Benzyl (E)-3-(2-bromo-5-meth­oxy­benzyl­idene)dithio­carbazate

Zheng Fan; Yan-Lan Huang; Zhao Wang; Han-Qi Guo; Shang Shan

doi:10.1107/S1600536811042826

. 2011 Oct 22;67(Pt 11):o3015. doi: 10.1107/S1600536811042826

Benzyl (E)-3-(2-bromo-5-methoxybenzylidene)dithiocarbazate

Zheng Fan ^a, Yan-Lan Huang ^b, Zhao Wang ^b, Han-Qi Guo ^b, Shang Shan ^b,^*

PMCID: PMC3247414 PMID: 22220032

Abstract

The title compound, C₁₆H₁₅BrN₂OS₂, was obtained from the condensation reaction of benzyl dithiocarbazate and 2-bromo-5-methoxylbenzaldehyde. In the molecule, the bromomethoxyphenyl ring and dithiocarbazate fragment are located on the opposite sides of the C=N double bond, showing the E conformation. The dithiocarbazate fragment is approximately planar (r.m.s deviation 0.0187 Å); its mean plane is oriented with respect to the bromomethoxyphenyl and phenyl rings at 7.60 (12) and 60.08 (9)°, respectively. In the crystal, inversion dimers linked by pairs of N—H⋯S hydrogen bonds occur. A short Br⋯Br contact of 3.5526 (12) Å is observed in the crystal structure.

Related literature

For the potential application 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. (2008a ▶,b ▶). For the synthesis, see: Hu et al. (2001 ▶).

Experimental

Crystal data

C₁₆H₁₅BrN₂OS₂
M _r = 395.33
Triclinic,
a = 6.260 (3) Å
b = 11.889 (5) Å
c = 12.235 (5) Å
α = 111.931 (5)°
β = 91.725 (4)°
γ = 99.771 (4)°
V = 828.1 (6) Å³
Z = 2
Mo Kα radiation
μ = 2.74 mm⁻¹
T = 294 K
0.32 × 0.28 × 0.19 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.56, T _max = 0.72
5637 measured reflections
2988 independent reflections
2379 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.069
S = 1.02
2988 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.30 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/S1600536811042826/xu5353sup1.cif

e-67-o3015-sup1.cif^{(16.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811042826/xu5353Isup2.hkl

e-67-o3015-Isup2.hkl^{(143.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811042826/xu5353Isup3.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—H2⋯S1ⁱ	0.86	2.56	3.402 (3)	167

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Symmetry code: (i) Inline graphic .

Acknowledgments

The work was supported by the Natural Science Foundation of Zhejiang Province, China (grant 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.

In the molecules, the methoxylphenyl ring and dithiocarbazate fragment are located on the opposite sides of the C═N double bond, showing the E-configuration. The dithiocarbazate fragment is approximately planar [r.m.s deviation 0.0187 Å]; the mean plane of dithiocarbazate is oriented with respect to the methoxylphenyl and phenyl rings at 7.60 (12) and 60.08 (9)°, similar to those found in related structures (Shan et al. 2008a, 2008b). Intermolecular N—H···S hydrogen bonding is observed in the crystal structure (Table 1). The short Br···Brⁱ contact of 3.5526 (12) Å is also present in the crystal structure [symmetry code: (i) 1-x,-y,-z].

Experimental

Benzyl dithiocarbazate was synthesized as described previously (Hu et al., 2001). Benzyl dithiocarbazate (0.40 g, 2 mmol) and 2-bromo-5-methoxybenzaldehyde (0.43 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, 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 colourless single crystals of the title compound.