): 1019 m; m(C=S): 770 w; m(Sn–O): 527 w.
CH3
N
N
C
HO
S
N
H
Crystal Structure Determinations and Refinements
X-ray crystallography analysis were carried out using a
KappaCCD diffractometer [11] using graphite-monochro-
Scheme 1 The molecular structure of H2L
˚
mated Mo Ka (k = 0.71073 A) radiation at room temper-
ature. Colorless and orange block crystals of the ligand and
of the complex were mounted on glass fibers with glue.
Diffraction data were collected up to h = 27.5° from both
crystals and the data reductions were performed with Denzo
[12]. The X-ray crystal structures were solved by the heavy
atom method and Direct Methods with SHELXS-97 [13],
and refined with anisotropic atomic displacement by full
matrix least-squares on F2 using SHELXL-97 [13].
Hydrogen atom positions were calculated at idealized
positions and refined isotropic using the riding model con-
straints to their parent atoms. The complex phenyl rings
were refined as rigid groups with fixed C–C bond lengths of
spectra were recorded on a VARIAN MERCURY PLUS
1
spectrometer (7.05 T) operating at 300 MHz for H and at
75.46 MHz for 13C.
Synthesis
All chemical were of reagent grade and were used without
further purification. N4-phenylthiosemicarbazide was pre-
pared from phenyl isothiocyanate and hydrazine monohy-
drate in an anhydrous mixture of ethanol/ether (1:1) with
stirring [10]. The 5-hydroxy-3-methyl-5-phenyl-(N4-phe-
nylthiosemicarbazone)pyrazoline ligand (H2L) was syn-
thesized by refluxing a 1:1 M ratio mixture of benzoyl
acetone and the semicarbazide in methanol. Cooling fol-
lowed by slow evaporation of the solvent produced single
crystals for X-ray study. Its structure is shown in Scheme 1.
H2L: Anal. Calcd for C17H17N3OS (311.40 g/mol): C
65.57, H 5.50, N 13.49, S 10.30%; Found: C 64.93, H 5.21,
N 13.38, S 10.23%, color: yellow, yield: 78%, m.p.:
139–140 °C. 1H NMR (300 MHz, CDCl3): d 2.11 (t, J 0.98;
3H, –CH3); 3.07 (d, J 0.96; 1Ha, –CHaHb); 3.47 (d, J 1.06;
1Hb, –CHaHb); 9.15 (s, 1H, –NH). 13C NMR (75.46 MHz,
CDCl3): d 16.44 (1C), 154.9 (2C), 55.5 (3C), 95.7 (4C);
144.6 (5C); 173.4 (12C); 138.0 (10C). IR (KBr), m(cm-1):
m(O–H): 3459 vs; m(N–H): 3337 vs; m m(C=N–N=C): 1590
vs; m(C=C): 1516 s, 1451 s, 1410 s; m(N–N): 959 m;
m(C=S): 858 m.
˚
1.39 A. Further details of the structure analysis for the
ligand and complex are summarized in Table 1.
Results and Discussion
Crystal Structure of H2L
The ORTEP plot of H2L is shown in Fig. 1 along with the
atom numbering scheme. Selected bond lengths and angles
with their estimated standard deviations are compiled in
Table 2. The structure obtained confirms the cyclization
reaction and the formation of the 5-hydroxy-4,5-dihydro-
pyrazoline derivative. The compound crystallizes in the
centrosymmetric space group Pbca and exhibits two intra-
molecular hydrogen bonds of type O1–H1ÁÁÁS1, with
˚
The complex [Ph2Sn(L)]ÁDMF was obtained by a gen-
eral method. 0.27 g (0.87 mmol) of H2L was dissolved in
10 ml of CHCl3. To this solution were added three drops of
Et3N, followed by the slow addition of 0.30 g (0.87 mmol)
Ph2SnCl2 dissolved in 10 ml of MeOH. The mixture was
stirred at room temperature for 24 h, and the yellow
product was filtered, washed with hexane and dried in air.
Orange single crystals suitable for X-ray crystallography
were obtained by recrystallization from DMF. [Ph2Sn(L)]Á
DMF: Anal. Calcd for C61H57N7O3S2Sn2 (1237.64 g/mol):
C 59.20, H 4.64, N 7.92, S 5.18% Found: C 58.87, H 4.56,
N 7.85, S 5.12%, color: yellow, yield: 67%, m.p.:
distance 3.107(2) A and angle 137° forming a pseudo six-
membered ring, and of type N3–H3ÁÁÁN2 with distance
2.612(2) and angle 108.9° forming a pseudo five-membered
ring, which help in stabilizing the structure. The
˚
N2–C2 = 1.280(3) A double bond length and the C2–C3 =
1.483(3), C3–C4 = 1.536(3), C4–N1 = 1.490(3) and
˚
N1–N2 = 1.406(3) A single bond lengths are very close to
those found in a similar pyrazoline derivative [4]. The
C11–S1 = 1.6770(19) bond length indicates double-bond
nature. As expected, the bond angles of O1–C4–C5 =
112.57(16), C3–C4–N1 = 100.39(15), O1–C4–C3 =
108.34(16) and C5–C4–N1 = 110.91(16)° indicate that the
C4 asymmetric center is sp3 hybridized.
1
160–162 °C. H NMR (300 MHz, CDCl3): d 2.45 (s, 3H,
123