Benzyl 3-[(E)-(furan-2-yl)methylidene]-2-methyldithiocarbazate

In the title compound, C14H14N2OS2, the furan ring exhibits rotational disorder over two orientations, with an occupancy ratio of 0.508 (7):0.492 (7). The furan and phenyl rings form dihedral angles of 8.2 (6) (major occupancy component), 14.8 (6) (minor occupancy component) and 73.65 (9)°, respectively, with the central residue (C4N2S2), indicating a twisted conformation for the molecule. The methyl group and the thione S atom are syn and the conformation about the imine bond is E. In the crystal, C—H⋯π interactions involving the phenyl ring are observed.

In the title compound, C 14 H 14 N 2 OS 2 , the furan ring exhibits rotational disorder over two orientations, with an occupancy ratio of 0.508 (7):0.492 (7). The furan and phenyl rings form dihedral angles of 8.2 (6) (major occupancy component), 14.8 (6) (minor occupancy component) and 73.65 (9) , respectively, with the central residue (C 4 N 2 S 2 ), indicating a twisted conformation for the molecule. The methyl group and the thione S atom are syn and the conformation about the imine bond is E. In the crystal, C-HÁ Á Á interactions involving the phenyl ring are observed. Mo K radiation = 0.36 mm À1 T = 298 K 0.5 Â 0.5 Â 0.3 mm  Table 1 Hydrogen-bond geometry (Å , ).  The eight atoms of the central residue (S1, S2, N1, N2, C7, C8, C9 and C10) are co-planar having a r.m.s. deviation for the fitted atoms of 0.002 Å. The maximum deviations from this plane are 0.043 (2) Å for the N2 atom and -0.033 (3) Å for the N1 atom. The molecule is twisted, the dihedral angles between the C 4 N 2 S 2 residue and the pendent 2-furanyl and phenyl rings being 14.8 (6) [or 8.22 (6) for the disordered part of the furanyl] and 73.65 (9)° respectively, as found in a similar compound (Shan et al., 2008).

Experimental
Single crystals of the title compound were prepared by following three steps.
Step 1 (Hazari et al., 2012). Synthesis of N-methyl-S-benzyldithiocarbazate. Potassium hydroxide (11.5 g) was dissolved in 60 ml of 90% ethanol and the mixture was cooled down to 273 K in an ice bath. Methyl hydrazine (11.1 ml) was added slowly with mechanical stirring. A solution of CS 2 (12 ml) was added dropwise from a burette with constant stirring over a period of 1 h. During the addition of CS 2 , the temperature of the reaction mixture was not allowed to rise above 279 K. A yellow colour was obtained. After adding carbon disulfide, benzyl chloride (25 ml) was added from a burette dropwise with vigorous mechanical stirring. After complete addition, the mixture was stirred for further 15 min, whereupon shining crystals appeared. The product was separated by filtration, washed with water, recrystallized from ethanol and dried in a vacuum desiccator over silica gel. Yield: 14.20 g. m.p. 373-374 K.
Step 2. Synthesis of the title molecule. A hot solution of furan-2-carbaldehyde (10 mmol) in absolute ethanol (40 ml) was mixed with a hot solution of N-methyl-S-benzyldithiocarbazate (10 mmol) in 40 ml of the same solvent. The mixture was refluxed for 6 h on a water bath. After reducing the volume, an off white product appeared which was filtered off.
This product was washed with ethanol several times and dried in a vacuum desiccator over silica gel Step 3. Crystallization. The product was dissolved in ethanol to which half volume of petroleum ether was added (2:1 v/v, 10 ml ethanol and 5 ml petroleum ether). The solution was left for several days after which crystals of the title compound deposited.

Refinement
All H atoms were placed in idealized positions and allowed to ride on their parent C atoms, with C-H bond lengths fixed to 0.93 (aromatic CH), 0.97 (methylene CH 2 ) or 0.96 Å (methyl CH 3 ). Displacement parameters were taken as U iso (H) = 1.5U eq (C9) for the methyl group and U iso (H) = 1.2U eq (carrier C) otherwise. The furan ring exhibits rotational disorder over two orientations. The occupancies for all sites were fixed to 0.5, since the refined occupancy for each part was very close to that distribution. In order to approximate the expected geometry for both furan groups, their bond lengths were restrained to be identical, with an effective standard deviation of 0.01 Å (command SAME in SHELXL97; Sheldrick, 2008).   Crystal packing for the title compound viewed along a.  Hydrogen-bond geometry (Å, º) Symmetry codes: (i) −x−1, −y, −z+1; (ii) −x+1, −y, −z+2.