Methyl 3-[(E)-1-(4-amino­phen­yl)ethyl­idene]dithio­carbazate

Shang Shan; Shan-Heng Wang; Yu-Liang Tian; Wen-Long Wang; Ying-Li Xu

doi:10.1107/S160053680801283X

. 2008 May 7;64(Pt 6):o1015. doi: 10.1107/S160053680801283X

Methyl 3-[(E)-1-(4-aminophenyl)ethylidene]dithiocarbazate

Shang Shan ^a,^*, Shan-Heng Wang ^a, Yu-Liang Tian ^a, Wen-Long Wang ^a, Ying-Li Xu ^a

PMCID: PMC2961396 PMID: 21202540

Abstract

The title compound, C₁₀H₁₃N₃S₂, was obtained from a condensation reaction of methyl dithiocarbazate and 4-aminoacetophenone. In the crystal structure, the nearly planar molecule assumes an E configuration, the benzene ring and dithiocarbazate group being located on opposite sides of the N=C bond. C—H⋯π interactions and N—H⋯S hydrogen bonding are present in the crystal structure.

Related literature

For general background, see: Okabe et al. (1993 ▶); Shan et al. (2003 ▶); Jiang (2007 ▶). For related structures, see: Shan et al. (2006 ▶); Zhang et al. (2005 ▶). For synthesis, see: Hu et al. (2001 ▶).

Experimental

Crystal data

C₁₀H₁₃N₃S₂
M _r = 239.35
Monoclinic,
a = 10.8247 (12) Å
b = 5.3673 (8) Å
c = 20.4549 (14) Å
β = 94.756 (12)°
V = 1184.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 295 (2) K
0.32 × 0.22 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.870, T _max = 0.926
10489 measured reflections
2682 independent reflections
1867 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.124
S = 1.07
2682 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.35 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 datablocks I, global. DOI: 10.1107/S160053680801283X/om2229sup1.cif

e-64-o1015-sup1.cif^{(16.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680801283X/om2229Isup2.hkl

e-64-o1015-Isup2.hkl^{(129KB, hkl)}

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
N1—H1A⋯S2ⁱ	0.90	2.83	3.722 (3)	170
N3—H3N⋯S2ⁱⁱ	0.94	2.59	3.483 (2)	159
C10—H10A⋯Cgⁱⁱⁱ	0.96	2.80	3.538 (3)	134

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg is the centroid of the benzene ring.

Acknowledgments

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

supplementary crystallographic information

Comment

As some phenylhydrazone derivatives have been shown to be potential DNA-damaging or mutagenic agents (Okabe et al., 1993), a series of new phenylhydrazone derivatives has been synthesized in our laboratory in past years, and several crystal structures of phenylhydrazone compounds have been determined by X-ray diffraction in order to research their structure-bioactivity relationship (Shan et al., 2003). Recent investigation discovered that sulfur-containing hydrazone compounds are benefit to promote the bioactivities of hydrazone (Jiang, 2007). As part of our ongoing investigation on hydrazone compounds, the title compound with dithiocarbazate component has recently been prepared and its crystal structure is reported here.

The structure of the title compound is shown in Fig. 1. The N2—C7 bond distance of 1.281 (3) Å indicates a typical C=N double bond. The molecule adopts an E configuration about the C=N double bond. The molecule has a nearly planar structure. The C8 atom is well co-planar with the benzene ring with a small atomic deviation of 0.028 (4) Å from the phenylmethylene mean plane. The dithiocarbazate moiety is slightly twisted to the phenylmethylene plane with a dihedral angle of 13.4 (1)°. The shorter N3—C9 bond distance of 1.345 (3) Å implies the N3 atom involved in the electron delocalization in the dithiocarbazate moiety.

It is notable that the N3—C9—S1 bond angle of 113.26 (15)° is much smaller than 120° expected for a sp² hybrid C atom and also much smaller than the corresponding N3—C9—S2 bond angle of 121.66 (16)°, which is similar to that found in related structures reported previously (Shan et al., 2006; Zhang et al., 2005).

Intermolecular C—H···π interaction is observed between C10-methyl group and the benzene ring of the adjacent molecule (Fig. 2), C10—H10a—Cgⁱ angle being 134° and C10···Cgⁱ and H10a···Cgⁱ separations being 3.538 (3) and 2.80 Å, respectively [where Cg is the centroid of the benzene ring and symmetry code (i) = 1 - x,1 - y,1 - z]. Molecules are also linked by intermolecular C—H···S hydrogen bonding (Table 1) to form the supra-molecular chain.

Experimental

Methyl dithiocarbazate was synthesized in the manner reported previously (Hu et al., 2001). Methyl dithiocarbazate (1.24 g, 10 mmol) and 4-aminoacetophenone (1.35 g, 10 mmol) were dissolved in ethanol (10 ml) and refluxed for 6 h. Yellow crystalline product appeared after cooling to room temperature. They were separated and washed with cold water three times. Single crystals of the title compound were obtained by recrystallization from a 2-propanol solution.