2,2′-[(1,3,4-Thia­diazole-2,5-di­yl)bis­(sulfanedi­yl)]diaceto­nitrile

Mague, J.T.; Akkurt, M.; Mohamed, S.K.; El-Saghier, A.M.M.; Albayati, M.R.

doi:10.1107/S1600536813032194

organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Page o1855

doi:10.1107/S1600536813032194

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2,2′-[(1,3,4-Thiadiazole-2,5-diyl)bis(sulfanediyl)]diacetonitrile

Joel T. Mague,^a Mehmet Akkurt,^b Shaaban K. Mohamed,^c,^d Ahmed M. M. El-Saghier ^e and Mustafa R. Albayati ^f ^*

^aDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, ^dChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, ^eDepartment of Chemistry, Faculty of Science, Sohag University, 82524 Sohag, Egypt, and ^fKirkuk University, College of Science, Department of Chemistry, Kirkuk, Iraq
^*Correspondence e-mail: shaabankamel@yahoo.com

(Received 22 November 2013; accepted 26 November 2013; online 30 November 2013)

In the title compound, C₆H₄N₄S₃, the 1,3,4-thiadiazole ring is essentially planar, with an r.m.s. deviation of 0.001 Å. The two N—C—S—C torsion angles in the molecule are −23.41 (15) and 0.62 (14)°. One acetonitrile group is above the plane of the 1,3,4-thiadiazole ring and the other is below it, indicating syn and anti orientations. In the crystal, C—H⋯N hydrogen bonds link the molecules into ribbons along [010].

CCDC reference: 973732

Related literature

For the broad spectrum of biological activities of thiadiazole-containing compounds, see: Padmavathi et al. (2009 ); Karegoudar et al. (2008 ); Wei et al. (2009 ); Gupta et al. (2009 ); Pattanayak et al. (2009 ); Cressier et al. (2009 ).

Experimental

Crystal data

C₆H₄N₄S₃
M_r = 228.34
Monoclinic, P 2₁ /c
a = 8.5305 (7) Å
b = 14.2102 (11) Å
c = 7.8803 (6) Å
β = 104.3810 (11)°
V = 925.32 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 150 K
0.24 × 0.08 × 0.06 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ) T_min = 0.82, T_max = 0.96
16625 measured reflections
2450 independent reflections
2155 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.074
S = 1.05
2450 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯N1ⁱ	0.99	2.60	3.407 (2)	139
C5—H5B⋯N3ⁱⁱ	0.99	2.35	3.267 (2)	153
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 973732

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813032194/hg5363sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813032194/hg5363Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813032194/hg5363Isup3.cml

checkCIF report

Comment top

Thiadiazole acts as a constrained pharmacophore. It is the core structure of several medicinal drugs such as acetazolamide, atibeprone, tebuthiuron and methazolamide. In addition, thiadiazole containing compounds have a wide spectrum of biological activities such as antimicrobial (Padmavathi et al., 2009), antiinflammatory (Karegoudar et al., 2008), anticancer (Wei et al., 2009), anticonvulsant (Gupta et al., 2009), antidepressant (Pattanayak et al., 2009), and antioxidant (Cressier et al., 2009). Based on such facts, the title compound has been synthesized in our lab as a precurser for further study.

The 1,3,4-thiadiazole ring (S1/N1/N2/C1/C2) of the title compound, (I, Fig. 1), is essentially planar [r.m.s deviation = 0.001 Å]. The N1–C1–S2–C3 and N2–C2–S3–C5 torsion angles in (I) are 23.41 (15) and -0.62 (14)°, respectively. The two acetonitrile groups [–C3(H₂)–C4≡N3 and –C5(H₂)–C6≡N4] of (I) are above and below the plane of the 1,3,4-thiadiazole ring, indicating syn- and anti- orientations, respectively.

In the crystal, molecules are linked by intermolecular C—H···N hydrogen bonds to form ribbons along the b-axis (Table 1, Fig. 2).

Related literature top

For the broad spectrum of biological activities of thiadiazole-containing compounds, see: Padmavathi et al. (2009); Karegoudar et al. (2008); Wei et al. (2009); Gupta et al. (2009); Pattanayak et al. (2009); Cressier et al. (2009).

Experimental top

A mixture of 1,3,4-thiadiazolidine-2,5-dithione (150 mg, 1 mmol), chloroacetonitrile (149 mg, 2 mmol), sodium acetate (36 mg, 0.5 mmol) in 30 ml e thanol was refluxed for 4 h. The reaction mixture was allowed to cool to room temperature to afford the solid product which was filtered off under vacuum, dried and recrystallized from ethanol. Pure single crystals were prepared by slow evaporation of an ethanolic solution of the title compound in air over 24 h. M·P. 396 K.

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Perspective view of the title molecule with 50% probability displacement ellipsoids.
	Fig. 2. The hydrogen bonding (dashed lines) viewed along the b-axis of the title compound. [Symmetry code: (b) 1 + x, ½ - y, ½ + z].

2,2'-[(1,3,4-Thiadiazole-2,5-diyl)bis(sulfanediyl)]diacetonitrile top

Crystal data top

C₆H₄N₄S₃	F(000) = 464
M_r = 228.34	D_x = 1.639 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9961 reflections
a = 8.5305 (7) Å	θ = 2.9–29.1°
b = 14.2102 (11) Å	µ = 0.76 mm⁻¹
c = 7.8803 (6) Å	T = 150 K
β = 104.3810 (11)°	Column, pale gold
V = 925.32 (13) Å³	0.24 × 0.08 × 0.06 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2450 independent reflections
Radiation source: fine-focus sealed tube	2155 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 8.3660 pixels mm^-1	θ_max = 29.1°, θ_min = 2.5°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −19→19
T_min = 0.82, T_max = 0.96	l = −10→10
16625 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.074	W = 1/[Σ²(FO²) + (0.0348P)² + 0.4414P] Where P = (FO² + 2FC²)/3
S = 1.05	(Δ/σ)_max < 0.001
2450 reflections	Δρ_max = 0.56 e Å⁻³
118 parameters	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₆H₄N₄S₃	V = 925.32 (13) Å³
M_r = 228.34	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5305 (7) Å	µ = 0.76 mm⁻¹
b = 14.2102 (11) Å	T = 150 K
c = 7.8803 (6) Å	0.24 × 0.08 × 0.06 mm
β = 104.3810 (11)°

Data collection top

Bruker SMART APEX CCD diffractometer	2450 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	2155 reflections with I > 2σ(I)
T_min = 0.82, T_max = 0.96	R_int = 0.040
16625 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.05	Δρ_max = 0.56 e Å⁻³
2450 reflections	Δρ_min = −0.24 e Å⁻³
118 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.24557 (4)	0.24679 (2)	0.77612 (5)	0.0199 (1)
S2	0.35261 (4)	0.45127 (3)	0.80614 (5)	0.0225 (1)
S3	−0.02136 (4)	0.11179 (3)	0.59651 (5)	0.0217 (1)
N1	0.07063 (16)	0.38153 (9)	0.61222 (18)	0.0246 (4)
N2	−0.01784 (15)	0.29982 (9)	0.56140 (18)	0.0232 (4)
N3	0.31454 (18)	0.46664 (10)	0.33409 (18)	0.0286 (4)
N4	−0.40861 (18)	0.23221 (12)	0.5806 (2)	0.0370 (5)
C1	0.20800 (17)	0.36440 (10)	0.72254 (19)	0.0188 (4)
C2	0.05731 (17)	0.22555 (10)	0.63639 (18)	0.0178 (4)
C3	0.29143 (18)	0.53720 (10)	0.6312 (2)	0.0223 (4)
C4	0.30417 (18)	0.49844 (10)	0.4636 (2)	0.0222 (4)
C5	−0.20837 (18)	0.14204 (11)	0.4383 (2)	0.0240 (4)
C6	−0.32061 (18)	0.19370 (11)	0.5168 (2)	0.0247 (4)
H3A	0.17830	0.55670	0.62240	0.0270*
H3B	0.36100	0.59370	0.65920	0.0270*
H5A	−0.18280	0.18080	0.34420	0.0290*
H5B	−0.26140	0.08360	0.38420	0.0290*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0170 (2)	0.0195 (2)	0.0210 (2)	−0.0004 (1)	0.0001 (1)	0.0025 (1)
S2	0.0207 (2)	0.0212 (2)	0.0224 (2)	−0.0041 (1)	−0.0007 (1)	0.0015 (1)
S3	0.0205 (2)	0.0189 (2)	0.0243 (2)	−0.0020 (1)	0.0029 (1)	−0.0006 (1)
N1	0.0195 (6)	0.0210 (6)	0.0302 (7)	−0.0028 (5)	0.0006 (5)	0.0037 (5)
N2	0.0185 (6)	0.0212 (6)	0.0274 (7)	−0.0031 (5)	0.0012 (5)	0.0025 (5)
N3	0.0310 (7)	0.0273 (7)	0.0261 (7)	−0.0034 (6)	0.0042 (6)	0.0016 (6)
N4	0.0244 (7)	0.0490 (9)	0.0352 (8)	0.0019 (7)	0.0031 (6)	−0.0032 (7)
C1	0.0195 (7)	0.0175 (6)	0.0194 (7)	−0.0010 (5)	0.0050 (5)	0.0017 (5)
C2	0.0156 (6)	0.0217 (7)	0.0164 (6)	−0.0014 (5)	0.0043 (5)	0.0004 (5)
C3	0.0232 (7)	0.0173 (7)	0.0260 (8)	0.0014 (5)	0.0051 (6)	0.0023 (6)
C4	0.0202 (7)	0.0180 (7)	0.0265 (8)	−0.0026 (5)	0.0025 (6)	0.0041 (6)
C5	0.0233 (7)	0.0272 (8)	0.0187 (7)	−0.0049 (6)	0.0000 (5)	−0.0028 (6)
C6	0.0187 (7)	0.0299 (8)	0.0215 (7)	−0.0047 (6)	−0.0026 (6)	0.0009 (6)

Geometric parameters (Å, º) top

S1—C1	1.7340 (15)	N3—C4	1.140 (2)
S1—C2	1.7333 (15)	N4—C6	1.142 (2)
S2—C1	1.7538 (15)	C3—C4	1.460 (2)
S2—C3	1.8184 (15)	C5—C6	1.460 (2)
S3—C2	1.7486 (15)	C3—H3A	0.9900
S3—C5	1.8155 (16)	C3—H3B	0.9900
N1—N2	1.3885 (19)	C5—H5A	0.9900
N1—C1	1.297 (2)	C5—H5B	0.9900
N2—C2	1.2984 (19)

C1—S1—C2	85.82 (7)	S3—C5—C6	112.64 (11)
C1—S2—C3	98.35 (7)	N4—C6—C5	178.33 (17)
C2—S3—C5	97.88 (7)	S2—C3—H3A	109.00
N2—N1—C1	111.85 (12)	S2—C3—H3B	109.00
N1—N2—C2	112.14 (13)	C4—C3—H3A	109.00
S1—C1—S2	121.11 (9)	C4—C3—H3B	109.00
S1—C1—N1	115.19 (11)	H3A—C3—H3B	108.00
S2—C1—N1	123.63 (11)	S3—C5—H5A	109.00
S1—C2—S3	121.93 (8)	S3—C5—H5B	109.00
S1—C2—N2	114.99 (11)	C6—C5—H5A	109.00
S3—C2—N2	123.07 (11)	C6—C5—H5B	109.00
S2—C3—C4	111.14 (10)	H5A—C5—H5B	108.00
N3—C4—C3	178.79 (16)

C2—S1—C1—S2	−177.61 (10)	C5—S3—C2—N2	0.62 (14)
C2—S1—C1—N1	−0.51 (12)	C2—S3—C5—C6	−68.78 (12)
C1—S1—C2—S3	179.01 (10)	C1—N1—N2—C2	0.16 (19)
C1—S1—C2—N2	0.61 (12)	N2—N1—C1—S1	0.32 (17)
C3—S2—C1—S1	153.44 (9)	N2—N1—C1—S2	177.33 (11)
C3—S2—C1—N1	−23.41 (15)	N1—N2—C2—S1	−0.57 (17)
C1—S2—C3—C4	−60.50 (12)	N1—N2—C2—S3	−178.96 (11)
C5—S3—C2—S1	−177.66 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···N1ⁱ	0.99	2.60	3.407 (2)	139
C5—H5B···N3ⁱⁱ	0.99	2.35	3.267 (2)	153

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···N1ⁱ	0.99	2.60	3.407 (2)	139
C5—H5B···N3ⁱⁱ	0.99	2.35	3.267 (2)	153

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

Acknowledgements

The authors thank Tulane University, Manchester Metropolitan University, Erciyes University and Sohag University for supporting this study.

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