5,5′-Diphenyl-2,2′-[butane-1,4-diylbis(sulfanedi­yl)]bis­(1,3,4-oxadiazole)

Wang, W.; Qiu, H.; Gao, Y.; Yao, H.-G.; Ji, M.

doi:10.1107/S1600536810042315

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2931

https://doi.org/10.1107/S1600536810042315

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5,5′-Diphenyl-2,2′-[butane-1,4-diylbis(sulfanediyl)]bis(1,3,4-oxadiazole)

Wei Wang,^a,^b ^* Hong Qiu,^b Yan Gao,^b Hong-Guo Yao ^b and Ming Ji ^c

^aSchool of Perfume and Aroma Technology, Shanghai Institute of Technology, Shanghai 200235, People's Republic of China, ^bSchool of Chemical Engineering, University of Science and Technology LiaoNing, Anshan 114051, People's Republic of China, and ^cLiaoyang Supervision and Examination Station of Product Quality, Liaoning Liaoyang 111000, People's Republic of China
^*Correspondence e-mail: zhao_submit@yahoo.com.cn

(Received 3 October 2010; accepted 19 October 2010; online 23 October 2010)

The complete molecule of the title compound, C₂₀H₁₈N₄O₂S₂, is generated by crystallographic inversion symmetry. The benzene ring is almost coplanar with the oxadiazole ring [dihedral angle = 7.2 (2)°].

Related literature

Experimental

Crystal data

C₂₀H₁₈N₄O₂S₂
M_r = 410.50
Monoclinic, P 2₁ /c
a = 12.202 (2) Å
b = 5.9317 (12) Å
c = 13.518 (3) Å
β = 104.04 (3)°
V = 949.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.942, T_max = 0.964
7030 measured reflections
1661 independent reflections
1323 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.128
S = 1.10
1661 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.33 e Å⁻³

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/S1600536810042315/zs2072sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042315/zs2072Isup2.hkl

checkCIF report

Comment top

Functionalized 1,3,4-oxadiazole derivatives are of interest because of their biological activity and their wide applications in medicine, coordination chemistry and their use as organic electroluminescent (EL) devices, since these compounds possess good electron-accepting properties (Bentiss et al., 2000; Navidpour et al., 2006; Hughes & Bryce, 2005). We report here the synthesis and crystal structure of the title compound, C₂₀H₁₈N₄O₂S₂ (I). In the structure of the title compound the molecule has an inversion centre at the mid-point of the central C10—C10ⁱ bond (symmetry code for (i): -x + 1,-y + 3, -z + 1), the asymmetric unit containing half a molecule (Fig. 1). The mean plane of the oxadiazole ring is almost coplanar with the mean plane of the attached benzene ring [dihedral angle 7.2 (2)°]. As a result of π-π conjugation, the C_sp²-S bond [S1—C8 = 1.729 (2) Å] is significantly shorter than the C_sp³-S bond [S1—C9 = 1.818 (2) Å].

Related literature top

Experimental top

A suspension of 5-phenyl-1,3,4-oxadiazole-2-thiol (2.0 mmol) and 1,4-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 title compound as a light yellow solid in 93% 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

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. A view of the molecule of (I) showing the atom-labelling scheme. Atoms of the inversion-related atoms are indicated by symmetry code 'A' (-x + 1,-y + 3, -z + 1). Displacement ellipsoids are drawn at the 35% probability level.

5,5'-diphenyl-2,2'-[butane-1,4-diylbis(sulfanediyl)]bis(1,3,4-oxadiazole) top

Crystal data top

C₂₀H₁₈N₄O₂S₂	F(000) = 428
M_r = 410.50	D_x = 1.436 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3017 reflections
a = 12.202 (2) Å	θ = 1.7–27.9°
b = 5.9317 (12) Å	µ = 0.31 mm⁻¹
c = 13.518 (3) Å	T = 113 K
β = 104.04 (3)°	Prism, colorless
V = 949.2 (3) Å³	0.20 × 0.18 × 0.12 mm
Z = 2

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1661 independent reflections
Radiation source: rotating anode	1323 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.053
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 1.7°
φ and ω scans	h = −12→14
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −7→6
T_min = 0.942, T_max = 0.964	l = −16→16
7030 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.128	w = 1/[σ²(F_o²) + (0.0778P)²] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1661 reflections	Δρ_max = 0.28 e Å⁻³
128 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.067 (10)

Crystal data top

C₂₀H₁₈N₄O₂S₂	V = 949.2 (3) Å³
M_r = 410.50	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.202 (2) Å	µ = 0.31 mm⁻¹
b = 5.9317 (12) Å	T = 113 K
c = 13.518 (3) Å	0.20 × 0.18 × 0.12 mm
β = 104.04 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1661 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1323 reflections with I > 2σ(I)
T_min = 0.942, T_max = 0.964	R_int = 0.053
7030 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.10	Δρ_max = 0.28 e Å⁻³
1661 reflections	Δρ_min = −0.33 e Å⁻³
128 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	0.43518 (5)	1.09305 (10)	0.65529 (4)	0.0256 (3)
O1	0.30541 (12)	0.7504 (3)	0.68093 (12)	0.0210 (4)
N1	0.19647 (17)	0.6825 (3)	0.52644 (14)	0.0265 (5)
N2	0.26743 (17)	0.8685 (3)	0.51955 (14)	0.0242 (5)
C1	0.2073 (2)	0.3923 (4)	0.77192 (18)	0.0278 (6)
H1	0.2568	0.4939	0.8155	0.033*
C2	0.1655 (2)	0.2040 (4)	0.81204 (19)	0.0292 (6)
H2	0.1869	0.1762	0.8834	0.035*
C3	0.0925 (2)	0.0563 (4)	0.7481 (2)	0.0291 (6)
H3	0.0657	−0.0740	0.7757	0.035*
C4	0.0589 (2)	0.0987 (4)	0.64463 (19)	0.0278 (6)
H4	0.0071	−0.0001	0.6016	0.033*
C5	0.1004 (2)	0.2843 (4)	0.60345 (18)	0.0258 (6)
H5	0.0778	0.3123	0.5322	0.031*
C6	0.17557 (19)	0.4300 (4)	0.66720 (17)	0.0185 (6)
C7	0.22137 (19)	0.6207 (4)	0.62076 (17)	0.0193 (6)
C8	0.3285 (2)	0.8996 (4)	0.61119 (17)	0.0214 (6)
C9	0.4184 (2)	1.2482 (4)	0.53652 (18)	0.0235 (6)
H9A	0.4274	1.1445	0.4817	0.028*
H9B	0.3417	1.3145	0.5166	0.028*
C10	0.5064 (2)	1.4340 (4)	0.55008 (17)	0.0216 (6)
H10A	0.5829	1.3674	0.5705	0.026*
H10B	0.4970	1.5378	0.6048	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0253 (4)	0.0301 (5)	0.0194 (4)	−0.0069 (3)	0.0015 (3)	0.0035 (2)
O1	0.0202 (9)	0.0232 (9)	0.0192 (9)	−0.0025 (7)	0.0038 (7)	0.0028 (6)
N1	0.0304 (12)	0.0260 (12)	0.0215 (11)	−0.0067 (10)	0.0035 (9)	−0.0009 (9)
N2	0.0293 (12)	0.0238 (11)	0.0191 (11)	−0.0046 (9)	0.0056 (9)	0.0011 (8)
C1	0.0193 (14)	0.0368 (16)	0.0239 (14)	−0.0036 (11)	−0.0014 (11)	0.0017 (10)
C2	0.0258 (14)	0.0363 (16)	0.0244 (13)	−0.0007 (12)	0.0039 (11)	0.0127 (11)
C3	0.0250 (14)	0.0234 (13)	0.0418 (16)	0.0021 (11)	0.0138 (12)	0.0038 (11)
C4	0.0325 (16)	0.0220 (14)	0.0316 (15)	−0.0059 (11)	0.0129 (12)	−0.0073 (10)
C5	0.0288 (14)	0.0296 (15)	0.0207 (13)	−0.0018 (11)	0.0093 (11)	−0.0062 (10)
C6	0.0180 (13)	0.0179 (13)	0.0214 (12)	0.0033 (10)	0.0084 (10)	−0.0013 (9)
C7	0.0160 (13)	0.0238 (14)	0.0171 (12)	0.0010 (10)	0.0020 (10)	−0.0039 (9)
C8	0.0202 (13)	0.0241 (14)	0.0196 (12)	0.0000 (10)	0.0045 (10)	0.0019 (9)
C9	0.0249 (13)	0.0244 (13)	0.0199 (12)	−0.0010 (11)	0.0031 (10)	0.0054 (10)
C10	0.0225 (13)	0.0212 (13)	0.0199 (13)	0.0021 (10)	0.0031 (10)	−0.0018 (9)

Geometric parameters (Å, º) top

S1—C8	1.729 (2)	C3—H3	0.9500
S1—C9	1.818 (2)	C4—C5	1.384 (3)
O1—C8	1.371 (3)	C4—H4	0.9500
O1—C7	1.378 (3)	C5—C6	1.396 (3)
N1—C7	1.290 (3)	C5—H5	0.9500
N1—N2	1.419 (3)	C6—C7	1.468 (3)
N2—C8	1.295 (3)	C9—C10	1.518 (3)
C1—C2	1.391 (3)	C9—H9A	0.9900
C1—C6	1.392 (3)	C9—H9B	0.9900
C1—H1	0.9500	C10—C10ⁱ	1.539 (4)
C2—C3	1.390 (4)	C10—H10A	0.9900
C2—H2	0.9500	C10—H10B	0.9900
C3—C4	1.382 (3)

C8—S1—C9	96.73 (11)	C1—C6—C7	121.2 (2)
C8—O1—C7	101.66 (17)	C5—C6—C7	118.3 (2)
C7—N1—N2	106.53 (18)	N1—C7—O1	112.81 (19)
C8—N2—N1	105.48 (18)	N1—C7—C6	128.2 (2)
C2—C1—C6	119.2 (2)	O1—C7—C6	118.9 (2)
C2—C1—H1	120.4	N2—C8—O1	113.5 (2)
C6—C1—H1	120.4	N2—C8—S1	129.42 (18)
C3—C2—C1	120.2 (2)	O1—C8—S1	117.02 (17)
C3—C2—H2	119.9	C10—C9—S1	109.62 (17)
C1—C2—H2	119.9	C10—C9—H9A	109.7
C4—C3—C2	120.2 (2)	S1—C9—H9A	109.7
C4—C3—H3	119.9	C10—C9—H9B	109.7
C2—C3—H3	119.9	S1—C9—H9B	109.7
C3—C4—C5	120.3 (2)	H9A—C9—H9B	108.2
C3—C4—H4	119.9	C9—C10—C10ⁱ	110.2 (2)
C5—C4—H4	119.9	C9—C10—H10A	109.6
C4—C5—C6	119.6 (2)	C10ⁱ—C10—H10A	109.6
C4—C5—H5	120.2	C9—C10—H10B	109.6
C6—C5—H5	120.2	C10ⁱ—C10—H10B	109.6
C1—C6—C5	120.5 (2)	H10A—C10—H10B	108.1

C7—N1—N2—C8	0.1 (2)	C1—C6—C7—N1	−176.7 (2)
C6—C1—C2—C3	−0.4 (4)	C5—C6—C7—N1	4.3 (4)
C1—C2—C3—C4	−1.5 (4)	C1—C6—C7—O1	6.5 (3)
C2—C3—C4—C5	2.0 (4)	C5—C6—C7—O1	−172.54 (19)
C3—C4—C5—C6	−0.6 (4)	N1—N2—C8—O1	−0.1 (3)
C2—C1—C6—C5	1.8 (3)	N1—N2—C8—S1	177.74 (17)
C2—C1—C6—C7	−177.2 (2)	C7—O1—C8—N2	0.0 (2)
C4—C5—C6—C1	−1.3 (3)	C7—O1—C8—S1	−178.11 (15)
C4—C5—C6—C7	177.7 (2)	C9—S1—C8—N2	6.4 (2)
N2—N1—C7—O1	−0.1 (2)	C9—S1—C8—O1	−175.89 (17)
N2—N1—C7—C6	−177.1 (2)	C8—S1—C9—C10	−178.33 (17)
C8—O1—C7—N1	0.1 (2)	S1—C9—C10—C10ⁱ	179.7 (2)
C8—O1—C7—C6	177.40 (19)

Symmetry code: (i) −x+1, −y+3, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₈N₄O₂S₂
M_r	410.50
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	12.202 (2), 5.9317 (12), 13.518 (3)
β (°)	104.04 (3)
V (Å³)	949.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.20 × 0.18 × 0.12

Data collection
Diffractometer	Rigaku Saturn CCD area-detector
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.942, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	7030, 1661, 1323
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.128, 1.10
No. of reflections	1661
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.33

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

Acknowledgements

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

References

Bentiss, F., Traisnel, M. & Lagrenee, M. (2000). Corros. Sci. 42, 127–146. Web of Science CrossRef CAS Google Scholar
Hughes, G. & Bryce, M. R. (2005). J. Mater. Chem. 15, 94–107. Web of Science CrossRef CAS Google Scholar
Navidpour, L., Shafaroodi, H., Abdi, K., Amini, M., Ghahremani, M. H., Dehpour, A. R. & Shafiee, A. (2006). Bioorg. Med. Chem. 14, 2507–2517. Web of Science CrossRef PubMed 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