Benzyl (E)-3-(2-methyl­benzyl­idene)dithio­carbazate

Shang Shan; Zhao Wang; Yan-Lan Huang; Han-Qi Guo; Deng-Feng Li

doi:10.1107/S1600536811033113

. 2011 Aug 27;67(Pt 9):o2497. doi: 10.1107/S1600536811033113

Benzyl (E)-3-(2-methylbenzylidene)dithiocarbazate

Shang Shan ^a,^*, Zhao Wang ^a, Yan-Lan Huang ^a, Han-Qi Guo ^a, Deng-Feng Li ^a

PMCID: PMC3200894 PMID: 22059047

Abstract

The title compound, C₁₆H₁₆N₂S₂, was obtained from the condensation reaction of benzyl dithiocarbazate and 2-methylbenzaldehyde. The asymmetric unit contains two independent molecules. In both molecules, the methylphenyl ring and the dithiocarbazate fragment are located on opposite sides of the C=N bond, showing an E conformation. In each molecule, the dithiocarbazate fragment is approximately planar, the r.m.s deviations being 0.018 and 0.025 Å. The mean plane of dithiocarbazate group is oriented at dihedral angles of 7.9 (3) and 68.24 (12)°, respectively, to the methylphenyl and phenyl rings in one molecule, while the corresponding angles in the other molecule are 10.9 (3) and 69.76 (16)°. Intermolecular N—H⋯S hydrogen bonding occurs in the crystal structure to generate inversion dimers for both molecules.

Related literature

For potential applications of hydrazone and its derivatives in the biological field, see: Okabe et al. (1993 ▶); Hu et al. (2001 ▶). For related structures, see: Shan et al. (2006 ▶, 2008a ▶,b ▶, 2011 ▶). For the synthesis, see: Hu et al. (2001 ▶).

Experimental

Crystal data

C₁₆H₁₆N₂S₂
M _r = 300.43
Monoclinic,
a = 21.976 (7) Å
b = 6.126 (3) Å
c = 23.099 (6) Å
β = 90.840 (4)°
V = 3109 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 294 K
0.29 × 0.23 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.85, T _max = 0.93
11281 measured reflections
5596 independent reflections
2739 reflections with I > 2σ(I)
R _int = 0.055

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.162
S = 1.02
5596 reflections
363 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO (Rigaku, 1998 ▶); data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811033113/xu5276sup1.cif

e-67-o2497-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811033113/xu5276Isup2.hkl

e-67-o2497-Isup2.hkl^{(268.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811033113/xu5276Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯S1ⁱ	0.86	2.56	3.400 (4)	165
N4—H4N⋯S3ⁱⁱ	0.86	2.77	3.577 (4)	157

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The work was supported by the Natural Science Foundation of Zhejiang Province, China (No. M203027).

supplementary crystallographic information

Comment

Hydrazone and its derivatives have shown the potential application in the biological field (Okabe et al., 1993; Hu et al., 2001). As part of the ongoing investigation on anti-cancer compounds, the title compound has recently been prepared in our laboratory and its crystal structure is presented here.

The asymmetric unit of the title compound contains two independent molecules. In both molecules, the methylphenyl ring and dithiocarbazate fragment are located on the opposite sides of the C═N bond, showing the E-configuration. This agrees with those found in the structures reported previously (Shan et al., 2006; Shan et al., 2008a,b). In each molecule, the dithiocarbazate fragment is approximately planar, the r.m.s deviation being 0.0177 and 0.0248 Å, respectively. The mean plane of dithiocarbazate is oriented with respect to the methylphenyl and phenyl rings at 7.9 (3) and 68.24 (12)° in the C1-containing molecule; while the corresponding angles are 10.9 (3) and 69.76 (16)° in the other molecule.

Intermolecular N—H···S hydrogen bonding occurs in the crystal structure (Table 1).

Experimental

Benzyl dithiocarbazate was synthesized as described previously (Hu et al., 2001). Benzyl dithiocarbazate (0.4 g, 2 mmol) and 2-methylbenzaldehyde (0.24 g, 2 mmol) were dissolved in ethanol (20 ml), then acetic acid (0.2 ml) was added to the ethanol solution with stirring. The mixture solution was refluxed for 6 h. After cooling to room temperature, yellow microcrystals appeared. The microcrystals were separated from the solution and washed with cold water three times. Recrystallization was performed twice with absolute methanol to obtain single crystals of the title compound.