Bis[(5-phenyl-1,3,4-thia­diazol-2-yl)sulfan­yl]methane

Wang, H.; Gao, Y.; Wang, W.

doi:10.1107/S1600536810044442

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3085

https://doi.org/10.1107/S1600536810044442

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Bis[(5-phenyl-1,3,4-thiadiazol-2-yl)sulfanyl]methane

He-wen Wang,^a ^* Yan Gao ^b and Wei Wang ^c,^b

^aCollege of Chemistry and Applied Chemistry, Huanggang Normal University, Huanggang 438000, People's Republic of China, ^bSchool of Chemical Engineering, University of Science and Technology LiaoNing, Anshan 114051, People's Republic of China, and ^cSchool of Perfume and Aroma Technology, Shanghai Institute of Technology, Shanghai 200235, People's Republic of China
^*Correspondence e-mail: wanghewenll@yahoo.com.cn

(Received 24 October 2010; accepted 31 October 2010; online 6 November 2010)

The asymmetric unit of the title compound, C₁₇H₁₂N₄S₄, contains one half-molecule situated on a twofold rotational axis. In the molecule, the thiadiazole and attached phenyl rings are twisted by 5.8 (3)°.

Related literature

For biological activity of 1,3,4-thiadiazole derivatives, see: Nakagawa et al. (1996 ); Wang et al. (1999 ); Carvalho et al. (2004 ); Riente et al. (2009 ); Poorrajab et al. (2009 ).

Experimental

Crystal data

C₁₇H₁₂N₄S₄
M_r = 400.55
Orthorhombic, P 2₁ 2₁ 2
a = 10.805 (2) Å
b = 19.287 (4) Å
c = 4.0738 (8) Å
V = 848.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.10 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.895, T_max = 0.945
6754 measured reflections
1477 independent reflections
1421 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.124
S = 1.03
1477 reflections
115 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.55 e Å⁻³
Absolute structure: Flack (1983 ), 554 Friedel pairs
Flack parameter: 0.16 (14)

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810044442/cv2783sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810044442/cv2783Isup2.hkl

checkCIF report

Comment top

1,3,4-Thiadiazole derivatives attracted considerable attention due to their broad spectrum of chemical and pharmaceutical properties (Nakagawa et al., 1996; Wang et al., 1999), with particular attention being paid to the anti-trypanosomal activities of Megazol and related compounds (Carvalho et al., 2004; Riente et al., 2009; Poorrajab et al., 2009). Herewith we report the synthesis and crystal structure of the title compound, (I), a new 1,3,4-thiadiazole derivative.

The molecular structure of (I) is shown in Fig.1. In the crystal structure, the molecule is situated on a two-fold rotational axis so asymmetric unit contains a half of the molecule. 1,3,4-Thiadiazole ring is planar with an r.m.s. deviation of 0.0048 (2)Å and maximum deviation of 0.0072 (2)Å for atom C7. The dihedral angle between the thiadiazole and attached phenyl rings is 5.8 (3)°. As a result of π-π conjugation, the C_sp²-S bond length [S2—C8 = 1.751 (3) Å] is significantly shorter than the C_sp³-S bond length [S2—C9 = 1.810 (2) Å].

Related literature top

For biological activity of 1,3,4-thiadiazole derivatives, see: Nakagawa et al. (1996); Wang et al. (1999); Carvalho et al. (2004); Riente et al. (2009); Poorrajab et al. (2009).

Experimental top

A suspension of 5-diphenyl-1,3,4-thiadiazol-2-thiol (2.0 mmol) and 1,1-dibromomethane (1.0 mmol) in ethanol (10 ml) was stirred at room temperature. The reaction progress was monitored via TLC. The resulting precipitate was filtered off, washed with cold ethanol, dried and purified to give the target product as light yellow solid in 95% yield. Crystals of (I) suitable for single-crystal X-ray analysis were grown by slow evaporation of a solution in chloroform-ethanol (1:1).

Structure description top

For biological activity of 1,3,4-thiadiazole derivatives, see: Nakagawa et al. (1996); Wang et al. (1999); Carvalho et al. (2004); Riente et al. (2009); Poorrajab et al. (2009).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of (I) showing the atom-labelling scheme and 35% probability displacement ellipsoids [symmetry code: (A) = -x,-y + 1,z].

Bis[(5-phenyl-1,3,4-thiadiazol-2-yl)sulfanyl]methane top

Crystal data top

C₁₇H₁₂N₄S₄	F(000) = 412
M_r = 400.55	D_x = 1.567 Mg m⁻³
Orthorhombic, P2₁2₁2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 2856 reflections
a = 10.805 (2) Å	θ = 2.1–27.9°
b = 19.287 (4) Å	µ = 0.57 mm⁻¹
c = 4.0738 (8) Å	T = 113 K
V = 848.9 (3) Å³	Prism, colourless
Z = 2	0.20 × 0.18 × 0.10 mm

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1477 independent reflections
Radiation source: rotating anode	1421 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.028
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 2.1°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −22→22
T_min = 0.895, T_max = 0.945	l = −4→4
6754 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.029	w = 1/[σ²(F_o²) + (0.110P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.124	(Δ/σ)_max = 0.001
S = 1.03	Δρ_max = 0.54 e Å⁻³
1477 reflections	Δρ_min = −0.55 e Å⁻³
115 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.049 (10)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 554 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.16 (14)

Crystal data top

C₁₇H₁₂N₄S₄	V = 848.9 (3) Å³
M_r = 400.55	Z = 2
Orthorhombic, P2₁2₁2	Mo Kα radiation
a = 10.805 (2) Å	µ = 0.57 mm⁻¹
b = 19.287 (4) Å	T = 113 K
c = 4.0738 (8) Å	0.20 × 0.18 × 0.10 mm

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1477 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1421 reflections with I > 2σ(I)
T_min = 0.895, T_max = 0.945	R_int = 0.028
6754 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.124	Δρ_max = 0.54 e Å⁻³
S = 1.03	Δρ_min = −0.55 e Å⁻³
1477 reflections	Absolute structure: Flack (1983), 554 Friedel pairs
115 parameters	Absolute structure parameter: 0.16 (14)
0 restraints

Special details top

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	Occ. (<1)
S1	0.19317 (6)	0.33910 (3)	0.3294 (2)	0.0215 (3)
S2	0.13644 (6)	0.47579 (4)	0.6577 (2)	0.0216 (3)
N1	−0.0251 (2)	0.29797 (13)	0.4770 (7)	0.0223 (6)
N2	−0.0161 (2)	0.36481 (13)	0.6002 (7)	0.0231 (6)
C1	−0.0141 (3)	0.16581 (16)	0.1495 (9)	0.0260 (7)
H1	−0.0904	0.1795	0.2453	0.031*
C2	−0.0048 (3)	0.10272 (16)	−0.0079 (9)	0.0289 (8)
H2	−0.0748	0.0731	−0.0206	0.035*
C3	0.1073 (3)	0.08236 (15)	−0.1485 (9)	0.0279 (7)
H3	0.1136	0.0389	−0.2568	0.033*
C4	0.2085 (3)	0.12546 (15)	−0.1299 (9)	0.0262 (7)
H4	0.2847	0.1117	−0.2264	0.031*
C5	0.1999 (3)	0.18852 (16)	0.0284 (8)	0.0234 (7)
H5	0.2704	0.2178	0.0420	0.028*
C6	0.0885 (3)	0.20960 (14)	0.1682 (8)	0.0196 (6)
C7	0.0747 (2)	0.27771 (15)	0.3277 (7)	0.0181 (6)
C8	0.0919 (3)	0.39217 (14)	0.5395 (8)	0.0192 (7)
C9	0.0000	0.5000	0.8888 (11)	0.0229 (10)
H9A	0.0223	0.5394	1.0330	0.027*	0.50
H9B	−0.0223	0.4606	1.0330	0.027*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0163 (4)	0.0229 (4)	0.0252 (5)	−0.0010 (3)	0.0012 (4)	−0.0011 (3)
S2	0.0221 (4)	0.0204 (4)	0.0223 (5)	−0.0011 (3)	−0.0018 (4)	0.0005 (3)
N1	0.0199 (12)	0.0197 (12)	0.0273 (14)	0.0005 (9)	−0.0006 (12)	0.0018 (12)
N2	0.0229 (12)	0.0200 (12)	0.0263 (15)	0.0006 (10)	0.0035 (11)	−0.0007 (12)
C1	0.0198 (14)	0.0279 (15)	0.0303 (18)	0.0002 (11)	0.0039 (16)	0.0029 (17)
C2	0.0258 (14)	0.0254 (15)	0.036 (2)	−0.0019 (12)	−0.0060 (17)	−0.0012 (16)
C3	0.0374 (17)	0.0206 (13)	0.0257 (17)	0.0052 (13)	0.0029 (17)	−0.0019 (15)
C4	0.0244 (14)	0.0254 (14)	0.0289 (18)	0.0079 (12)	0.0013 (15)	0.0031 (16)
C5	0.0208 (14)	0.0232 (14)	0.0260 (17)	0.0012 (12)	−0.0002 (15)	0.0041 (14)
C6	0.0189 (14)	0.0209 (14)	0.0191 (15)	0.0028 (11)	−0.0046 (13)	0.0043 (14)
C7	0.0162 (13)	0.0216 (13)	0.0166 (14)	0.0000 (11)	−0.0015 (13)	0.0033 (13)
C8	0.0206 (14)	0.0198 (12)	0.0170 (15)	0.0038 (11)	−0.0010 (13)	−0.0001 (12)
C9	0.029 (2)	0.0235 (19)	0.016 (2)	−0.0003 (17)	0.000	0.000

Geometric parameters (Å, º) top

S1—C8	1.726 (3)	C2—H2	0.9500
S1—C7	1.744 (3)	C3—C4	1.376 (5)
S2—C8	1.751 (3)	C3—H3	0.9500
S2—C9	1.810 (2)	C4—C5	1.380 (5)
N1—C7	1.298 (4)	C4—H4	0.9500
N1—N2	1.387 (4)	C5—C6	1.391 (4)
N2—C8	1.304 (4)	C5—H5	0.9500
C1—C2	1.379 (5)	C6—C7	1.473 (4)
C1—C6	1.396 (4)	C9—S2ⁱ	1.810 (2)
C1—H1	0.9500	C9—H9A	0.9900
C2—C3	1.396 (4)	C9—H9B	0.9900

C8—S1—C7	86.51 (14)	C4—C5—H5	119.8
C8—S2—C9	99.02 (10)	C6—C5—H5	119.8
C7—N1—N2	113.0 (2)	C5—C6—C1	119.2 (3)
C8—N2—N1	111.8 (2)	C5—C6—C7	121.9 (3)
C2—C1—C6	120.1 (3)	C1—C6—C7	118.9 (3)
C2—C1—H1	119.9	N1—C7—C6	124.0 (3)
C6—C1—H1	119.9	N1—C7—S1	113.8 (2)
C1—C2—C3	120.1 (3)	C6—C7—S1	122.2 (2)
C1—C2—H2	119.9	N2—C8—S1	114.9 (2)
C3—C2—H2	119.9	N2—C8—S2	124.5 (2)
C4—C3—C2	119.8 (3)	S1—C8—S2	120.57 (17)
C4—C3—H3	120.1	S2—C9—S2ⁱ	117.3 (2)
C2—C3—H3	120.1	S2—C9—H9A	108.0
C3—C4—C5	120.3 (3)	S2ⁱ—C9—H9A	108.0
C3—C4—H4	119.9	S2—C9—H9B	108.0
C5—C4—H4	119.9	S2ⁱ—C9—H9B	108.0
C4—C5—C6	120.5 (3)	H9A—C9—H9B	107.2

C7—N1—N2—C8	−0.5 (4)	C1—C6—C7—N1	5.7 (5)
C6—C1—C2—C3	0.1 (5)	C5—C6—C7—S1	4.3 (4)
C1—C2—C3—C4	0.0 (5)	C1—C6—C7—S1	−173.9 (3)
C2—C3—C4—C5	0.3 (6)	C8—S1—C7—N1	−1.1 (2)
C3—C4—C5—C6	−0.6 (5)	C8—S1—C7—C6	178.6 (3)
C4—C5—C6—C1	0.7 (5)	N1—N2—C8—S1	−0.4 (3)
C4—C5—C6—C7	−177.6 (3)	N1—N2—C8—S2	179.9 (2)
C2—C1—C6—C5	−0.4 (5)	C7—S1—C8—N2	0.8 (3)
C2—C1—C6—C7	177.9 (3)	C7—S1—C8—S2	−179.5 (2)
N2—N1—C7—C6	−178.6 (2)	C9—S2—C8—N2	4.3 (3)
N2—N1—C7—S1	1.1 (3)	C9—S2—C8—S1	−175.34 (19)
C5—C6—C7—N1	−176.0 (3)	C8—S2—C9—S2ⁱ	−76.74 (11)

Symmetry code: (i) −x, −y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₂N₄S₄
M_r	400.55
Crystal system, space group	Orthorhombic, P2₁2₁2
Temperature (K)	113
a, b, c (Å)	10.805 (2), 19.287 (4), 4.0738 (8)
V (Å³)	848.9 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.57
Crystal size (mm)	0.20 × 0.18 × 0.10

Data collection
Diffractometer	Rigaku Saturn CCD area-detector
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.895, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	6754, 1477, 1421
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.124, 1.03
No. of reflections	1477
No. of parameters	115
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.55
Absolute structure	Flack (1983), 554 Friedel pairs
Absolute structure parameter	0.16 (14)

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We thank the Doctoral Foundation of Huanggang Normal University (grant No. 09CD155).

References

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