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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1132.
Published online 2008 May 21. doi:  10.1107/S1600536808014608
PMCID: PMC2961342

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

Abstract

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 [triangle]); Toumi et al. (2007 [triangle]).

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Object name is e-64-o1132-scheme1.jpg

Experimental

Crystal data

  • C6H12N2S4
  • M r = 240.42
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1132-efi1.jpg
  • a = 10.683 (2) Å
  • b = 7.193 (1) Å
  • c = 8.309 (2) Å
  • β = 117.66 (2)°
  • V = 565.5 (2) Å3
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.088
  • S = 1.06
  • 885 reflections
  • 37 parameters
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.22 e Å−3

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014608/dn2348sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014608/dn2348Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

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.

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).

Refinement

All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.96 Å (methyl) with Uiso(H) = 1.5Ueq(C).

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]

Crystal data

C6H12N2S4F000 = 252
Mr = 240.42Dx = 1.412 Mg m3
Monoclinic, C2/mMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yCell parameters from 25 reflections
a = 10.683 (2) Åθ = 10–15º
b = 7.193 (1) ŵ = 0.79 mm1
c = 8.309 (2) ÅT = 298 (2) K
β = 117.66 (2)ºPlate, yellow
V = 565.5 (2) Å30.50 × 0.29 × 0.22 mm
Z = 2

Data collection

Enraf–Nonius CAD-4 EXPRESS diffractometerRint = 0.027
Radiation source: fine-focus sealed tubeθmax = 30.0º
Monochromator: graphiteθmin = 2.8º
T = 298(2) Kh = −14→14
ω/2θ scansk = −1→10
Absorption correction: ψ scan(North et al., 1968)l = −11→11
Tmin = 0.79, Tmax = 0.842 standard reflections
1994 measured reflections every 120 min
885 independent reflections intensity decay: 2%
701 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.088  w = 1/[σ2(Fo2) + (0.0422P)2 + 0.172P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
885 reflectionsΔρmax = 0.26 e Å3
37 parametersΔρmin = −0.22 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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 (Å2)

xyzUiso*/Ueq
S10.83746 (5)0.50000.78339 (7)0.0648 (2)
S20.58364 (5)0.50000.85038 (7)0.0605 (2)
N10.57245 (14)0.50000.5218 (2)0.0493 (4)
C10.65298 (17)0.50000.6951 (2)0.0435 (4)
C20.7394 (3)0.50001.0710 (3)0.0695 (7)
H2A0.71090.50001.16500.104*
H2B0.79480.60901.08240.104*
C30.8586 (3)0.50000.5812 (4)0.0732 (8)
H3A0.95740.50000.61400.110*
H3B0.81480.60900.51070.110*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0283 (2)0.1133 (6)0.0464 (3)0.0000.01185 (19)0.000
S20.0414 (3)0.0984 (5)0.0439 (3)0.0000.0217 (2)0.000
N10.0286 (6)0.0772 (12)0.0392 (7)0.0000.0132 (6)0.000
C10.0302 (7)0.0566 (11)0.0413 (8)0.0000.0146 (6)0.000
C20.0619 (13)0.1011 (19)0.0380 (9)0.0000.0168 (9)0.000
C30.0475 (11)0.116 (2)0.0656 (13)0.0000.0339 (10)0.000

Geometric parameters (Å, °)

S1—C11.7550 (18)N1—N1i1.417 (3)
S1—C31.796 (3)C2—H2A0.9600
S2—C11.7609 (19)C2—H2B0.9600
S2—C21.816 (2)C3—H3A0.9600
N1—C11.290 (2)C3—H3B0.9600
C1—S1—C3102.32 (10)S2—C2—H2A109.5
C1—S2—C2103.88 (10)S2—C2—H2B109.5
C1—N1—N1i111.67 (18)H2A—C2—H2B109.5
N1—C1—S1120.29 (14)S1—C3—H3A109.5
N1—C1—S2121.90 (13)S1—C3—H3B109.5
S1—C1—S2117.81 (10)H3A—C3—H3B109.5

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2348).

References

  • Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII Report ORNL-6895. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA.
  • Duisenberg, A. J. M. (1992). J. Appl. Cryst.25, 92–96.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Macíček, J. & Yordanov, A. (1992). J. Appl. Cryst.25, 73–80.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Pomes Hernandez, R., Gómez González, A., Rosado Pérez, A., Nápoles Frías, B. M., Toscano, R. A. & Quincoces Suárez, J. (1996). Acta Cryst. C52, 2941–2942.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Toumi, M., Ben Amor, F., Raouafi, N., Bordeau, M., Driss, A. & Boujlel, K. (2007). Acta Cryst. E63, o2735.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography