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.

Related literature

For related literature, see: Pomes Hernandez et al. (1996); Toumi et al. (2007).

Experimental

Crystal data

• C₆H₁₂N₂S₄

• M_r = 240.42

• Monoclinic, C 2/m

• a = 10.683 (2) Å

• b = 7.193 (1) Å

• c = 8.309 (2) Å

• β = 117.66 (2)°

• V = 565.5 (2) ų

• Z = 2

• Mo Kα radiation

• μ = 0.79 mm⁻¹

• T = 298 (2) K

• 0.50 × 0.29 × 0.22 mm

Data collection

• Enraf–Nonius CAD-4 EXPRESS diffractometer

• Absorption correction: ψ scan (North et al., 1968) T_min = 0.79, T_max = 0.84

• 1994 measured reflections

• 885 independent reflections

• 701 reflections with I > 2σ(I)

• R_int = 0.027

• 2 standard reflections frequency: 120 min intensity decay: 2%

Refinement

• R[F² > 2σ(F²)] = 0.032

• wR(F²) = 0.088

• S = 1.06

• 885 reflections

• 37 parameters

• H-atom parameters constrained

• Δρ_max = 0.26 e Å⁻³

• Δρ_min = −0.22 e Å⁻³

Data collection: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Supporting information

S1. Comment

The structure is built up of C₆H₁₂N₂S₄ molecules which lie on mirror planes perpendicular to [0 1 0] direction. The molecule is centrosymetric around N1—N1ⁱ bond (i: 1 - x, 1 - y, 1 - z) (figure 1).

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.

Related literature

For related literature, see: Pomes Hernandez et al. (1996); Toumi et al. (2007).

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 ¹H, ¹³C NMR and MS spectra analysis. ¹H NMR (CDCl₃, 300 MHz): 2.45 (s, 6 H, CH₃) and 2.52 (s, 6 H, CH₃). ¹³C NMR (CDCl₃, 75 MHz): 13.8 (CH₃); 15.3 (CH₃) and 163.5 (C=N). MS (EI) (%): m/z = 240 (35 / M+.); 193 (20); (m-MeS); 120 (100); (M-(MeS)2 C=N).

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).

Computing details

Data collection: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); cell refinement: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. Molecular view of the title compound with the atom-labelling scheme. Thermal ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii. [Symmetry code: (i) 1-x, 1-y, 1-z]

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

Crystal data

C6H12N2S4	F(000) = 252
Mr = 240.42	Dx = 1.412 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 25 reflections
a = 10.683 (2) Å	θ = 10–15°
b = 7.193 (1) Å	µ = 0.79 mm^−1
c = 8.309 (2) Å	T = 298 K
β = 117.66 (2)°	Plate, yellow
V = 565.5 (2) Å^3	0.50 × 0.29 × 0.22 mm
Z = 2

Data collection

Enraf–Nonius CAD-4 EXPRESS diffractometer	701 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 30.0°, θmin = 2.8°
ω/2θ scans	h = −14→14
Absorption correction: ψ scan (North et al., 1968)	k = −1→10
Tmin = 0.79, Tmax = 0.84	l = −11→11
1994 measured reflections	2 standard reflections every 120 min
885 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0422P)^2 + 0.172P] where P = (Fo^2 + 2Fc^2)/3
885 reflections	(Δ/σ)max = 0.001
37 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −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 F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.83746 (5)	0.5000	0.78339 (7)	0.0648 (2)
S2	0.58364 (5)	0.5000	0.85038 (7)	0.0605 (2)
N1	0.57245 (14)	0.5000	0.5218 (2)	0.0493 (4)
C1	0.65298 (17)	0.5000	0.6951 (2)	0.0435 (4)
C2	0.7394 (3)	0.5000	1.0710 (3)	0.0695 (7)
H2A	0.7109	0.5000	1.1650	0.104*
H2B	0.7948	0.6090	1.0824	0.104*
C3	0.8586 (3)	0.5000	0.5812 (4)	0.0732 (8)
H3A	0.9574	0.5000	0.6140	0.110*
H3B	0.8148	0.6090	0.5107	0.110*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0283 (2)	0.1133 (6)	0.0464 (3)	0.000	0.01185 (19)	0.000
S2	0.0414 (3)	0.0984 (5)	0.0439 (3)	0.000	0.0217 (2)	0.000
N1	0.0286 (6)	0.0772 (12)	0.0392 (7)	0.000	0.0132 (6)	0.000
C1	0.0302 (7)	0.0566 (11)	0.0413 (8)	0.000	0.0146 (6)	0.000
C2	0.0619 (13)	0.1011 (19)	0.0380 (9)	0.000	0.0168 (9)	0.000
C3	0.0475 (11)	0.116 (2)	0.0656 (13)	0.000	0.0339 (10)	0.000

Geometric parameters (Å, º)

S1—C1	1.7550 (18)	N1—N1^i	1.417 (3)
S1—C3	1.796 (3)	C2—H2A	0.9600
S2—C1	1.7609 (19)	C2—H2B	0.9600
S2—C2	1.816 (2)	C3—H3A	0.9600
N1—C1	1.290 (2)	C3—H3B	0.9600
C1—S1—C3	102.32 (10)	S2—C2—H2A	109.5
C1—S2—C2	103.88 (10)	S2—C2—H2B	109.5
C1—N1—N1^i	111.67 (18)	H2A—C2—H2B	109.5
N1—C1—S1	120.29 (14)	S1—C3—H3A	109.5
N1—C1—S2	121.90 (13)	S1—C3—H3B	109.5
S1—C1—S2	117.81 (10)	H3A—C3—H3B	109.5

Symmetry code: (i) −x+1, −y+1, −z+1.