1,2-Bis[bis(methylsulfanyl)methylene]hydrazine

The title compound, C6H12N2S4, was obtained as a by-product (8%) during the reaction of the electrogenerated cyanomethyl anion with phenylamine, carbon disulfide and methyl iodide. The molecule, with the exception of 8 H atoms, lies on a crystallographic mirror plane and is arranged around an inversion centre located at the mid-point of the N—N bond.

The title compound, C 6 H 12 N 2 S 4 , was obtained as a by-product (8%) during the reaction of the electrogenerated cyanomethyl anion with phenylamine, carbon disulfide and methyl iodide. The molecule, with the exception of 8 H atoms, lies on a crystallographic mirror plane and is arranged around an inversion centre located at the mid-point of the N-N bond.

S1. Comment
The structure is built up of C 6 H 12 N 2 S 4 molecules which lie on mirror planes perpendicular to [0 1 0] direction. The The asymetric unit is built up by a nitrogen atom N1 bonded to C1 carbon which is bonded to sulfur atoms S1 and S2, each of them is bonded to a carbon atom. The values of the bond distance C1=N1 (1.283 Å), the bond distance average C -S (1.782 (3) Å), the angle S1C1S2 (117.6 (1)°) and the angles average CSC (103 (1)°) agree with those found in compounds having such bonds (Pomes Hernandez et al., 1996;Toumi et al., 2007). The deviations of H1 and H3 atoms from the plane of the molecule are 0.79 (2)Å and 0.71 (2)Å respectively.

S2. Experimental
The title compound was obtained from the electrolysis of a mixture of acetonitrile (ACN) (70 ml) and hexamethylphosphorotriamide (HMPT) (6 ml), under galvanostatic conditions (I = 105 mA, Q = 1,2 F/mol), in the presence of tetraethylammonium hexafluorophosphate (TEAPF6) (350 mg) as supporting electrolyte. At the end of the electrolysis, the hydrazone (diarylhydrazone) was added and the solution was kept under continuous stirring for one hour, the carbon disulfide was added (20 mmol) after 15 minutes of stirring and finally the methyl iodide was introduced and the solution was kept under stirring over night. After the removal of acetonitrile under reduced pressure, the residue was quenched with water and extracted with diethyl ether. The resulting product was chromatographed on silica gel (mesh 60, ethyl acetate / cyclohexane 1 / 9) to afford a pure product (yield 8%). Crystals suitable for X-ray analysis were grown by slow evaporation of dichloromethane solution.
The title compound was characterized by 1 H, 13 C NMR and MS spectra analysis. 1

S3. Refinement
All H atoms attached to C atoms were fixed geometrically and treated as riding with C-H = 0.96 Å (methyl) with U iso (H) = 1.5U eq (C).   where P = (F o 2 + 2F c 2 )/3 (Δ/σ) max = 0.001 Δρ max = 0.26 e Å −3 Δρ min = −0.22 e Å −3 Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.