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Acta Crystallogr Sect E Struct Rep Online. 2008 April 1; 64(Pt 4): o709.
Published online 2008 March 14. doi:  10.1107/S1600536808006600
PMCID: PMC2960970

2,3,4-Tribromo­thio­phene

Abstract

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 [triangle]); Murakami et al. (2002 [triangle]); Xie et al. (1997 [triangle], 1998 [triangle]). For information on halogen(...)halogen contacts, see: Pedireddi et al. (1994 [triangle]). For details of the Cambridge Structural Database, see: Allen (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o709-scheme1.jpg

Experimental

Crystal data

  • C4HBr3S
  • M r = 320.84
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o709-efi1.jpg
  • 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 [triangle]) T min = 0.434, T max = 0.710
  • 12082 measured reflections
  • 2163 independent reflections
  • 1852 reflections with I > 2σ(I)
  • R int = 0.092
  • θmax = 23.7°

Refinement

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

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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.

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The crystals were small and very weakly diffracting and little data were obtainable beyond θ = 23°. This clearly contributes to the relatively high R factor and poor precision of the data in this determination. The C-bound H atoms were placed geometrically (C—H = 0.95 Å) and refined as riding with Uiso(H) = 1.2Ueq(C). A number of high peaks were found in the final difference map in the vicinity of the Br atoms in both molecules. The deepest hole is 0.98Å from Br3B.

Figures

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.

Crystal data

C4HBr3SF000 = 1168
Mr = 320.84Dx = 2.987 Mg m3
Orthorhombic, Pna21Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 1448 reflections
a = 12.4529 (11) Åθ = 3.4–21.9º
b = 3.9724 (4) ŵ = 17.14 mm1
c = 28.846 (3) ÅT = 91 (2) K
V = 1426.9 (2) Å3Plate, colourless
Z = 80.17 × 0.06 × 0.02 mm

Data collection

Bruker APEXII CCD area-detector diffractometer2163 independent reflections
Radiation source: fine-focus sealed tube1852 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.092
T = 91(2) Kθmax = 23.7º
ω scansθmin = 1.4º
Absorption correction: multi-scan(SADABS; Bruker, 2006)h = −14→14
Tmin = 0.434, Tmax = 0.710k = −4→4
12082 measured reflectionsl = −32→32

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.061  w = 1/[σ2(Fo2) + (0.1079P)2 + 95.665P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.172(Δ/σ)max = 0.001
S = 0.86Δρmax = 3.39 e Å3
2163 reflectionsΔρmin = −1.30 e Å3
109 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), 1050 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.11 (6)
Secondary atom site location: difference Fourier map

Special details

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)

xyzUiso*/Ueq
S1A0.6553 (5)0.6506 (19)0.2528 (2)0.0307 (15)
C1A0.723 (2)0.726 (7)0.2042 (10)0.0307 (15)
H1A0.79160.83110.20150.037*
C2A0.6527 (19)0.592 (6)0.1649 (8)0.0229 (6)
Br2A0.69172 (17)0.6009 (6)0.10260 (10)0.0229 (6)
C3A0.5527 (17)0.441 (7)0.1819 (9)0.021 (5)
Br3A0.44805 (17)0.2573 (6)0.14378 (10)0.0183 (7)
C4A0.5485 (18)0.455 (6)0.2298 (8)0.0197 (6)
Br4A0.43447 (16)0.3131 (7)0.26658 (9)0.0197 (6)
S1B0.6092 (5)0.3531 (17)0.3764 (2)0.0268 (14)
C1B0.542 (2)0.270 (6)0.4273 (10)0.0268 (14)
H1B0.47430.16170.43110.032*
C2B0.6136 (18)0.407 (7)0.4637 (8)0.0227 (6)
Br2B0.57498 (17)0.4088 (6)0.52692 (10)0.0227 (6)
C3B0.7118 (17)0.544 (6)0.4479 (8)0.016 (5)
Br3B0.82097 (17)0.7329 (6)0.48587 (10)0.0193 (7)
C4B0.7212 (17)0.523 (6)0.4001 (8)0.0206 (6)
Br4B0.83237 (18)0.6820 (7)0.36312 (9)0.0206 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S1A0.017 (3)0.039 (4)0.037 (4)0.000 (3)−0.004 (3)0.002 (3)
C1A0.017 (3)0.039 (4)0.037 (4)0.000 (3)−0.004 (3)0.002 (3)
C2A0.0147 (12)0.0294 (16)0.0246 (13)−0.0022 (10)0.0041 (10)0.0019 (12)
Br2A0.0147 (12)0.0294 (16)0.0246 (13)−0.0022 (10)0.0041 (10)0.0019 (12)
C3A0.005 (10)0.035 (14)0.024 (13)0.008 (10)−0.002 (9)−0.006 (12)
Br3A0.0104 (11)0.0209 (16)0.0237 (16)−0.0040 (9)−0.0040 (10)−0.0015 (9)
C4A0.0138 (12)0.0212 (11)0.0243 (14)−0.0028 (9)0.0055 (9)−0.0012 (14)
Br4A0.0138 (12)0.0212 (11)0.0243 (14)−0.0028 (9)0.0055 (9)−0.0012 (14)
S1B0.023 (3)0.023 (3)0.034 (4)0.004 (3)0.001 (3)−0.005 (3)
C1B0.023 (3)0.023 (3)0.034 (4)0.004 (3)0.001 (3)−0.005 (3)
C2B0.0142 (11)0.0305 (15)0.0235 (13)−0.0007 (10)0.0037 (10)0.0040 (12)
Br2B0.0142 (11)0.0305 (15)0.0235 (13)−0.0007 (10)0.0037 (10)0.0040 (12)
C3B0.016 (11)0.015 (11)0.017 (12)0.000 (9)0.000 (9)0.002 (10)
Br3B0.0090 (11)0.0200 (16)0.0290 (17)0.0022 (10)−0.0020 (10)−0.0028 (10)
C4B0.0125 (11)0.0198 (10)0.0295 (15)0.0030 (10)0.0056 (10)0.0023 (14)
Br4B0.0125 (11)0.0198 (10)0.0295 (15)0.0030 (10)0.0056 (10)0.0023 (14)

Geometric parameters (Å, °)

S1A—C4A1.68 (2)S1B—C4B1.69 (2)
S1A—C1A1.66 (3)S1B—C1B1.72 (3)
C1A—C2A1.53 (4)C1B—C2B1.48 (4)
C1A—H1A0.9500C1B—H1B0.9500
C2A—C3A1.47 (3)C2B—C3B1.41 (3)
C2A—Br2A1.86 (2)C2B—Br2B1.89 (2)
C3A—C4A1.38 (3)C3B—C4B1.39 (3)
C3A—Br3A1.86 (2)C3B—Br3B1.90 (2)
C4A—Br4A1.86 (2)C4B—Br4B1.86 (2)
C4A—S1A—C1A98.9 (13)C4B—S1B—C1B97.7 (12)
C2A—C1A—S1A105.5 (17)C2B—C1B—S1B103.8 (17)
C2A—C1A—H1A127.2C2B—C1B—H1B128.1
S1A—C1A—H1A127.2S1B—C1B—H1B128.1
C3A—C2A—C1A112 (2)C3B—C2B—C1B116 (2)
C3A—C2A—Br2A123.5 (18)C3B—C2B—Br2B122.1 (17)
C1A—C2A—Br2A123.9 (18)C1B—C2B—Br2B122.1 (18)
C4A—C3A—C2A110 (2)C4B—C3B—C2B112 (2)
C4A—C3A—Br3A125.6 (19)C4B—C3B—Br3B122.4 (17)
C2A—C3A—Br3A124.0 (19)C2B—C3B—Br3B125.8 (17)
C3A—C4A—S1A112.5 (18)C3B—C4B—S1B110.9 (17)
C3A—C4A—Br4A125.9 (18)C3B—C4B—Br4B127.9 (18)
S1A—C4A—Br4A121.4 (14)S1B—C4B—Br4B121.1 (14)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1A—H1A···Br3Ai0.953.043.89 (3)149
C1A—H1A···Br4Ai0.952.963.68 (3)134
C1B—H1B···Br3Bii0.952.933.79 (3)151
C1B—H1B···Br4Bii0.952.973.66 (2)131

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2706).

References

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