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

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.

The title compound, C 10 H 13 N 3 S 2 , was obtained from a condensation reaction of methyl dithiocarbazate and 4aminoacetophenone. 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-HÁ Á Á interactions and N-HÁ Á ÁS hydrogen bonding are present in the crystal structure.

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 structurebioactivity 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 sp 2 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).

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.

Refinement
H atoms bonded to N atoms were located in a difference Fourier map and refined as riding in their as-found relative positions with U iso (H) = 1.2U eq (N). Methyl H atoms were placed in calculated positions with C-H = 0.96 Å and torsion angles were supplementary materials sup-2 refined to fit the electron density, U iso (H) = 1.5U eq (C). Aromatic H atoms were placed in calculated positions with C-H = 0.93 Å and refined in riding mode with U iso (H) = 1.2U eq (C). Fig. 1. The molecular structure of the title compound with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).  as those based on F, and R-factors based on ALL data will be even larger.