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access1,2-Bis[bis(methylsulfanyl)methylene]hydrazine
aLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis El Manar, 2092 El Manar I Tunis, Tunisia, and bLaboratoire de Chimie Analytique et Electrochimie, Faculté des Sciences de Tunis, Université de Tunis El Manar, 2092 El Manar I Tunis, Tunisia
*Correspondence e-mail: ahmed.driss@fst.rnu.tn
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.
![[Scheme 1]](dn2348scheme1.gif)
Experimental
Crystal data
|
Data collection: CAD-4 EXPRESS (Duisenberg, 1992![[Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92-96.]](../../../../../../logos/arrows/e_arr.gif "Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92-96.")
; Macíček & Yordanov, 1992); cell 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
contains datablocks I, global. DOI: 10.1107/S1600536808014608/dn2348sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808014608/dn2348Isup2.hkl
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 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).
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).
Data collection: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); cell 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).
![[Figure 1]](./dn2348fig1thm.gif) | 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] |
| 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) Å3 | 0.50 × 0.29 × 0.22 mm |
| Z = 2 |
| 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 on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.088 | H-atom parameters constrained |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.0422P)2 + 0.172P] where P = (Fo2 + 2Fc2)/3 |
| 885 reflections | (Δ/σ)max = 0.001 |
| 37 parameters | Δρmax = 0.26 e Å−3 |
| 0 restraints | Δρmin = −0.22 e Å−3 |
| C6H12N2S4 | V = 565.5 (2) Å3 |
| Mr = 240.42 | Z = 2 |
| Monoclinic, C2/m | Mo Kα radiation |
| a = 10.683 (2) Å | µ = 0.79 mm−1 |
| b = 7.193 (1) Å | T = 298 K |
| c = 8.309 (2) Å | 0.50 × 0.29 × 0.22 mm |
| β = 117.66 (2)° |
| Enraf–Nonius CAD-4 EXPRESS diffractometer | 701 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.027 |
| Tmin = 0.79, Tmax = 0.84 | 2 standard reflections every 120 min |
| 1994 measured reflections | intensity decay: 2% |
| 885 independent reflections |
| R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
| wR(F2) = 0.088 | H-atom parameters constrained |
| S = 1.06 | Δρmax = 0.26 e Å−3 |
| 885 reflections | Δρmin = −0.22 e Å−3 |
| 37 parameters |
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. |
| 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* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| 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 |
| S1—C1 | 1.7550 (18) | N1—N1i | 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—N1i | 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. |
Experimental details
| Crystal data | |
| Chemical formula | C6H12N2S4 |
| Mr | 240.42 |
| Crystal system, space group | Monoclinic, C2/m |
| Temperature (K) | 298 |
| a, b, c (Å) | 10.683 (2), 7.193 (1), 8.309 (2) |
| β (°) | 117.66 (2) |
| V (Å3) | 565.5 (2) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.79 |
| Crystal size (mm) | 0.50 × 0.29 × 0.22 |
| Data collection | |
| Diffractometer | Enraf–Nonius CAD-4 EXPRESS diffractometer |
| Absorption correction | ψ scan (North et al., 1968) |
| Tmin, Tmax | 0.79, 0.84 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 1994, 885, 701 |
| Rint | 0.027 |
| (sin θ/λ)max (Å−1) | 0.703 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.088, 1.06 |
| No. of reflections | 885 |
| No. of parameters | 37 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.26, −0.22 |
Computer programs: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
References
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. Google Scholar
Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92–96. CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Macíček, J. & Yordanov, A. (1992). J. Appl. Cryst. 25, 73–80. CrossRef Web of Science IUCr Journals Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
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. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Toumi, M., Ben Amor, F., Raouafi, N., Bordeau, M., Driss, A. & Boujlel, K. (2007). Acta Cryst. E63, o2735. Web of Science CSD CrossRef IUCr Journals Google Scholar
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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.