Benzyl 3-[(E)-2-nitro­benzyl­idene]dithio­carbazate

Shang Shan; Yan-Lan Huang; Han-Qi Guo; Deng-Feng Li; Jian Sun

doi:10.1107/S1600536811028686

. 2011 Jul 23;67(Pt 8):o2107. doi: 10.1107/S1600536811028686

Benzyl 3-[(E)-2-nitrobenzylidene]dithiocarbazate

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

PMCID: PMC3213549 PMID: 22091126

Abstract

The title compound, C₁₅H₁₃N₃O₂S₂, was obtained from a condensation reaction of benzyl dithiocarbazate and 2-nitrobenzaldehyde. In the molecule, the nearly planar dithiocarbazate fragment [r.m.s deviation = 0.0264 Å] is oriented at dihedral angles of 7.25 (17) and 74.09 (9)°with respect to the two benzene rings. The nitro group is twisted by a dihedral angle of 22.4 (7)° to the attached benzene ring. The nitrobenzene ring and dithiocarbazate fragment are located on the opposite sides of the C=N bond, showing an E configuration. In the crystal, molecules are linked via intermolecular N—H⋯S hydrogen bonds, forming centrosymmetric supramolecular dimers. Weak C—H⋯π interaction is also observed in the crystal structure.

Related literature

For 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

C₁₅H₁₃N₃O₂S₂
M _r = 331.40
Monoclinic,
a = 4.673 (2) Å
b = 28.498 (6) Å
c = 11.735 (5) Å
β = 94.070 (4)°
V = 1558.8 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 294 K
0.38 × 0.25 × 0.23 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.87, T _max = 0.94
6957 measured reflections
2814 independent reflections
1925 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.147
S = 1.05
2814 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; 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/S1600536811028686/xu5268sup1.cif

e-67-o2107-sup1.cif^{(16.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811028686/xu5268Isup2.hkl

e-67-o2107-Isup2.hkl^{(135.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811028686/xu5268Isup3.cml

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

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

Cg is the centroid of the C10–C15 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1ⁱ	0.86	2.51	3.359 (3)	171
C9—H9B⋯Cgⁱⁱ	0.97	2.50	3.410 (4)	156

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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 molecular structure of the title compound is shown in Fig. 1. In the molecule the nearly planar dithiocarbazate fragment [r.m.s deviation 0.0264 Å] is oriented with respect to the two benzene rings at 7.25 (17) and 74.09 (9)°, respectively. The nitro group is twisted to the attached-benzene ring with a dihedral angle of 22.4 (7)°. The N1—C7 bond length of 1.272 (4) Å indicates a typical C═N double bonds. The nitrobenzene ring and dithiocarbazate fragment are located on the opposite positions of the C═N bonds, showing the E-configuration, which agrees with those found in related compounds (Shan et al., 2006; Shan et al., 2008a,b); Shan et al. 2011). In the crystal the molecules are linked to each other via intermolecular N—H···S hydrogen bonding to form the centro-symmetric supramolecular dimer (Table 1). Weak C—H···π interaction is also observed in the crystal structure.

Experimental

Benzyl dithiocarbazate was synthesized as described previously (Hu et al., 2001). Benzyl dithiocarbazate (0.4 g, 2 mmol) and 2-nitrobenzaldehyde (0.3 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.