2-Sulfanyl­idene-1,3-di­thiolo[4,5-b]pyrazine-5,6-dicarbo­nitrile

Tomura, M.

doi:10.1107/S2414314617010239

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 7| July 2017| x171023

https://doi.org/10.1107/S2414314617010239

Open

access

2-Sulfanylidene-1,3-dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile

Masaaki Tomura ^a ^*

^aInstitute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan
^*Correspondence e-mail: tomura@ims.ac.jp

Edited by M. Weil, Vienna University of Technology, Austria (Received 30 June 2017; accepted 10 July 2017; online 13 July 2017)

In the title compound, C₇N₄S₃, the molecular entity consisting of a 1,3-dithiole-2-thione with a fused pyrazine ring is planar, with an r.m.s. deviation of 0.042 (3) Å from the least-squares plane. In the crystal, molecules are linked via short intermolecular S⋯N contacts [3.251 (4) and 3.308 (3) Å] between the S atom of the thiocarbonyl group and N atoms of the cyano groups.

Keywords: crystal structure; 1,3-dithiole-2-thione; intermolecular S⋯N contacts.

CCDC reference: 1561227

Structure description

Molecules containing an 1,3-dithiolo[4,5-b]pyrazine-2-thione framework are important synthetic precursors of multi-dimensional organic superconductors and conductors. Intermolecular S⋯N and S⋯S contacts involving peripheral S and N atoms may increase the dimensionality in the solid state and suppress metal–insulator transitions (Williams et al., 1992 ; Ishiguro et al., 1998 ). In addition, such contacts may lead to the formation of unique molecular networks which have special functions, such as inclusion properties (Yamashita & Tomura, 1998 ). Fused pyrazine units are expected to extend the π-conjugated system, resulting in decreased Coulombic repulsion (Tomura & Yamashita, 1995 ; Belo et al., 2004 ; Nomura et al., 2009 ), and coordinate to transition metals (Imakubo et al., 2006 ; Rabaça & Almeida, 2010 ; Imakubo & Murayama, 2013 ), constructing organometallic coordination polymers. We report here the molecular and crystal structure of the title compound.

The title compound crystallizes in the space group P2₁2₁2₁ with one molecule in the asymmetric unit. The molecular structure is shown in Fig. 1. The molecular geometry is comparable to that found in the parent thione (2-thioxo-1,3-dithiolo[4,5-b]pyrazine; Rabaça et al., 2013 ), although the parent molecule lies on a mirror plane. The molecular entity of the title compound is planar, with an r.m.s. deviation of 0.042 (3) Å from the least-squares plane. In the crystal, a short intermolecular S⋯N contact [3.251 (4) Å for S1—N4(−x + $[{1\over 2}]$ , −y + 1, z − $[{1\over 2}]$ )] is observed between the S atom of the thiocarbonyl group and the N atom of the cyano group, constructing a zigzag molecular tape network extending along the c axis (Fig. 2). The molecular tapes are linked via short intertape S⋯N interactions [3.308 (3) Å for S1⋯N3(−x − $[{1\over 2}]$ , −y + 1, z − $[{1\over 2}]$ )].

Figure 1
The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
A partial view along the b axis of the crystal packing of the title compound. Dashed lines show the intermolecular S⋯N contacts.

Synthesis and crystallization

According to the literature method of Tomura et al. (1994 ), the title compound was synthesized by the reaction of 2,3-dichloropyrazine-5,6-dicarbonitrile with sodium sulfide and thiophosgene. The details will be reported elsewhere. Decomposition point: 463 K, MS (EI): m/z 236 (M⁺). Orange crystals suitable for X-ray analysis were grown from an acetonitrile solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. One reflection (205) was omitted due to bad agreement between the observed and calculated intensities.

Table 1
Experimental details

Crystal data
Chemical formula	C₇N₄S₃
M_r	236.29
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	6.1657 (15), 7.0875 (19), 20.883 (6)
V (Å³)	912.6 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.77
Crystal size (mm)	0.30 × 0.30 × 0.05

Data collection
Diffractometer	Rigaku/MSC Mercury CCD
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995 )
T_min, T_max	0.825, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8289, 2561, 2314
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.721

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.103, 1.11
No. of reflections	2561
No. of parameters	127
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.35
Absolute structure	Flack x determined using 803 quotients [(I⁺) − (I⁻)]/[(I⁺) + (I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.07 (4)
Computer programs: CrystalClear (Rigaku/MSC, 2006 ), SIR2014 (Burla et al., 2015 ), SHELXL2016 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1561227

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617010239/wm4053sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010239/wm4053Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617010239/wm4053Isup3.cml

checkCIF report

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear (Rigaku/MSC, 2006); data reduction: CrystalClear (Rigaku/MSC, 2006); program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015).

2-Sulfanylidene-1,3-dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile top

Crystal data top

C₇N₄S₃	D_x = 1.720 Mg m⁻³
M_r = 236.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 3015 reflections
a = 6.1657 (15) Å	θ = 2.0–30.7°
b = 7.0875 (19) Å	µ = 0.77 mm⁻¹
c = 20.883 (6) Å	T = 173 K
V = 912.6 (4) Å³	Prism, orange
Z = 4	0.30 × 0.30 × 0.05 mm
F(000) = 472

Data collection top

Rigaku/MSC Mercury CCD diffractometer	2561 independent reflections
Radiation source: Rotating Anode	2314 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.031
Detector resolution: 14.7059 pixels mm^-1	θ_max = 30.8°, θ_min = 2.0°
φ & ω scans	h = −8→6
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −9→8
T_min = 0.825, T_max = 1.000	l = −23→28
8289 measured reflections

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)] = 0.041	w = 1/[σ²(F_o²) + (0.0486P)² + 0.1364P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.103	(Δ/σ)_max < 0.001
S = 1.11	Δρ_max = 0.29 e Å⁻³
2561 reflections	Δρ_min = −0.35 e Å⁻³
127 parameters	Absolute structure: Flack x determined using 803 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.07 (4)

Special details top

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 > 2sigma(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
S1	−0.17153 (16)	0.55587 (14)	−0.06252 (4)	0.0479 (3)
S2	−0.21351 (14)	0.62442 (14)	0.07652 (4)	0.0434 (2)
S3	0.17499 (14)	0.43326 (12)	0.02606 (4)	0.0410 (2)
N1	−0.0522 (4)	0.5875 (4)	0.19453 (13)	0.0339 (6)
N2	0.3228 (4)	0.4055 (4)	0.14587 (13)	0.0334 (6)
N3	0.0894 (5)	0.6018 (5)	0.35380 (15)	0.0451 (7)
N4	0.6025 (5)	0.3496 (4)	0.28648 (16)	0.0445 (7)
C1	−0.0756 (6)	0.5386 (5)	0.00956 (17)	0.0394 (7)
C2	−0.0230 (5)	0.5554 (5)	0.13276 (16)	0.0338 (6)
C3	0.1080 (5)	0.5255 (4)	0.23255 (15)	0.0309 (6)
C4	0.2925 (5)	0.4362 (4)	0.20854 (15)	0.0318 (6)
C5	0.1642 (5)	0.4634 (4)	0.10837 (15)	0.0314 (6)
C6	0.0915 (5)	0.5664 (5)	0.30048 (17)	0.0359 (7)
C7	0.4656 (5)	0.3844 (5)	0.25174 (16)	0.0344 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0596 (6)	0.0427 (5)	0.0414 (5)	−0.0048 (5)	−0.0122 (4)	0.0016 (4)
S2	0.0366 (4)	0.0517 (5)	0.0420 (5)	0.0053 (4)	−0.0011 (3)	0.0079 (4)
S3	0.0506 (5)	0.0391 (4)	0.0334 (4)	0.0080 (4)	0.0024 (3)	−0.0008 (4)
N1	0.0301 (12)	0.0343 (14)	0.0373 (15)	0.0020 (11)	0.0040 (10)	0.0041 (12)
N2	0.0384 (12)	0.0283 (13)	0.0336 (14)	0.0020 (11)	0.0032 (11)	−0.0004 (11)
N3	0.0508 (15)	0.0473 (18)	0.0374 (17)	0.0067 (14)	0.0070 (13)	−0.0006 (14)
N4	0.0460 (15)	0.0421 (18)	0.0456 (18)	0.0097 (13)	−0.0026 (13)	−0.0061 (14)
C1	0.0476 (17)	0.0293 (17)	0.0413 (19)	−0.0061 (14)	−0.0025 (14)	0.0033 (14)
C2	0.0352 (14)	0.0302 (15)	0.0361 (17)	−0.0020 (12)	0.0029 (12)	0.0062 (13)
C3	0.0323 (13)	0.0273 (16)	0.0330 (16)	0.0001 (11)	0.0046 (11)	0.0042 (12)
C4	0.0334 (13)	0.0263 (14)	0.0356 (16)	0.0004 (12)	0.0052 (12)	0.0039 (12)
C5	0.0341 (14)	0.0263 (14)	0.0337 (16)	0.0005 (12)	0.0037 (12)	0.0017 (12)
C6	0.0349 (14)	0.0333 (16)	0.0395 (19)	0.0041 (13)	0.0061 (12)	0.0042 (14)
C7	0.0345 (15)	0.0311 (16)	0.0376 (17)	0.0036 (13)	0.0041 (13)	−0.0022 (14)

Geometric parameters (Å, º) top

S1—C1	1.622 (4)	N2—C4	1.340 (4)
S2—C2	1.732 (3)	N3—C6	1.141 (4)
S2—C1	1.746 (4)	N4—C7	1.140 (4)
S3—C5	1.733 (3)	C2—C5	1.420 (4)
S3—C1	1.750 (4)	C3—C4	1.395 (4)
N1—C2	1.322 (4)	C3—C6	1.452 (5)
N1—C3	1.341 (4)	C4—C7	1.445 (4)
N2—C5	1.319 (4)

S1···N4ⁱ	3.251 (4)	S1···N3ⁱⁱ	3.308 (3)

C2—S2—C1	96.57 (17)	N1—C3—C6	117.5 (3)
C5—S3—C1	96.24 (16)	C4—C3—C6	120.0 (3)
C2—N1—C3	114.9 (3)	N2—C4—C3	122.6 (3)
C5—N2—C4	115.2 (3)	N2—C4—C7	117.7 (3)
S1—C1—S2	122.6 (2)	C3—C4—C7	119.6 (3)
S1—C1—S3	122.5 (2)	N2—C5—C2	122.2 (3)
S2—C1—S3	114.9 (2)	N2—C5—S3	121.5 (2)
N1—C2—C5	122.6 (3)	C2—C5—S3	116.3 (2)
N1—C2—S2	121.4 (2)	N3—C6—C3	176.4 (4)
C5—C2—S2	116.0 (2)	N4—C7—C4	177.7 (4)
N1—C3—C4	122.4 (3)

C2—S2—C1—S1	179.2 (2)	N1—C3—C4—N2	−0.2 (5)
C2—S2—C1—S3	−1.0 (2)	C6—C3—C4—N2	−175.7 (3)
C5—S3—C1—S1	−179.3 (2)	N1—C3—C4—C7	175.8 (3)
C5—S3—C1—S2	1.0 (2)	C6—C3—C4—C7	0.3 (4)
C3—N1—C2—C5	−0.4 (5)	C4—N2—C5—C2	1.3 (4)
C3—N1—C2—S2	179.7 (2)	C4—N2—C5—S3	−179.4 (2)
C1—S2—C2—N1	−179.4 (3)	N1—C2—C5—N2	−0.7 (5)
C1—S2—C2—C5	0.7 (3)	S2—C2—C5—N2	179.2 (2)
C2—N1—C3—C4	0.8 (4)	N1—C2—C5—S3	−180.0 (3)
C2—N1—C3—C6	176.4 (3)	S2—C2—C5—S3	−0.1 (3)
C5—N2—C4—C3	−0.9 (4)	C1—S3—C5—N2	−179.8 (3)
C5—N2—C4—C7	−177.0 (3)	C1—S3—C5—C2	−0.6 (3)

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

Acknowledgements

The author would like to thank the Instrument Center of the Institute for Molecular Science for the X-ray crystallographic analysis.

Funding information

Funding for this research was provided by: Inter-University Research Institute Corporation, National Institutes of Natural Sciences, Institute for Molecular Science.

References

Belo, D., Santos, I. C. & Almeida, M. (2004). Polyhedron, 23, 1351–1359. Web of Science CSD CrossRef CAS Google Scholar
Burla, M. C., Caliandro, R., Carrozzini, B., Cascarano, G. L., Cuocci, C., Giacovazzo, C., Mallamo, M., Mazzone, A. & Polidori, G. (2015). J. Appl. Cryst. 48, 306–309. Web of Science CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Imakubo, T., Kibune, M., Yoshino, H., Shirahata, T. & Yoza, K. (2006). J. Mater. Chem. 16, 4110–4116. Web of Science CSD CrossRef CAS Google Scholar
Imakubo, T. & Murayama, R. (2013). CrystEngComm, 15, 3072–3075. Web of Science CSD CrossRef CAS Google Scholar
Ishiguro, T., Yamaji, K. & Saito, G. (1998). Organic Superconductors, edited by P. Fulde, Springer Series Solid-State Science, Vol. 88. Berlin, Heidelberg: Springer. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Nomura, M., Tsukano, E., Fujita-Takayama, C., Sugiyama, T. & Kajitani, M. (2009). J. Organomet. Chem. 694, 3116–3124. Web of Science CSD CrossRef CAS Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Rabaça, S. & Almeida, M. (2010). Coord. Chem. Rev. 254, 1493–1508. Google Scholar
Rabaça, S., Oliveira, S., Santos, I. C. & Almeida, M. (2013). Tetrahedron Lett. 54, 6635–6639. Google Scholar
Rigaku/MSC (2006). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tomura, M., Tanaka, S. & Yamashita, Y. (1994). Synth. Met. 64, 197–202. CSD CrossRef CAS Web of Science Google Scholar
Tomura, M. & Yamashita, Y. (1995). J. Mater. Chem. 5, 1753–1754. CrossRef CAS Web of Science Google Scholar
Williams, J. M., Ferraro, J. R., Thorn, R. J., Carlson, K. D., Geiser, U., Wang, H. H., Kini, A. M. & Whangbo, M. H. (1992). In Organic Superconductors. Englewood Cliffs, NJ: Prentice Hall. Google Scholar
Yamashita, Y. & Tomura, M. (1998). J. Mater. Chem. 8, 1933–1944. Web of Science CrossRef CAS Google Scholar