3,3′-Bithio­phene

Costa, J.C.S.; Gomes, L.R.; Santos, L.M.N.B.F.; Low, J.N.

doi:10.1107/S1600536810010342

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o916

doi:10.1107/S1600536810010342

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3,3′-Bithiophene

José C. S. Costa,^a Ligia R. Gomes,^b Luís M. N. B. F. Santos ^a and John Nicolson Low ^c ^*

^aCentro de Investigação em Química, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre, 687, P-4169 007 Porto, Portugal, ^bREQUIMTE , Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre, 687, P-4169 007 Porto, Portugal, and ^cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: jnlow111@googlemail.com

(Received 10 March 2010; accepted 19 March 2010; online 24 March 2010)

The title compound, C₈H₆S₂, is disordered [occupancy ratio = 0.839 (2):0.161 (2)] and sits across a centre of symmetry. In the crystal, the molecules are linked by a weak C—H⋯π interaction.

Related literature

For a discussion of the disorder in this compound, see: Visser et al. (1968 ). For thiophene C–S bond distances, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₆S₂
M_r = 166.25
Orthorhombic, P c c n
a = 7.5187 (7) Å
b = 18.2181 (17) Å
c = 5.5029 (5) Å
V = 753.77 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.62 mm⁻¹
T = 150 K
0.60 × 0.40 × 0.04 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.709, T_max = 0.976
11635 measured reflections
1151 independent reflections
987 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.101
S = 1.10
1151 reflections
59 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg and Cg′ are the centroids of the thiophene ring in the major and minor occupancy disorder components, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cgⁱ	0.95	2.86	3.6039 (17)	136
C2—H2⋯Cg′ⁱ	0.95	2.86	3.607 (5)	136
Symmetry code: (i) $[-x+{\script{1\over 2}}, y, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810010342/om2327sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810010342/om2327Isup2.hkl

checkCIF report

Comment top

The disorder in the title compound was discussed briefly by Visser et al. (1968). However, this paper gives no coordinates and the structure determination was at room temperature. This is a low temerature determination. A view of the major, 0.839 (2), site occupancy, and minor, 0.161 (2), site occupancy, components are shown in Fig. 1. There is a weak C–H···π interaction, C2–H2···Cg(thiophene) (0.5-x, y, z-0.5) in which H2···Cg is 2.86Å and C2···Cg is 3.6039 (17) Å. The angle at H2 ia 136° for the major component. The C2···Cg2 distance for the minor component is 3.607 (5) Å. The H2···Cg distance and angle at H2 are the same.

Related literature top

For a discussion of the disorder in this compound, see: Visser et al. (1968). For thiophene C–S bond distances, see: Allen et al. (1987).

Experimental top

The compound was obtained commercially and re-crystallised from dichloromethane.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title compound with our numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The molecule sits across the centre-of-symmetry at (0.5,0.5,0.5). The bonds in the minor component are marked as dotted lines.

3,3'-bithiophene top

Crystal data top

C₈H₆S₂	D_x = 1.465 Mg m⁻³
M_r = 166.25	Melting point: 406 K
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
a = 7.5187 (7) Å	Cell parameters from 124 reflections
b = 18.2181 (17) Å	θ = 2.8–30.5°
c = 5.5029 (5) Å	µ = 0.62 mm⁻¹
V = 753.77 (12) Å³	T = 150 K
Z = 4	Plate, yellow
F(000) = 344	0.60 × 0.40 × 0.04 mm

Data collection top

Bruker SMART APEXII diffractometer	1151 independent reflections
Radiation source: fine-focus sealed tube	987 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω scans	θ_max = 30.6°, θ_min = 4.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→10
T_min = 0.709, T_max = 0.976	k = −23→26
11635 measured reflections	l = −7→7

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0478P)² + 0.3736P] where P = (F_o² + 2F_c²)/3
1151 reflections	(Δ/σ)_max = 0.001
59 parameters	Δρ_max = 0.48 e Å⁻³
6 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₈H₆S₂	V = 753.77 (12) Å³
M_r = 166.25	Z = 4
Orthorhombic, Pccn	Mo Kα radiation
a = 7.5187 (7) Å	µ = 0.62 mm⁻¹
b = 18.2181 (17) Å	T = 150 K
c = 5.5029 (5) Å	0.60 × 0.40 × 0.04 mm

Data collection top

Bruker SMART APEXII diffractometer	1151 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	987 reflections with I > 2σ(I)
T_min = 0.709, T_max = 0.976	R_int = 0.039
11635 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	6 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.10	Δρ_max = 0.48 e Å⁻³
1151 reflections	Δρ_min = −0.33 e Å⁻³
59 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.44974 (10)	0.67774 (2)	0.55925 (11)	0.03155 (18)	0.839 (2)
C5A	0.446 (2)	0.6612 (2)	0.5331 (18)	0.0246 (5)	0.161 (2)
H5A	0.4003	0.7061	0.4718	0.030*	0.161 (2)
C2	0.4207 (2)	0.59508 (6)	0.4154 (2)	0.0255 (3)
H2	0.3574	0.5891	0.2673	0.031*
C3	0.50025 (17)	0.53842 (7)	0.5407 (2)	0.0199 (3)
C4	0.58337 (19)	0.56308 (7)	0.7572 (3)	0.0262 (3)
H4	0.6439	0.5314	0.8666	0.031*
C5	0.5674 (8)	0.63775 (10)	0.7926 (7)	0.0246 (5)	0.839 (2)
H5	0.6150	0.6636	0.9277	0.030*	0.839 (2)
S1A	0.5658 (13)	0.65626 (13)	0.7988 (13)	0.0391 (12)	0.161 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0353 (3)	0.0217 (2)	0.0377 (3)	0.0028 (2)	0.0068 (2)	0.00256 (18)
C5A	0.0243 (10)	0.0215 (10)	0.0279 (10)	−0.0028 (13)	0.0000 (8)	−0.0033 (10)
C2	0.0264 (7)	0.0274 (6)	0.0227 (6)	0.0032 (5)	0.0010 (5)	0.0039 (5)
C3	0.0152 (6)	0.0247 (6)	0.0198 (6)	0.0022 (5)	0.0025 (5)	0.0022 (5)
C4	0.0234 (7)	0.0303 (7)	0.0249 (6)	0.0026 (5)	−0.0034 (5)	−0.0015 (5)
C5	0.0243 (10)	0.0215 (10)	0.0279 (10)	−0.0028 (13)	0.0000 (8)	−0.0033 (10)
S1A	0.040 (2)	0.0276 (17)	0.049 (2)	−0.001 (2)	0.0038 (15)	−0.0074 (17)

Geometric parameters (Å, º) top

S1—C2	1.7152 (9)	C3—C4	1.4181 (19)
S1—C5	1.7215 (10)	C3—C3ⁱ	1.470 (3)
C5A—C2	1.3802 (10)	C4—C5	1.3794 (10)
C5A—S1A	1.7203 (10)	C4—S1A	1.7180 (10)
C5A—H5A	0.9500	C4—H4	0.9500
C2—C3	1.3778 (19)	C5—H5	0.9500
C2—H2	0.9500

C2—S1—C5	92.19 (8)	C4—C3—C3ⁱ	123.98 (15)
C2—C5A—S1A	115.2 (3)	C5—C4—C3	113.15 (13)
C2—C5A—H5A	122.4	C3—C4—S1A	113.04 (17)
S1A—C5A—H5A	122.4	C5—C4—H4	123.4
C3—C2—C5A	111.1 (2)	C3—C4—H4	123.4
C3—C2—S1	111.81 (10)	S1A—C4—H4	123.5
C3—C2—H2	124.1	C4—C5—S1	110.87 (12)
C5A—C2—H2	124.9	C4—C5—H5	124.6
S1—C2—H2	124.1	S1—C5—H5	124.6
C2—C3—C4	111.98 (11)	C4—S1A—C5A	88.8 (2)
C2—C3—C3ⁱ	124.05 (15)

S1A—C5A—C2—C3	−0.2 (15)	C3ⁱ—C3—C4—C5	179.3 (3)
C5—S1—C2—C3	−0.6 (3)	C2—C3—C4—S1A	−1.3 (5)
C5A—C2—C3—C4	1.0 (8)	C3ⁱ—C3—C4—S1A	178.5 (4)
S1—C2—C3—C4	0.73 (16)	C3—C4—C5—S1	0.1 (5)
C5A—C2—C3—C3ⁱ	−178.8 (8)	C2—S1—C5—C4	0.3 (4)
S1—C2—C3—C3ⁱ	−179.03 (14)	C3—C4—S1A—C5A	1.0 (10)
C2—C3—C4—C5	−0.5 (3)	C2—C5A—S1A—C4	−0.4 (14)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg and Cg' are the centroids of the thiophene ring in the major and minor occupancy disorder components, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cgⁱⁱ	0.95	2.86	3.6039 (17)	136
C2—H2···Cg'ⁱⁱ	0.95	2.86	3.607 (5)	136

Symmetry code: (ii) −x+1/2, y, z−1/2.

Experimental details

Crystal data
Chemical formula	C₈H₆S₂
M_r	166.25
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	150
a, b, c (Å)	7.5187 (7), 18.2181 (17), 5.5029 (5)
V (Å³)	753.77 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.62
Crystal size (mm)	0.60 × 0.40 × 0.04

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.709, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	11635, 1151, 987
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.716

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.101, 1.10
No. of reflections	1151
No. of parameters	59
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.33

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg and Cg' are the centroids of the thiophene ring in the major and minor occupancy disorder components, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cgⁱ	0.95	2.86	3.6039 (17)	136
C2—H2···Cg'ⁱ	0.95	2.86	3.607 (5)	136

Symmetry code: (i) −x+1/2, y, z−1/2.

Acknowledgements

LRG thanks the Fundação para o Ensino e Cultura Fernando Pessoa for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2004). APEXII, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Visser, G. J., Heeres, G. J., Wolters, J. & Vos, A. (1968). Acta Cryst. B24, 467–473. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar