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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1217.
Published online 2008 June 7. doi:  10.1107/S160053680801667X
PMCID: PMC2961747

1,2-Bis(1,3-dithiol-2-yl­idene)hydrazine

Abstract

The title mol­ecule, C6H4N2S4, has a crystallographically imposed centre of symmetry located at the mid-point of the N—N single bond. The mol­ecule is essentially planar: the two five-membered rings form a dihedral angle of 0.17 (6)°. The crystal packing exhibits short inter­molecular S(...)S contacts of 3.549 (2) Å.

Related literature

For general background, see: Yoshita et al. (1983 [triangle]); Moore et al., (1998 [triangle]); Taniguchi et al. (2003 [triangle]). For useful properties of related compounds, see: Andreu et al., (2004 [triangle]); Guerin et al. (2002 [triangle]). For the synthesis of the starting material, 2-methyl­thio-1,3-dithiol­ium iodide, see: Challenger et al. (1953 [triangle]).

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Object name is e-64-o1217-scheme1.jpg

Experimental

Crystal data

  • C6H4N2S4
  • M r = 232.35
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1217-efi1.jpg
  • a = 3.9664 (3) Å
  • b = 10.122 (6) Å
  • c = 11.301 (8) Å
  • β = 97.39 (3)°
  • V = 449.9 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.99 mm−1
  • T = 291 (2) K
  • 0.09 × 0.08 × 0.08 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.919, T max = 0.929
  • 4256 measured reflections
  • 1022 independent reflections
  • 935 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.024
  • wR(F 2) = 0.067
  • S = 1.07
  • 1022 reflections
  • 55 parameters
  • H-atom parameters constrained
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Selected interatomic distance (Å)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680801667X/cv2414sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680801667X/cv2414Isup2.hkl

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

Acknowledgments

The authors acknowledge financial support from the National Natural Science Foundation of China (grant No. 20662010), the Specialized Research Fund for the Doctoral Programme of Higher Education (grant No. 20060184001) and the Open Project of the State Key Laboratory of Supra­molecular Structure and Materials, Jilin University.

supplementary crystallographic information

Comment

Within the field of molecular conductors, tetrathiafulvalene and its π-derivatives have played a leading role in the formation of organic charge-transfer complexes (Yoshita et al. 1983; Moore et al., 1998; Taniguchi et al. 2003). One of the important strategies for the molecular design is to incorporate the nitrogen atom instead of carbon atoms to the conjugated spacer to modulate electron-donating properties (Andreu et al., 2004; Guerin et al., 2002). As a π-extended tetrathiafulvalene, we synthesized the title compound by incorporation an azino spacer between two 1,3-dithiole units.

The X-ray structure determination reveals that the title complex, (I) (Fig. 1), crystallizes in the monoclinic space group P21/n space group.There is a half of the molecule in the asymmetric unit, and the inversion center lies on the mid-point of N—N bond. Two five-membered rings make a dihedral angle of 0.17 (6)°. In the absence of classical hydrogen bonds, the crystal packing exhibits short intermolecular S···S contacts of 3.549 (2) Å.

Experimental

2-Methylthio-1,3-dithiolium iodide (Challenger et al., 1953) (0.15 g, 0.54 mmol) and hydrazine monohydrate (0.13 g, 0.27 mmol) were dissovled in acetic acid (10 ml). The reaction mixture was refluxed for 2 h and then cooled to room temperature. The resulting solution was concentrated in vacuo. The yellow solid obtained was subjected to column chromatography (silica gel, dichloromethane) to afford the title compound as a pale yellow solid (0.08 g, 63.8% m.p. 481–483 K). Single crystals suitable for X-ray diffraction were prepared by slow evaporation of an acetone solution at room temperature.

Refinement

H atoms were placed at calculated positions with C—H = 0.93 Å, and refined as riding, with Uiso(H) = 1.2 Ueq(C).

Figures

Fig. 1.
The molecular structure of (I) showing the atom numbering and 30% probalility displacement ellipsoids [symmetry code: (A) 2 - x, 1 - y, 1 - z].

Crystal data

C6H4N2S4F000 = 236
Mr = 232.35Dx = 1.715 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3828 reflections
a = 3.9664 (3) Åθ = 3.6–27.5º
b = 10.122 (6) ŵ = 1.00 mm1
c = 11.301 (8) ÅT = 291 (2) K
β = 97.39 (3)ºBlock, yellow
V = 449.9 (4) Å30.09 × 0.08 × 0.08 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer1022 independent reflections
Radiation source: fine-focus sealed tube935 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 291(2) Kθmax = 27.5º
ω scansθmin = 3.6º
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)h = −4→5
Tmin = 0.919, Tmax = 0.929k = −13→13
4256 measured reflectionsl = −14→14

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.067  w = 1/[σ2(Fo2) + (0.0401P)2 + 0.0828P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1022 reflectionsΔρmax = 0.46 e Å3
55 parametersΔρmin = −0.18 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Experimental. (See detailed section in the paper)
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
C11.0199 (3)0.62381 (14)0.40299 (12)0.0288 (3)
C20.9210 (4)0.87204 (16)0.36541 (15)0.0433 (4)
H20.86680.96070.37320.052*
C31.0268 (5)0.82730 (15)0.26661 (14)0.0410 (4)
H31.04950.88320.20280.049*
N11.0475 (3)0.50484 (12)0.44228 (10)0.0355 (3)
S11.12148 (10)0.66082 (4)0.26068 (3)0.03701 (14)
S20.88557 (10)0.76025 (4)0.48070 (3)0.03796 (14)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0330 (7)0.0293 (6)0.0243 (6)−0.0017 (5)0.0050 (5)0.0016 (5)
C20.0545 (9)0.0273 (7)0.0482 (9)0.0034 (7)0.0067 (7)0.0046 (7)
C30.0528 (9)0.0313 (8)0.0382 (8)−0.0033 (6)0.0040 (7)0.0095 (6)
N10.0512 (8)0.0299 (6)0.0268 (6)0.0005 (5)0.0110 (5)0.0014 (4)
S10.0519 (3)0.0332 (2)0.0278 (2)−0.00120 (15)0.01239 (16)0.00342 (13)
S20.0487 (3)0.0337 (2)0.0333 (2)0.00350 (15)0.01252 (17)−0.00133 (14)

Geometric parameters (Å, °)

C1—N11.283 (2)C2—H20.9300
C1—S11.7480 (17)C3—S11.7296 (19)
C1—S21.7558 (16)C3—H30.9300
C2—C31.322 (2)N1—N1i1.407 (2)
C2—S21.7448 (18)
S1···S2ii3.549 (2)
N1—C1—S1120.00 (11)C2—C3—S1117.41 (12)
N1—C1—S2125.66 (11)C2—C3—H3121.3
S1—C1—S2114.35 (8)S1—C3—H3121.3
C3—C2—S2118.24 (13)C1—N1—N1i111.41 (14)
C3—C2—H2120.9C3—S1—C195.53 (8)
S2—C2—H2120.9C2—S2—C194.47 (9)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1/2, −y+3/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2414).

References

  • Andreu, R., Garin, J., Lopez, C., Orduna, J. & Levillian, E. (2004). Tetrahedron Lett.45, 8211–8214.
  • Challenger, F., Mason, E. A., Holdsworth, E. C. & Emmott, R. (1953). J. Chem. Soc. pp. 292–304.
  • Guerin, D., Lorcy, D., Carlier, R., Los, S. & Piekara-Sady, L. (2002). J. Solid State Chem.168, 590–596.
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Moore, A. J., Bryce, M. R., Batsanov, A. S., Green, A., Howard, J. A. K., Mckervey, M. A., McGuigan, P., Ledoux, I., Orti, E., Viruela, R., Viruela, P. M. & Tarbï, B. J. (1998). J. Mater. Chem.8, 1173–1184.
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalStructure Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Taniguchi, H., Miyashita, M., Uchiyama, K., Satoh, K., Mori, N., Okamoto, H., Miyagawa, K., Kanoda, K., Hedo, M. & Uwatoko, Y. (2003). J. Phys. Soc. Jpn, 72, 468–471.
  • Yoshita, Z., Kawase, T., Awaji, H., Sugimoto, I., Sugimoto, T. & Yoneta, S. (1983). Tetrahedron Lett.24, 3460–3472.

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