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

Li, H.; Su, C.; Li, B.; Chen, T.; Yin, B.

doi:10.1107/S160053680801667X

organic compounds

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Volume 64| Part 7| July 2008| Page o1217

doi:10.1107/S160053680801667X

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

Hong-ai Li,^a Chang Su,^a Bao Li,^b Tie Chen ^a and Bing-zhu Yin ^a ^*

^aKey Laboratory of Organism Functional Factors of Changbai Mountain, Yanbian University, Ministry of Education, Yanji 133002, People's Republic of China, and ^bState Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China
^*Correspondence e-mail: zqcong@ybu.edu.cn

(Received 20 May 2008; accepted 31 May 2008; online 7 June 2008)

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

Experimental

Crystal data

C₆H₄N₂S₄
M_r = 232.35
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.024
wR(F²) = 0.067
S = 1.07
1022 reflections
55 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Selected interatomic distance (Å)

S1⋯S2ⁱ	3.549 (2)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

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].

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

Crystal data top

C₆H₄N₂S₄	F(000) = 236
M_r = 232.35	D_x = 1.715 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3828 reflections
a = 3.9664 (3) Å	θ = 3.6–27.5°
b = 10.122 (6) Å	µ = 1.00 mm⁻¹
c = 11.301 (8) Å	T = 291 K
β = 97.39 (3)°	Block, yellow
V = 449.9 (4) Å³	0.09 × 0.08 × 0.08 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	1022 independent reflections
Radiation source: fine-focus sealed tube	935 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 3.6°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −4→5
T_min = 0.919, T_max = 0.929	k = −13→13
4256 measured reflections	l = −14→14

Refinement top

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.067	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0401P)² + 0.0828P] where P = (F_o² + 2F_c²)/3
1022 reflections	(Δ/σ)_max < 0.001
55 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₆H₄N₂S₄	V = 449.9 (4) Å³
M_r = 232.35	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.9664 (3) Å	µ = 1.00 mm⁻¹
b = 10.122 (6) Å	T = 291 K
c = 11.301 (8) Å	0.09 × 0.08 × 0.08 mm
β = 97.39 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1022 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	935 reflections with I > 2σ(I)
T_min = 0.919, T_max = 0.929	R_int = 0.021
4256 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.067	H-atom parameters constrained
S = 1.07	Δρ_max = 0.46 e Å⁻³
1022 reflections	Δρ_min = −0.18 e Å⁻³
55 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
C1	1.0199 (3)	0.62381 (14)	0.40299 (12)	0.0288 (3)
C2	0.9210 (4)	0.87204 (16)	0.36541 (15)	0.0433 (4)
H2	0.8668	0.9607	0.3732	0.052*
C3	1.0268 (5)	0.82730 (15)	0.26661 (14)	0.0410 (4)
H3	1.0495	0.8832	0.2028	0.049*
N1	1.0475 (3)	0.50484 (12)	0.44228 (10)	0.0355 (3)
S1	1.12148 (10)	0.66082 (4)	0.26068 (3)	0.03701 (14)
S2	0.88557 (10)	0.76025 (4)	0.48070 (3)	0.03796 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0330 (7)	0.0293 (6)	0.0243 (6)	−0.0017 (5)	0.0050 (5)	0.0016 (5)
C2	0.0545 (9)	0.0273 (7)	0.0482 (9)	0.0034 (7)	0.0067 (7)	0.0046 (7)
C3	0.0528 (9)	0.0313 (8)	0.0382 (8)	−0.0033 (6)	0.0040 (7)	0.0095 (6)
N1	0.0512 (8)	0.0299 (6)	0.0268 (6)	0.0005 (5)	0.0110 (5)	0.0014 (4)
S1	0.0519 (3)	0.0332 (2)	0.0278 (2)	−0.00120 (15)	0.01239 (16)	0.00342 (13)
S2	0.0487 (3)	0.0337 (2)	0.0333 (2)	0.00350 (15)	0.01252 (17)	−0.00133 (14)

Geometric parameters (Å, º) top

C1—N1	1.283 (2)	C2—H2	0.9300
C1—S1	1.7480 (17)	C3—S1	1.7296 (19)
C1—S2	1.7558 (16)	C3—H3	0.9300
C2—C3	1.322 (2)	N1—N1ⁱ	1.407 (2)
C2—S2	1.7448 (18)

S1···S2ⁱⁱ	3.549 (2)

N1—C1—S1	120.00 (11)	C2—C3—S1	117.41 (12)
N1—C1—S2	125.66 (11)	C2—C3—H3	121.3
S1—C1—S2	114.35 (8)	S1—C3—H3	121.3
C3—C2—S2	118.24 (13)	C1—N1—N1ⁱ	111.41 (14)
C3—C2—H2	120.9	C3—S1—C1	95.53 (8)
S2—C2—H2	120.9	C2—S2—C1	94.47 (9)

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

Experimental details

Crystal data
Chemical formula	C₆H₄N₂S₄
M_r	232.35
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	3.9664 (3), 10.122 (6), 11.301 (8)
β (°)	97.39 (3)
V (Å³)	449.9 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.00
Crystal size (mm)	0.09 × 0.08 × 0.08

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.919, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	4256, 1022, 935
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.067, 1.07
No. of reflections	1022
No. of parameters	55
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.18

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Selected interatomic distances (Å) top

S1···S2ⁱ

3.549 (2)

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

Acknowledgements

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.

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