2,3,4-Tribromo­thio­phene

Kuriger, T.M.; Moratti, S.C.; Simpson, J.

doi:10.1107/S1600536808006600

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o709

doi:10.1107/S1600536808006600

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2,3,4-Tribromothiophene

Tony M. Kuriger,^a Stephen C. Moratti ^a and Jim Simpson ^a ^*

^aDepartment of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
^*Correspondence e-mail: jsimpson@alkali.otago.ac.nz

(Received 7 March 2008; accepted 9 March 2008; online 14 March 2008)

In the title compound, C₄HBr₃S, there are two essentially planar molecules in the asymmetric unit. In the crystal structure, bifurcated C—H⋯Br hydrogen bonds link the molecules into chains. Weak Br⋯Br interactions [Br⋯Br = 3.634 (4)–3.691 (4) Å] then lead to undulating sheets in the bc plane.

Related literature

For related polybromothiophene structures, see: Helmholdt et al. (2007 ); Murakami et al. (2002 ); Xie et al. (1997 , 1998 ). For information on halogen⋯halogen contacts, see: Pedireddi et al. (1994 ). For details of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₄HBr₃S
M_r = 320.84
Orthorhombic, P n a 2₁
a = 12.4529 (11) Å
b = 3.9724 (4) Å
c = 28.846 (3) Å
V = 1426.9 (2) Å³
Z = 8
Mo Kα radiation
μ = 17.14 mm⁻¹
T = 91 (2) K
0.17 × 0.06 × 0.02 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.434, T_max = 0.710
12082 measured reflections
2163 independent reflections
1852 reflections with I > 2σ(I)
R_int = 0.092
θ_max = 23.7°

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.172
S = 0.86
2163 reflections
109 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 3.39 e Å⁻³
Δρ_min = −1.30 e Å⁻³
Absolute structure: Flack (1983 ), 1050 Friedel pairs
Flack parameter: 0.11 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1A—H1A⋯Br3Aⁱ	0.95	3.04	3.89 (3)	149
C1A—H1A⋯Br4Aⁱ	0.95	2.96	3.68 (3)	134
C1B—H1B⋯Br3Bⁱⁱ	0.95	2.93	3.79 (3)	151
C1B—H1B⋯Br4Bⁱⁱ	0.95	2.97	3.66 (2)	131
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker 2006); cell refinement: APEX2 and SAINT (Bruker 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ) and TITAN (Hunter & Simpson, 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN; molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ) and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808006600/hb2706sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808006600/hb2706Isup2.hkl

checkCIF report

Comment top

Brominated thiophenes are very important intermediates in the construction of thiophene oligomers and polymers for use in optoelectronics. In some cases, it is important to have one or two α-positions free for further oxidative coupling. The 2,3,4-tribromo derivative is not easy to access, as the 2- and 5-positions are normally substituted first, and so it is normally synthesized via debromination from tetrabromothiophene (Xie et al., 1998).

The asymmetric unit of the title compound, (I), C₈H₂Br₆S₂, consists of two discrete tribromothiophene molecules A & B (Fig. 1). Each molecule is essentially planar with r.m.s. deviations from the mean planes through all non-hydrogen atoms of 0.0194 and 0.0286 Å for A and B respectively. The dihedral angle between the A and B ring planes is 0.9 (4)° but they are well separated with a centroid to centroid distance of 6.3 Å.

In the crystal of (I) bifurcated C—H···Br hydrogen bonds (Table 1) form chains of like molecules that pack in an obverse fashion along a. The structure is further stabilized by an extensive network of weak Br···Br interactions with Br···Br distances in the range 3.634 (4)Å (Br3A···Br2Bⁱ, i = 1 - x, 1 - y, -1/2 + z; θ₁ = 156.7° and θ₂ = 117.5°) (Pedireddi et al., 1994) to 3.691 (4)Å (Br3A···Br2Aⁱⁱ ii = -1/2 + x, 1/2 - y, z; θ₁ = 161.8° and θ₂ = 84.7°). These contacts link the chains of molecules into undulating sheets in the bc plane (Fig. 2).

Related literature top

For related polybromothiophene structures, see: Helmholdt et al. (2007); Murakami et al. (2002); Xie et al. (1997, 1998). For information on halogen···halogen contacts, see: Pedireddi et al. (1994). For related literature, see: Allen (2002).

Experimental top

2,3,4-Tribromothiophene, prepared by the method of Xie et al. (1998), was dissolved in methanol. Colourless plates of (I) were grown by slow diffusion of water into the solution.

Computing details top

Data collection: APEX2 (Bruker 2006); cell refinement: APEX2 (Bruker 2006) and SAINT (Bruker 2006); data reduction: SAINT (Bruker 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The asymmetric unit of (I), with 50% displacement ellipsoids for the non-hydrogen atoms.
	Fig. 2. Crystal packing of (I) with C—H···Br hydrogen bonds and Br···Br interactions drawn as dashed lines.

2,3,4-Tribromothiophene top

Crystal data top

C₄HBr₃S	F(000) = 1168
M_r = 320.84	D_x = 2.987 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 1448 reflections
a = 12.4529 (11) Å	θ = 3.4–21.9°
b = 3.9724 (4) Å	µ = 17.14 mm⁻¹
c = 28.846 (3) Å	T = 91 K
V = 1426.9 (2) Å³	Plate, colourless
Z = 8	0.17 × 0.06 × 0.02 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2163 independent reflections
Radiation source: fine-focus sealed tube	1852 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.092
ω scans	θ_max = 23.7°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −14→14
T_min = 0.434, T_max = 0.710	k = −4→4
12082 measured reflections	l = −32→32

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)] = 0.061	H-atom parameters constrained
wR(F²) = 0.172	w = 1/[σ²(F_o²) + (0.1079P)² + 95.665P] where P = (F_o² + 2F_c²)/3
S = 0.86	(Δ/σ)_max = 0.001
2163 reflections	Δρ_max = 3.39 e Å⁻³
109 parameters	Δρ_min = −1.30 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1050 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.11 (6)

Crystal data top

C₄HBr₃S	V = 1426.9 (2) Å³
M_r = 320.84	Z = 8
Orthorhombic, Pna2₁	Mo Kα radiation
a = 12.4529 (11) Å	µ = 17.14 mm⁻¹
b = 3.9724 (4) Å	T = 91 K
c = 28.846 (3) Å	0.17 × 0.06 × 0.02 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2163 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	1852 reflections with I > 2σ(I)
T_min = 0.434, T_max = 0.710	R_int = 0.092
12082 measured reflections	θ_max = 23.7°

Refinement top

R[F² > 2σ(F²)] = 0.061	H-atom parameters constrained
wR(F²) = 0.172	w = 1/[σ²(F_o²) + (0.1079P)² + 95.665P] where P = (F_o² + 2F_c²)/3
S = 0.86	Δρ_max = 3.39 e Å⁻³
2163 reflections	Δρ_min = −1.30 e Å⁻³
109 parameters	Absolute structure: Flack (1983), 1050 Friedel pairs
1 restraint	Absolute structure parameter: 0.11 (6)

Special details top

Experimental. As the crystals were small and very weakly diffracting, data were collected using 55 sec exposures per frame.

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
S1A	0.6553 (5)	0.6506 (19)	0.2528 (2)	0.0307 (15)
C1A	0.723 (2)	0.726 (7)	0.2042 (10)	0.0307 (15)
H1A	0.7916	0.8311	0.2015	0.037*
C2A	0.6527 (19)	0.592 (6)	0.1649 (8)	0.0229 (6)
Br2A	0.69172 (17)	0.6009 (6)	0.10260 (10)	0.0229 (6)
C3A	0.5527 (17)	0.441 (7)	0.1819 (9)	0.021 (5)
Br3A	0.44805 (17)	0.2573 (6)	0.14378 (10)	0.0183 (7)
C4A	0.5485 (18)	0.455 (6)	0.2298 (8)	0.0197 (6)
Br4A	0.43447 (16)	0.3131 (7)	0.26658 (9)	0.0197 (6)
S1B	0.6092 (5)	0.3531 (17)	0.3764 (2)	0.0268 (14)
C1B	0.542 (2)	0.270 (6)	0.4273 (10)	0.0268 (14)
H1B	0.4743	0.1617	0.4311	0.032*
C2B	0.6136 (18)	0.407 (7)	0.4637 (8)	0.0227 (6)
Br2B	0.57498 (17)	0.4088 (6)	0.52692 (10)	0.0227 (6)
C3B	0.7118 (17)	0.544 (6)	0.4479 (8)	0.016 (5)
Br3B	0.82097 (17)	0.7329 (6)	0.48587 (10)	0.0193 (7)
C4B	0.7212 (17)	0.523 (6)	0.4001 (8)	0.0206 (6)
Br4B	0.83237 (18)	0.6820 (7)	0.36312 (9)	0.0206 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.017 (3)	0.039 (4)	0.037 (4)	0.000 (3)	−0.004 (3)	0.002 (3)
C1A	0.017 (3)	0.039 (4)	0.037 (4)	0.000 (3)	−0.004 (3)	0.002 (3)
C2A	0.0147 (12)	0.0294 (16)	0.0246 (13)	−0.0022 (10)	0.0041 (10)	0.0019 (12)
Br2A	0.0147 (12)	0.0294 (16)	0.0246 (13)	−0.0022 (10)	0.0041 (10)	0.0019 (12)
C3A	0.005 (10)	0.035 (14)	0.024 (13)	0.008 (10)	−0.002 (9)	−0.006 (12)
Br3A	0.0104 (11)	0.0209 (16)	0.0237 (16)	−0.0040 (9)	−0.0040 (10)	−0.0015 (9)
C4A	0.0138 (12)	0.0212 (11)	0.0243 (14)	−0.0028 (9)	0.0055 (9)	−0.0012 (14)
Br4A	0.0138 (12)	0.0212 (11)	0.0243 (14)	−0.0028 (9)	0.0055 (9)	−0.0012 (14)
S1B	0.023 (3)	0.023 (3)	0.034 (4)	0.004 (3)	0.001 (3)	−0.005 (3)
C1B	0.023 (3)	0.023 (3)	0.034 (4)	0.004 (3)	0.001 (3)	−0.005 (3)
C2B	0.0142 (11)	0.0305 (15)	0.0235 (13)	−0.0007 (10)	0.0037 (10)	0.0040 (12)
Br2B	0.0142 (11)	0.0305 (15)	0.0235 (13)	−0.0007 (10)	0.0037 (10)	0.0040 (12)
C3B	0.016 (11)	0.015 (11)	0.017 (12)	0.000 (9)	0.000 (9)	0.002 (10)
Br3B	0.0090 (11)	0.0200 (16)	0.0290 (17)	0.0022 (10)	−0.0020 (10)	−0.0028 (10)
C4B	0.0125 (11)	0.0198 (10)	0.0295 (15)	0.0030 (10)	0.0056 (10)	0.0023 (14)
Br4B	0.0125 (11)	0.0198 (10)	0.0295 (15)	0.0030 (10)	0.0056 (10)	0.0023 (14)

Geometric parameters (Å, º) top

S1A—C4A	1.68 (2)	S1B—C4B	1.69 (2)
S1A—C1A	1.66 (3)	S1B—C1B	1.72 (3)
C1A—C2A	1.53 (4)	C1B—C2B	1.48 (4)
C1A—H1A	0.9500	C1B—H1B	0.9500
C2A—C3A	1.47 (3)	C2B—C3B	1.41 (3)
C2A—Br2A	1.86 (2)	C2B—Br2B	1.89 (2)
C3A—C4A	1.38 (3)	C3B—C4B	1.39 (3)
C3A—Br3A	1.86 (2)	C3B—Br3B	1.90 (2)
C4A—Br4A	1.86 (2)	C4B—Br4B	1.86 (2)

C4A—S1A—C1A	98.9 (13)	C4B—S1B—C1B	97.7 (12)
C2A—C1A—S1A	105.5 (17)	C2B—C1B—S1B	103.8 (17)
C2A—C1A—H1A	127.2	C2B—C1B—H1B	128.1
S1A—C1A—H1A	127.2	S1B—C1B—H1B	128.1
C3A—C2A—C1A	112 (2)	C3B—C2B—C1B	116 (2)
C3A—C2A—Br2A	123.5 (18)	C3B—C2B—Br2B	122.1 (17)
C1A—C2A—Br2A	123.9 (18)	C1B—C2B—Br2B	122.1 (18)
C4A—C3A—C2A	110 (2)	C4B—C3B—C2B	112 (2)
C4A—C3A—Br3A	125.6 (19)	C4B—C3B—Br3B	122.4 (17)
C2A—C3A—Br3A	124.0 (19)	C2B—C3B—Br3B	125.8 (17)
C3A—C4A—S1A	112.5 (18)	C3B—C4B—S1B	110.9 (17)
C3A—C4A—Br4A	125.9 (18)	C3B—C4B—Br4B	127.9 (18)
S1A—C4A—Br4A	121.4 (14)	S1B—C4B—Br4B	121.1 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1A—H1A···Br3Aⁱ	0.95	3.04	3.89 (3)	149
C1A—H1A···Br4Aⁱ	0.95	2.96	3.68 (3)	134
C1B—H1B···Br3Bⁱⁱ	0.95	2.93	3.79 (3)	151
C1B—H1B···Br4Bⁱⁱ	0.95	2.97	3.66 (2)	131

Symmetry codes: (i) x+1/2, −y+3/2, z; (ii) x−1/2, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₄HBr₃S
M_r	320.84
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	91
a, b, c (Å)	12.4529 (11), 3.9724 (4), 28.846 (3)
V (Å³)	1426.9 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	17.14
Crystal size (mm)	0.17 × 0.06 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.434, 0.710
No. of measured, independent and observed [I > 2σ(I)] reflections	12082, 2163, 1852
R_int	0.092
θ_max (°)	23.7
(sin θ/λ)_max (Å⁻¹)	0.566

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.172, 0.86
No. of reflections	2163
No. of parameters	109
No. of restraints	1
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.1079P)² + 95.665P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	3.39, −1.30
Absolute structure	Flack (1983), 1050 Friedel pairs
Absolute structure parameter	0.11 (6)

Computer programs: , APEX2 (Bruker 2006) and SAINT (Bruker 2006), SAINT (Bruker 2006), SHELXS97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999), SHELXL97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1A—H1A···Br3Aⁱ	0.95	3.04	3.89 (3)	149
C1A—H1A···Br4Aⁱ	0.95	2.96	3.68 (3)	134
C1B—H1B···Br3Bⁱⁱ	0.95	2.93	3.79 (3)	151
C1B—H1B···Br4Bⁱⁱ	0.95	2.97	3.66 (2)	131

Symmetry codes: (i) x+1/2, −y+3/2, z; (ii) x−1/2, −y+1/2, z.

Acknowledgements

This work was supported by grant No UOO-X0404 from the New Economy Research Fund of the New Zealand Foundation for Research Science and Technology. We also thank the University of Otago for the purchase of the diffractometer.

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