2,5-Diamino­thio­phene-3,4-dicarbonitrile

Ziegler, C.J.; Nemykin, V.N.

doi:10.1107/S1600536812034678

organic compounds

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Volume 68| Part 9| September 2012| Page o2693

doi:10.1107/S1600536812034678

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2,5-Diaminothiophene-3,4-dicarbonitrile

Christopher J. Ziegler ^a ^* and Victor N. Nemykin ^b

^aDepartment of Chemistry, University of Akron, Akron, OH 44325-3601, USA, and ^bDepartment of Chemistry & Biochemistry, University of Minnesota Duluth, Duluth, MN 55812, USA
^*Correspondence e-mail: ziegler@uakron.edu

(Received 12 July 2012; accepted 3 August 2012; online 11 August 2012)

In the title compound, C₆H₄N₄S, the planar molecule lies across a crystallographic mirror plane. In the crystal, the molecules form centrosymmetric dimers through cyclic amino N—H⋯N hydrogen-bonding associations with cyano N-atom acceptors [graph set R₂²(12)] and these dimers are extended through amine–cyano N—H⋯N associations into a three-dimensional network.

Related literature

For the synthesis of this and related compounds via the reaction of tetracyanoethylene with hydrogen sulfide, see: Cairns et al. (1957 ); Middleton et al. (1958 ); Middleton (1959 ). For the use of this compound as a reagent, see: Nemykin et al. (2012 ). For graph-set analysis, see: Etter et al. (1990 ). For details of the weighting scheme, see: Prince (1982 ); Watkin (1994 ).

Experimental

Crystal data

C₆H₄N₄S
M_r = 164.19
Orthorhombic, P b c n
a = 3.9231 (2) Å
b = 13.8213 (12) Å
c = 12.6465 (11) Å
V = 685.72 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 123 K
0.41 × 0.24 × 0.16 mm

Data collection

Rigaku RAPID II diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.69, T_max = 0.94
2260 measured reflections
783 independent reflections
492 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.116
S = 0.99
769 reflections
51 parameters
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2⋯N2ⁱ	0.87	2.29	3.106 (5)	156
N1—H1⋯N2ⁱⁱ	0.88	2.38	3.196 (5)	153
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: CrystalClear (Rigaku, 2009 ); cell refinement: HKL-2000 (Otwinowski & Minor, 1997 ); data reduction: CrystalClear; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: CAMERON (Watkin et al., 1996 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812034678/zs2223sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812034678/zs2223Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812034678/zs2223Isup3.cml

checkCIF report

Comment top

The synthesis of the title compound 2,5-diamino-3,4-dicyanothiophene, C₆H₄N₄S, and similar compounds has previously been reported (Cairns et al., 1957; Middleton, 1959) and chemical transformations of this compound and its usage in macrocyclic chemistry have also been described (Middleton et al., 1958; Nemykin et al., 20120. In the structure of the title compound the planar molecule lies across a crystallograpic mirror plane (Fig. 1). The C—S bond length is 1.750 (4) Å and the C—C bond distances are unequal [1.358 (5) Å for C1—C2 and 1.458 (7) Å for C2—C2ⁱ [for symmetry code (i): -x+2, y, -z+3/2]. The C—N_amine bond distance [1.358 (5) Å] shows some double-bond character and the C2—C3 bond length [1.422 (5) Å] is shorter than expected for a single bond. The cyanide C3—N2 bond length is 1.149 (5) Å.

In the crystal, the molecules form centrosymmetric cyclic dimers through amino N—H···N hydrogen-bonding associations with cyano N-atom acceptors (Table 1) [graph set R²₂(12) (Etter et al., 1990)] and these dimers are extended into a three-dimensional structure through N—H···N amine···cyano group associations. The thiophene molecules form antiparallel stacks down a, with a thiophene-thiophene ring centroid separation of 3.923 (2) Å.

Related literature top

For the synthesis of this and related compounds via the reaction of tetracyanoethylene with hydrogen sulfide, see: Cairns et al. (1957); Middleton et al. (1958); Middleton (1959). For the use of this compound as a reagent, see: Nemykin et al. (2012). For graph-set analysis, see : Etter et al. (1990). For details of the weighting scheme, see: Prince (1982); Watkin (1994).

Experimental top

The title compound was prepared using an earlier published procedure via the reaction of tetracyanoethylene and hydrogen sulfide (Cairns et al., 1957) and characterized by ¹H and ¹³C NMR spectroscopy. The single crystal used for the X-ray analysis was obtained by slow cooling of a saturated solution in DMSO.

Computing details top

Data collection: CrystalClear (Rigaku, 2009); cell refinement: HKL-2000 (Otwinowski & Minor, 1997); data reduction: CrystalClear (Rigaku, 2009); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures top

Fig. 1. The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius. For symmetry code (i): -x+2, y, -z+3/2.

2,5-Diaminothiophene-3,4-dicarbonitrile top

Crystal data top

C₆H₄N₄S	D_x = 1.590 Mg m⁻³
M_r = 164.19	Melting point: 513 K
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 783 reflections
a = 3.9231 (2) Å	θ = 2–27°
b = 13.8213 (12) Å	µ = 0.40 mm⁻¹
c = 12.6465 (11) Å	T = 123 K
V = 685.72 (9) Å³	Plate, brown
Z = 4	0.41 × 0.24 × 0.16 mm
F(000) = 336

Data collection top

Rigaku RAPID II diffractometer	783 independent reflections
Radiation source: Mo Ka	492 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: ψ scan (North et al., 1968)	h = −5→5
T_min = 0.69, T_max = 0.94	k = −13→17
2260 measured reflections	l = −13→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.116	Method, part 1, Chebychev polynomial, (Watkin, 1994; Prince, 1982) [weight] = 1.0/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1]T_n-1(x)] where A_i are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] [1-(deltaF/6*sigmaF)²]² A_i are: 57.9 74.5 21.5
S = 0.99	(Δ/σ)_max = 0.0000992
769 reflections	Δρ_max = 0.65 e Å⁻³
51 parameters	Δρ_min = −0.63 e Å⁻³
0 restraints

Crystal data top

C₆H₄N₄S	V = 685.72 (9) Å³
M_r = 164.19	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 3.9231 (2) Å	µ = 0.40 mm⁻¹
b = 13.8213 (12) Å	T = 123 K
c = 12.6465 (11) Å	0.41 × 0.24 × 0.16 mm

Data collection top

Rigaku RAPID II diffractometer	783 independent reflections
Absorption correction: ψ scan (North et al., 1968)	492 reflections with I > 2σ(I)
T_min = 0.69, T_max = 0.94	R_int = 0.054
2260 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 0.99	Δρ_max = 0.65 e Å⁻³
769 reflections	Δρ_min = −0.63 e Å⁻³
51 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Rigaku XStream 2000 open-flow nitrogen cryostat with a nominal stability of 0.1 K.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	1.0000	0.75078 (10)	0.7500	0.0189
C1	0.8517 (10)	0.6628 (3)	0.6618 (3)	0.0184
N1	0.7035 (9)	0.6908 (2)	0.5697 (2)	0.0205
H2	0.6326	0.6473	0.5246	0.0500*
H1	0.6790	0.7530	0.5557	0.0500*
C2	0.9146 (10)	0.5716 (3)	0.6988 (3)	0.0188
C3	0.8190 (10)	0.4873 (3)	0.6416 (3)	0.0211
N2	0.7390 (11)	0.4203 (2)	0.5938 (3)	0.0286

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0243 (7)	0.0137 (5)	0.0188 (6)	0.0000	−0.0041 (6)	0.0000
C1	0.0202 (19)	0.0184 (17)	0.0166 (16)	−0.0027 (16)	0.0025 (15)	−0.0009 (13)
N1	0.0285 (19)	0.0152 (14)	0.0177 (14)	0.0003 (14)	−0.0060 (14)	0.0012 (11)
C2	0.023 (2)	0.0153 (16)	0.0181 (17)	−0.0018 (15)	0.0016 (16)	−0.0027 (14)
C3	0.024 (2)	0.0213 (19)	0.0176 (17)	0.0006 (17)	−0.0003 (16)	0.0021 (15)
N2	0.040 (2)	0.0205 (16)	0.0249 (17)	−0.0053 (17)	−0.0034 (18)	−0.0021 (13)

Geometric parameters (Å, º) top

S1—C1ⁱ	1.750 (4)	N1—H1	0.884
S1—C1	1.750 (4)	C2—C2ⁱ	1.458 (7)
C1—N1	1.358 (5)	C2—C3	1.422 (5)
C1—C2	1.367 (5)	C3—N2	1.149 (5)
N1—H2	0.874

C1ⁱ—S1—C1	91.9 (3)	H2—N1—H1	120.2
S1—C1—N1	119.4 (3)	C2ⁱ—C2—C1	112.8 (2)
S1—C1—C2	111.3 (3)	C2ⁱ—C2—C3	125.0 (2)
N1—C1—C2	129.3 (3)	C1—C2—C3	122.3 (3)
C1—N1—H2	120.0	C2—C3—N2	178.6 (4)
C1—N1—H1	119.8

Symmetry code: (i) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···N2ⁱⁱ	0.87	2.29	3.106 (5)	156
N1—H1···N2ⁱⁱⁱ	0.88	2.38	3.196 (5)	153

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

Experimental details

Crystal data
Chemical formula	C₆H₄N₄S
M_r	164.19
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	123
a, b, c (Å)	3.9231 (2), 13.8213 (12), 12.6465 (11)
V (Å³)	685.72 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.41 × 0.24 × 0.16

Data collection
Diffractometer	Rigaku RAPID II diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.69, 0.94
No. of measured, independent and observed [I > 2σ(I)] reflections	2260, 783, 492
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.116, 0.99
No. of reflections	769
No. of parameters	51
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.63

Computer programs: CrystalClear (Rigaku, 2009), HKL-2000 (Otwinowski & Minor, 1997), SHELXS86 (Sheldrick, 2008), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···N2ⁱ	0.87	2.29	3.106 (5)	156
N1—H1···N2ⁱⁱ	0.88	2.38	3.196 (5)	153

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

Acknowledgements

This study was supported by the National Science Foundation (grants CHE-0922366 and CHE-1110455).

References

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