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

Li, S.; Zhang, J.; Jia, X.; Gao, Y.; Wang, W.

doi:10.1107/S1600536811006064

organic compounds

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Volume 67| Part 3| March 2011| Page o681

doi:10.1107/S1600536811006064

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

Shao-feng Li,^a Jing-jing Zhang,^a Xiao-yu Jia,^a Yan Gao ^a and Wei Wang ^a,^b ^*

^aSchool of Chemical Engineering, University of Science and Technology LiaoNing, Anshan 114051, People's Republic of China, and ^bSchool of Perfume and Aroma Technology, Shanghai Institute of Technology, Shanghai 200235, People's Republic of China
^*Correspondence e-mail: zhao_submit@yahoo.com.cn

(Received 14 February 2011; accepted 17 February 2011; online 23 February 2011)

The asymmetric unit of the title compound, C₂₀H₁₈N₄S₄, contains one half-molecule situated on a twofold rotation axis, in which the thiadiazole and phenyl rings are twisted by 7.2 (3)°. In the crystal, weak intermolecular C—H⋯π interactions link the molecules into layers parallel to (103).

Related literature

For the biological activity of 1,3,4-triazole derivatives, see: Nakagawa et al. (1996 ); Wang et al. (1999 ). For the crystal structure of bis(5-phenyl-1,3,4-thiadiazol-2-ylsulfanyl)methane, see: Wang et al. (2010 ).

Experimental

Crystal data

C₂₀H₁₈N₄S₄
M_r = 442.62
Monoclinic, P 2₁ /c
a = 5.7976 (7) Å
b = 13.4393 (14) Å
c = 12.9784 (12) Å
β = 99.120 (7)°
V = 998.44 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.49 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 = 0.908, T_max = 0.953
9992 measured reflections
2384 independent reflections
1870 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.088
S = 1.06
2384 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯Cgⁱ	0.99	2.70	3.540 (2)	144
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: 10.1107/S1600536811006064/cv5053sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811006064/cv5053Isup2.hkl

checkCIF report

Comment top

1,3,4-Thiadiazole derivatives exhibit a wide spectrum of biological activities (Nakagawa et al., 1996; Wang et al., 1999). Recently, we have published the crystal structure of bis(5-phenyl-1,3,4-thiadiazol-2-ylsulfanyl)methane (Wang et al., 2010). Herewith we report the crystal structure of the title compound, (I).

In (I) (Fig. 1), the molecule is situated on a twofold rotational axis so asymmetric unit contains a half of the molecule. The dihedral angle between the thiadiazole and the attached benzene rings is 7.2 (3)° indicating that two rings are almost parallel. As a result of π-π conjugation, the C_sp²-S bond [S2—C8 = 1.742 (2) Å] is significantly shorter than the C_sp³-S bond [S2—C9 = 1.813 (2) Å].

In the crystal structure, weak intermolecular C—H···π interactions (Table 1) link molecules into layers parallel to (103) plane.

Related literature top

For the biological activity of 1,3,4-triazole derivatives, see: Nakagawa et al. (1996); Wang et al. (1999). For the crystal structure of bis(5-phenyl-1,3,4-thiadiazol-2-ylsulfanyl)methane, see: Wang et al. (2010).

Experimental top

A suspension of 5-diphenyl-1,3,4-thiadiazol-2-thiol (2.0 mmol) and 1,1-dibromobutane (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 85% yield. Crystals of (I) suitable for single-crystal X-ray analysis were grown by slow evaporation of a solution in chloroform-ethanol (1:1).

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 the molecule of (I) showing the atom-labelling scheme [symmetry code: (A)-x + 1, -y + 1, -z]. Displacement ellipsoids are drawn at the 85% probability level.

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

Crystal data top

C₂₀H₁₈N₄S₄	F(000) = 460
M_r = 442.62	D_x = 1.472 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3630 reflections
a = 5.7976 (7) Å	θ = 1.5–27.9°
b = 13.4393 (14) Å	µ = 0.49 mm⁻¹
c = 12.9784 (12) Å	T = 113 K
β = 99.120 (7)°	Prism, colorless
V = 998.44 (18) Å³	0.20 × 0.18 × 0.10 mm
Z = 2

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2384 independent reflections
Radiation source: rotating anode	1870 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.038
Detector resolution: 14.63 pixels mm^-1	θ_max = 27.9°, θ_min = 2.2°
ϕ and ω scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −17→17
T_min = 0.908, T_max = 0.953	l = −15→16
9992 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0495P)²] where P = (F_o² + 2F_c²)/3
2384 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₀H₁₈N₄S₄	V = 998.44 (18) Å³
M_r = 442.62	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.7976 (7) Å	µ = 0.49 mm⁻¹
b = 13.4393 (14) Å	T = 113 K
c = 12.9784 (12) Å	0.20 × 0.18 × 0.10 mm
β = 99.120 (7)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2384 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1870 reflections with I > 2σ(I)
T_min = 0.908, T_max = 0.953	R_int = 0.038
9992 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.06	Δρ_max = 0.49 e Å⁻³
2384 reflections	Δρ_min = −0.22 e Å⁻³
127 parameters

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
S1	1.18924 (6)	0.48167 (3)	0.35236 (3)	0.01929 (12)
S2	0.94277 (7)	0.60479 (3)	0.17655 (3)	0.02206 (13)
N1	0.8027 (2)	0.39565 (9)	0.36814 (10)	0.0221 (3)
N2	0.7508 (2)	0.46308 (10)	0.28684 (10)	0.0206 (3)
C1	1.3577 (3)	0.34573 (11)	0.54385 (12)	0.0210 (3)
H1	1.4506	0.3955	0.5185	0.025*
C2	1.4532 (3)	0.28628 (12)	0.62747 (12)	0.0213 (3)
H2	1.6099	0.2969	0.6601	0.026*
C3	1.3224 (3)	0.21206 (12)	0.66341 (12)	0.0237 (4)
H3	1.3889	0.1710	0.7199	0.028*
C4	1.0921 (3)	0.19787 (12)	0.61620 (13)	0.0259 (4)
H4	1.0013	0.1469	0.6409	0.031*
C5	0.9936 (3)	0.25738 (12)	0.53341 (12)	0.0216 (3)
H5	0.8363	0.2469	0.5015	0.026*
C6	1.1262 (3)	0.33270 (11)	0.49711 (11)	0.0173 (3)
C7	1.0225 (3)	0.39663 (11)	0.40992 (12)	0.0171 (3)
C8	0.9342 (3)	0.51325 (11)	0.27088 (12)	0.0175 (3)
C9	0.6507 (3)	0.59299 (11)	0.10328 (12)	0.0211 (3)
H9A	0.5373	0.5895	0.1527	0.025*
H9B	0.6143	0.6531	0.0597	0.025*
C10	0.6215 (2)	0.50122 (11)	0.03322 (12)	0.0205 (3)
H10A	0.6445	0.4405	0.0769	0.025*
H10B	0.7419	0.5018	−0.0130	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01581 (19)	0.0215 (2)	0.0199 (2)	−0.00349 (15)	0.00081 (16)	0.00081 (15)
S2	0.0213 (2)	0.0229 (2)	0.0209 (2)	−0.00350 (16)	−0.00005 (17)	0.00217 (16)
N1	0.0185 (7)	0.0276 (7)	0.0199 (7)	−0.0024 (6)	0.0025 (6)	0.0024 (6)
N2	0.0171 (6)	0.0260 (7)	0.0185 (7)	−0.0008 (6)	0.0021 (5)	0.0017 (5)
C1	0.0198 (8)	0.0196 (8)	0.0232 (9)	−0.0048 (6)	0.0025 (7)	−0.0012 (6)
C2	0.0160 (7)	0.0247 (8)	0.0224 (9)	−0.0007 (6)	−0.0003 (6)	−0.0022 (7)
C3	0.0249 (8)	0.0251 (9)	0.0208 (8)	0.0021 (7)	0.0027 (7)	0.0039 (7)
C4	0.0235 (8)	0.0267 (9)	0.0286 (9)	−0.0040 (7)	0.0072 (7)	0.0057 (7)
C5	0.0155 (7)	0.0267 (8)	0.0223 (9)	−0.0040 (6)	0.0025 (6)	−0.0008 (7)
C6	0.0189 (7)	0.0175 (7)	0.0159 (8)	−0.0003 (6)	0.0041 (6)	−0.0036 (6)
C7	0.0168 (7)	0.0184 (7)	0.0169 (8)	−0.0024 (6)	0.0052 (6)	−0.0038 (6)
C8	0.0172 (7)	0.0208 (8)	0.0140 (8)	0.0004 (6)	0.0010 (6)	−0.0040 (6)
C9	0.0194 (8)	0.0221 (8)	0.0207 (9)	0.0017 (6)	−0.0008 (7)	0.0015 (6)
C10	0.0184 (8)	0.0224 (8)	0.0194 (8)	0.0023 (6)	−0.0007 (6)	0.0003 (6)

Geometric parameters (Å, º) top

S1—C8	1.7289 (15)	C3—H3	0.9500
S1—C7	1.7400 (15)	C4—C5	1.388 (2)
S2—C8	1.7417 (16)	C4—H4	0.9500
S2—C9	1.8126 (15)	C5—C6	1.397 (2)
N1—C7	1.303 (2)	C5—H5	0.9500
N1—N2	1.3872 (17)	C6—C7	1.471 (2)
N2—C8	1.303 (2)	C9—C10	1.526 (2)
C1—C2	1.390 (2)	C9—H9A	0.9900
C1—C6	1.393 (2)	C9—H9B	0.9900
C1—H1	0.9500	C10—C10ⁱ	1.531 (3)
C2—C3	1.379 (2)	C10—H10A	0.9900
C2—H2	0.9500	C10—H10B	0.9900
C3—C4	1.391 (2)

C8—S1—C7	86.82 (7)	C1—C6—C7	120.63 (14)
C8—S2—C9	100.29 (7)	C5—C6—C7	120.18 (13)
C7—N1—N2	112.95 (13)	N1—C7—C6	124.58 (14)
C8—N2—N1	112.01 (12)	N1—C7—S1	113.64 (12)
C2—C1—C6	120.32 (15)	C6—C7—S1	121.78 (11)
C2—C1—H1	119.8	N2—C8—S1	114.58 (12)
C6—C1—H1	119.8	N2—C8—S2	126.30 (12)
C3—C2—C1	120.49 (14)	S1—C8—S2	119.11 (9)
C3—C2—H2	119.8	C10—C9—S2	112.94 (11)
C1—C2—H2	119.8	C10—C9—H9A	109.0
C2—C3—C4	119.44 (15)	S2—C9—H9A	109.0
C2—C3—H3	120.3	C10—C9—H9B	109.0
C4—C3—H3	120.3	S2—C9—H9B	109.0
C5—C4—C3	120.70 (15)	H9A—C9—H9B	107.8
C5—C4—H4	119.6	C9—C10—C10ⁱ	111.00 (16)
C3—C4—H4	119.6	C9—C10—H10A	109.4
C4—C5—C6	119.84 (15)	C10ⁱ—C10—H10A	109.4
C4—C5—H5	120.1	C9—C10—H10B	109.4
C6—C5—H5	120.1	C10ⁱ—C10—H10B	109.4
C1—C6—C5	119.19 (14)	H10A—C10—H10B	108.0

C7—N1—N2—C8	−0.54 (19)	C1—C6—C7—S1	6.9 (2)
C6—C1—C2—C3	1.7 (2)	C5—C6—C7—S1	−172.53 (12)
C1—C2—C3—C4	−0.9 (2)	C8—S1—C7—N1	0.48 (12)
C2—C3—C4—C5	0.2 (3)	C8—S1—C7—C6	−179.80 (13)
C3—C4—C5—C6	−0.2 (3)	N1—N2—C8—S1	0.93 (17)
C2—C1—C6—C5	−1.8 (2)	N1—N2—C8—S2	−179.93 (11)
C2—C1—C6—C7	178.80 (14)	C7—S1—C8—N2	−0.81 (13)
C4—C5—C6—C1	1.1 (2)	C7—S1—C8—S2	179.98 (10)
C4—C5—C6—C7	−179.52 (15)	C9—S2—C8—N2	−7.85 (16)
N2—N1—C7—C6	−179.79 (13)	C9—S2—C8—S1	171.26 (9)
N2—N1—C7—S1	−0.08 (17)	C8—S2—C9—C10	−75.00 (13)
C1—C6—C7—N1	−173.44 (15)	S2—C9—C10—C10ⁱ	−175.61 (14)
C5—C6—C7—N1	7.2 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···Cgⁱⁱ	0.99	2.70	3.540 (2)	144

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

Experimental details

Crystal data
Chemical formula	C₂₀H₁₈N₄S₄
M_r	442.62
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	5.7976 (7), 13.4393 (14), 12.9784 (12)
β (°)	99.120 (7)
V (Å³)	998.44 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.20 × 0.18 × 0.10

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.908, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	9992, 2384, 1870
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.088, 1.06
No. of reflections	2384
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.22

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

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···Cgⁱ	0.99	2.70	3.540 (2)	144

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

Acknowledgements

We gratefully acknowledge the support of the Key Laboratory Project of Liaoning Province (grant No. 2008S127) and the Doctoral Starting Foundation of Liaoning Province (grant No. 20071103).

References

Nakagawa, Y., Nishimura, K., Izumi, K., Kinoshita, K., Kimura, T. & Kurihara, N. (1996). J. Pestic. Sci. 21, 195–201. CrossRef CAS Google Scholar
Rigaku/MSC (2005). CrystalClear. Molecular Structure Corporation, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Y. G., Cao, L., Yan, J., Ye, W. F., Zhou, Q. C. & Lu, B. X. (1999). Chem. J. Chin. Univ. 20, 1903–1905. CAS Google Scholar
Wang, H., Gao, Y. & Wang, W. (2010). Acta Cryst. E66, o3085. Web of Science CSD CrossRef IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o681

doi:10.1107/S1600536811006064

Open

access