Acta Cryst. (2009). E65, o2119 [ doi:10.1107/S1600536809030864 ]
In the crystal structure of the title compound, C12H6Br2S3, the molecules are planar (r.m.s. deviation = 0.06 Å). Consecutive molecules do not stack in a planar fashion. There is an angle of 81.7 (12)° between the planes of the closest molecules.
Synthesis was carried out following literature procedures (Hoffman) as follows: to a a solution of terthiophene dissolved in chloroform was added 2 equivalents of N-bromosuccinimde and the reaction mixture was stirred at room temperature for 2 h. The reaction mixture was then extracted with water and product obtained by evaporation of chloroform and recrystallized twice from hexanes. The crystals were very thin, hence the large number in the second weighting scheme.
The structure was solved using SHELXS97 and refined using SHELXL97 (Sheldrick, 2008). The space group Pcc2 was determined based on systematic absences and intensity statistics. A direct-methods solution was calculated which provided most non-hydrogen atoms from the E-map. Full-matrix least squares / difference Fourier cycles were performed which located the remaining non-hydrogen atoms. All non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were placed in ideal positions and refined as riding atoms with relative isotropic displacement parameters. The final full matrix least squares refinement converged to R1 = 0.0527 and wR2 = 0.1169 (F2, all data).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).
![[Figure 1]](./ng2619fig1thm.gif)
| Fig. 1. 2,5-bis(5-bromothiophen-2-yl)thiophene. |
![[Figure 2]](./ng2619fig2thm.gif)
| Fig. 2. Crystal packing viewed along the a axis. |
| C12H6Br2S3 | F(000) = 784 |
| Mr = 406.17 | Dx = 2.005 Mg m−3 |
| Orthorhombic, Pcc2 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2 -2c | Cell parameters from 903 reflections |
| a = 7.6216 (16) Å | θ = 2.7–27.5° |
| b = 30.003 (6) Å | µ = 6.46 mm−1 |
| c = 5.8841 (13) Å | T = 173 K |
| V = 1345.5 (5) Å3 | Plate, pale yellow |
| Z = 4 | 0.37 × 0.24 × 0.10 mm |
| Siemens SMART Platform CCD diffractometer | 3045 independent reflections |
| Radiation source: fine-focus sealed tube | 2818 reflections with I > 2σ(I) |
| graphite | Rint = 0.035 |
| ω scans | θmax = 27.5°, θmin = 2.7° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2008a) | h = −9→9 |
| Tmin = 0.184, Tmax = 0.524 | k = −38→38 |
| 9565 measured reflections | l = −7→7 |
| 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)] = 0.053 | H-atom parameters constrained |
| wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0403P)2 + 2.9087P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.25 | (Δ/σ)max = 0.001 |
| 3045 reflections | Δρmax = 1.24 e Å−3 |
| 155 parameters | Δρmin = −0.62 e Å−3 |
| 1 restraint | Absolute structure: Flack (1983), 1341 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.00 (7) |
| C12H6Br2S3 | V = 1345.5 (5) Å3 |
| Mr = 406.17 | Z = 4 |
| Orthorhombic, Pcc2 | Mo Kα radiation |
| a = 7.6216 (16) Å | µ = 6.46 mm−1 |
| b = 30.003 (6) Å | T = 173 K |
| c = 5.8841 (13) Å | 0.37 × 0.24 × 0.10 mm |
| Siemens SMART Platform CCD diffractometer | 3045 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2008a) | 2818 reflections with I > 2σ(I) |
| Tmin = 0.184, Tmax = 0.524 | Rint = 0.035 |
| 9565 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
| wR(F2) = 0.114 | Δρmax = 1.24 e Å−3 |
| S = 1.25 | Δρmin = −0.62 e Å−3 |
| 3045 reflections | Absolute structure: Flack (1983), 1341 Friedel pairs |
| 155 parameters | Flack parameter: 0.00 (7) |
| 1 restraint |
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. The structure refined as a merohedral inversion twin, whose mass ratio converged to 61:39. |
| x | y | z | Uiso*/Ueq | ||
| Br1 | 0.69877 (9) | 0.96042 (2) | 1.02236 (11) | 0.0374 (2) | |
| Br2 | 0.71126 (13) | 0.54014 (2) | 0.07093 (13) | 0.0532 (3) | |
| S1 | 0.6713 (2) | 0.86007 (5) | 0.9031 (3) | 0.0271 (3) | |
| S2 | 0.81817 (19) | 0.76622 (5) | 0.3646 (3) | 0.0232 (3) | |
| S3 | 0.6749 (2) | 0.62433 (5) | 0.3757 (3) | 0.0279 (3) | |
| C1 | 0.7418 (8) | 0.9124 (2) | 0.8288 (11) | 0.0253 (13) | |
| C2 | 0.8278 (8) | 0.9124 (2) | 0.6263 (12) | 0.0287 (14) | |
| H2 | 0.8761 | 0.9384 | 0.5584 | 0.034* | |
| C3 | 0.8376 (7) | 0.86976 (19) | 0.5284 (11) | 0.0238 (12) | |
| H3 | 0.8933 | 0.8642 | 0.3868 | 0.029* | |
| C4 | 0.7597 (7) | 0.8370 (2) | 0.6553 (10) | 0.0215 (12) | |
| C5 | 0.7360 (7) | 0.7908 (2) | 0.6122 (10) | 0.0172 (12) | |
| C6 | 0.6539 (7) | 0.75937 (18) | 0.7416 (10) | 0.0197 (12) | |
| H6 | 0.6009 | 0.7660 | 0.8838 | 0.024* | |
| C7 | 0.6546 (7) | 0.71661 (19) | 0.6471 (10) | 0.0201 (12) | |
| H7 | 0.6016 | 0.6916 | 0.7182 | 0.024* | |
| C8 | 0.7397 (8) | 0.71439 (19) | 0.4407 (12) | 0.0190 (12) | |
| C9 | 0.7621 (7) | 0.67576 (19) | 0.2972 (10) | 0.0175 (11) | |
| C10 | 0.8467 (8) | 0.6726 (2) | 0.0932 (10) | 0.0233 (12) | |
| H10 | 0.9036 | 0.6972 | 0.0231 | 0.028* | |
| C11 | 0.8421 (8) | 0.62914 (19) | −0.0055 (11) | 0.0249 (12) | |
| H11 | 0.8927 | 0.6216 | −0.1479 | 0.030* | |
| C12 | 0.7553 (9) | 0.5999 (2) | 0.1323 (12) | 0.0269 (13) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0447 (4) | 0.0317 (4) | 0.0359 (4) | 0.0053 (3) | 0.0051 (4) | −0.0089 (3) |
| Br2 | 0.0814 (7) | 0.0272 (4) | 0.0512 (7) | −0.0077 (4) | 0.0045 (5) | −0.0099 (4) |
| S1 | 0.0315 (8) | 0.0282 (7) | 0.0217 (8) | −0.0025 (6) | 0.0079 (6) | −0.0021 (6) |
| S2 | 0.0252 (7) | 0.0259 (7) | 0.0185 (7) | −0.0031 (6) | 0.0045 (6) | 0.0006 (6) |
| S3 | 0.0338 (8) | 0.0234 (7) | 0.0263 (8) | −0.0046 (6) | 0.0066 (7) | 0.0012 (7) |
| C1 | 0.028 (3) | 0.025 (3) | 0.023 (3) | 0.002 (2) | −0.005 (3) | −0.003 (3) |
| C2 | 0.023 (3) | 0.029 (3) | 0.035 (3) | −0.002 (2) | −0.003 (3) | 0.009 (3) |
| C3 | 0.026 (3) | 0.024 (3) | 0.021 (3) | 0.000 (2) | 0.006 (3) | 0.004 (3) |
| C4 | 0.018 (3) | 0.030 (3) | 0.017 (3) | 0.003 (2) | 0.000 (2) | 0.000 (2) |
| C5 | 0.012 (3) | 0.026 (3) | 0.013 (3) | −0.001 (2) | −0.003 (2) | −0.004 (2) |
| C6 | 0.019 (3) | 0.023 (3) | 0.017 (3) | −0.001 (2) | −0.001 (2) | 0.001 (2) |
| C7 | 0.012 (3) | 0.026 (3) | 0.022 (3) | 0.000 (2) | −0.001 (2) | 0.005 (2) |
| C8 | 0.014 (2) | 0.017 (3) | 0.026 (3) | −0.002 (2) | 0.004 (2) | 0.010 (2) |
| C9 | 0.016 (3) | 0.015 (3) | 0.021 (3) | 0.002 (2) | −0.001 (2) | 0.000 (2) |
| C10 | 0.020 (3) | 0.029 (3) | 0.021 (3) | 0.002 (2) | −0.001 (2) | 0.003 (2) |
| C11 | 0.028 (3) | 0.023 (3) | 0.024 (3) | 0.005 (2) | 0.004 (3) | −0.006 (2) |
| C12 | 0.035 (3) | 0.022 (3) | 0.024 (3) | −0.004 (3) | 0.000 (3) | −0.006 (3) |
| Br1—C1 | 1.864 (6) | C4—C5 | 1.419 (8) |
| Br2—C12 | 1.858 (6) | C5—C6 | 1.365 (8) |
| S1—C1 | 1.717 (7) | C6—C7 | 1.398 (8) |
| S1—C4 | 1.749 (6) | C6—H6 | 0.9500 |
| S2—C8 | 1.725 (6) | C7—C8 | 1.379 (9) |
| S2—C5 | 1.750 (6) | C7—H7 | 0.9500 |
| S3—C12 | 1.722 (7) | C8—C9 | 1.444 (8) |
| S3—C9 | 1.742 (6) | C9—C10 | 1.366 (8) |
| C1—C2 | 1.360 (10) | C10—C11 | 1.428 (8) |
| C2—C3 | 1.404 (9) | C10—H10 | 0.9500 |
| C2—H2 | 0.9500 | C11—C12 | 1.367 (9) |
| C3—C4 | 1.370 (8) | C11—H11 | 0.9500 |
| C3—H3 | 0.9500 | ||
| C1—S1—C4 | 91.7 (3) | C7—C6—H6 | 122.9 |
| C8—S2—C5 | 92.3 (3) | C8—C7—C6 | 113.4 (5) |
| C12—S3—C9 | 91.2 (3) | C8—C7—H7 | 123.3 |
| C2—C1—S1 | 111.9 (5) | C6—C7—H7 | 123.3 |
| C2—C1—Br1 | 128.4 (5) | C7—C8—C9 | 127.6 (5) |
| S1—C1—Br1 | 119.8 (4) | C7—C8—S2 | 110.4 (5) |
| C1—C2—C3 | 112.7 (6) | C9—C8—S2 | 122.1 (5) |
| C1—C2—H2 | 123.6 | C10—C9—C8 | 128.7 (5) |
| C3—C2—H2 | 123.6 | C10—C9—S3 | 110.6 (4) |
| C4—C3—C2 | 114.0 (6) | C8—C9—S3 | 120.7 (4) |
| C4—C3—H3 | 123.0 | C9—C10—C11 | 114.2 (6) |
| C2—C3—H3 | 123.0 | C9—C10—H10 | 122.9 |
| C3—C4—C5 | 131.2 (5) | C11—C10—H10 | 122.9 |
| C3—C4—S1 | 109.7 (5) | C12—C11—C10 | 110.9 (5) |
| C5—C4—S1 | 119.1 (4) | C12—C11—H11 | 124.5 |
| C6—C5—C4 | 129.3 (5) | C10—C11—H11 | 124.5 |
| C6—C5—S2 | 109.7 (4) | C11—C12—S3 | 113.0 (5) |
| C4—C5—S2 | 121.0 (4) | C11—C12—Br2 | 126.3 (5) |
| C5—C6—C7 | 114.3 (5) | S3—C12—Br2 | 120.6 (4) |
| C5—C6—H6 | 122.9 | ||
| C4—S1—C1—C2 | 0.0 (5) | C6—C7—C8—C9 | −179.1 (6) |
| C4—S1—C1—Br1 | −179.1 (4) | C6—C7—C8—S2 | −0.3 (6) |
| S1—C1—C2—C3 | 0.1 (7) | C5—S2—C8—C7 | 0.0 (5) |
| Br1—C1—C2—C3 | 179.1 (5) | C5—S2—C8—C9 | 179.0 (5) |
| C1—C2—C3—C4 | −0.2 (8) | C7—C8—C9—C10 | −179.5 (6) |
| C2—C3—C4—C5 | 177.2 (6) | S2—C8—C9—C10 | 1.8 (9) |
| C2—C3—C4—S1 | 0.2 (7) | C7—C8—C9—S3 | 0.8 (9) |
| C1—S1—C4—C3 | −0.1 (5) | S2—C8—C9—S3 | −178.0 (3) |
| C1—S1—C4—C5 | −177.6 (5) | C12—S3—C9—C10 | 0.2 (5) |
| C3—C4—C5—C6 | −178.4 (7) | C12—S3—C9—C8 | 180.0 (5) |
| S1—C4—C5—C6 | −1.6 (9) | C8—C9—C10—C11 | −179.2 (6) |
| C3—C4—C5—S2 | 2.0 (9) | S3—C9—C10—C11 | 0.6 (7) |
| S1—C4—C5—S2 | 178.8 (3) | C9—C10—C11—C12 | −1.3 (8) |
| C8—S2—C5—C6 | 0.2 (5) | C10—C11—C12—S3 | 1.4 (7) |
| C8—S2—C5—C4 | 179.8 (5) | C10—C11—C12—Br2 | 178.2 (5) |
| C4—C5—C6—C7 | −180.0 (5) | C9—S3—C12—C11 | −1.0 (5) |
| S2—C5—C6—C7 | −0.4 (7) | C9—S3—C12—Br2 | −177.9 (4) |
| C5—C6—C7—C8 | 0.4 (7) |
This work was supported in part by Research Development Grants from the Pennsylvania State University and partially by the MRSEC Program of the National Science Foundation under Award Number DMR-0819885. The author also acknowledges William W. Brennessel, Victor G. Young Jr and the X-Ray Crystallographic Laboratory at the University of Minnesota.
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Dibromothiophenes are important building blocks in materials chemistry. They are mainly used in the prepartaion of various thiophene oligomers and polymers utilizing coupling reactions such as Stille and Suzuki couplings.
For literature related to the synthesis see: Hoffman & Carlsen (1999) and Mei (2009). For a recent review on synthesis and applications of oligothiophenes,see: Mishra (2009).