Acta Cryst. (2008). E64, o2306 [ doi:10.1107/S1600536808036143 ]
The molecule of the title compound, C40H46S2, reveals Ci symmetry. An inversion centre is located at the mid-point of the C-C bond of the biphenyl unit; the asymmetric unit comprises one-half of the molecule. The conjugated backbone is nearly planar, with a mean deviation of 0.041 Å.
The synthesis of 4,4'-bis-[2-(3,4-dibutyl-2-thienylethynyl)]biphenyl was performed as previously described (Liu et al., 2005).
Yellow needles were grown from an ethanol/hexane solution by slow evaporation.
Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO (Rigaku, 2001); data reduction: RAPID-AUTO (Rigaku, 2001); 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).
![[Figure 1]](./kp2189fig1thm.gif)
| Fig. 1. View of the title compound, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability. To generate the molecule symmetry code -x, -y, -z + 2 is applied. |
![[Figure 2]](./kp2189fig2thm.gif)
| Fig. 2. View of the packing mode along a axis of (I). |
| C40H46S2 | V = 849.7 (3) Å3 |
| Mr = 590.89 | Z = 1 |
| Triclinic, P1 | F(000) = 318 |
| a = 9.2040 (18) Å | Dx = 1.155 Mg m−3 |
| b = 9.3640 (19) Å | Mo Kα radiation, λ = 0.71073 Å |
| c = 10.582 (2) Å | µ = 0.18 mm−1 |
| α = 85.69 (3)° | T = 293 K |
| β = 85.18 (3)° | Neddle, yellow |
| γ = 69.41 (3)° | 0.62 × 0.40 × 0.07 mm |
| Rigaku R-AXIS RAPID IP diffractometer | 3595 independent reflections |
| Radiation source: fine-focus sealed tube | 2287 reflections with I > 2σ(I) |
| graphite | Rint = 0.0000 |
| Detector resolution: 0.76 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
| Oscillation scans | h = 0→11 |
| Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995) | k = −10→12 |
| Tmin = 0.805, Tmax = 0.992 | l = −13→13 |
| 3595 measured reflections |
| 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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.241 | H-atom parameters constrained |
| S = 1.07 | w = 1/[σ2(Fo2) + (0.1672P)2 + 0.1626P] where P = (Fo2 + 2Fc2)/3 |
| 3595 reflections | (Δ/σ)max < 0.001 |
| 190 parameters | Δρmax = 0.44 e Å−3 |
| 0 restraints | Δρmin = −0.42 e Å−3 |
| C40H46S2 | γ = 69.41 (3)° |
| Mr = 590.89 | V = 849.7 (3) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 9.2040 (18) Å | Mo Kα radiation |
| b = 9.3640 (19) Å | µ = 0.18 mm−1 |
| c = 10.582 (2) Å | T = 293 K |
| α = 85.69 (3)° | 0.62 × 0.40 × 0.07 mm |
| β = 85.18 (3)° |
| Rigaku R-AXIS RAPID IP diffractometer | 3595 independent reflections |
| Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995) | 2287 reflections with I > 2σ(I) |
| Tmin = 0.805, Tmax = 0.992 | Rint = 0.0000 |
| 3595 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.067 | H-atom parameters constrained |
| wR(F2) = 0.241 | Δρmax = 0.44 e Å−3 |
| S = 1.07 | Δρmin = −0.42 e Å−3 |
| 3595 reflections | Absolute structure: ? |
| 190 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.34733 (8) | 0.37884 (8) | 0.02833 (7) | 0.0512 (3) | |
| C1 | −0.2000 (4) | 0.5223 (4) | 0.3588 (3) | 0.0657 (9) | |
| H1A | −0.1334 | 0.5778 | 0.3558 | 0.079* | |
| C2 | −0.3290 (4) | 0.5588 (4) | 0.4443 (3) | 0.0615 (8) | |
| H2A | −0.3467 | 0.6388 | 0.4973 | 0.074* | |
| C3 | −0.4314 (3) | 0.4808 (3) | 0.4534 (2) | 0.0393 (5) | |
| C4 | −0.4016 (4) | 0.3655 (4) | 0.3702 (4) | 0.0750 (12) | |
| H4A | −0.4696 | 0.3116 | 0.3721 | 0.090* | |
| C5 | −0.2733 (4) | 0.3276 (5) | 0.2840 (4) | 0.0816 (13) | |
| H5A | −0.2573 | 0.2494 | 0.2295 | 0.098* | |
| C6 | −0.1694 (3) | 0.4041 (3) | 0.2779 (2) | 0.0439 (6) | |
| C7 | −0.0335 (3) | 0.3631 (3) | 0.1922 (3) | 0.0476 (6) | |
| C8 | 0.0798 (3) | 0.3289 (3) | 0.1211 (2) | 0.0440 (6) | |
| C9 | 0.2138 (3) | 0.2853 (3) | 0.0369 (2) | 0.0415 (6) | |
| C10 | 0.2565 (3) | 0.1695 (3) | −0.0473 (2) | 0.0387 (5) | |
| C11 | 0.3994 (3) | 0.1568 (3) | −0.1180 (2) | 0.0419 (6) | |
| C12 | 0.4587 (3) | 0.2635 (3) | −0.0862 (3) | 0.0497 (7) | |
| H12 | 0.5507 | 0.2720 | −0.1235 | 0.060* | |
| C13 | 0.1620 (3) | 0.0701 (3) | −0.0634 (3) | 0.0463 (6) | |
| H13A | 0.0948 | 0.0719 | 0.0126 | 0.056* | |
| H13B | 0.2317 | −0.0344 | −0.0728 | 0.056* | |
| C14 | 0.4717 (3) | 0.0371 (3) | −0.2152 (3) | 0.0515 (7) | |
| H14A | 0.4910 | −0.0630 | −0.1731 | 0.062* | |
| H14B | 0.3969 | 0.0498 | −0.2784 | 0.062* | |
| C15 | 0.0618 (3) | 0.1215 (3) | −0.1791 (3) | 0.0503 (6) | |
| H15A | 0.1267 | 0.1352 | −0.2527 | 0.060* | |
| H15B | 0.0233 | 0.0412 | −0.1960 | 0.060* | |
| C16 | 0.6214 (3) | 0.0406 (3) | −0.2825 (3) | 0.0498 (7) | |
| H16A | 0.6965 | 0.0293 | −0.2201 | 0.060* | |
| H16B | 0.6025 | 0.1390 | −0.3274 | 0.060* | |
| C17 | −0.0748 (3) | 0.2680 (4) | −0.1618 (3) | 0.0575 (7) | |
| H17A | −0.0376 | 0.3445 | −0.1336 | 0.069* | |
| H17B | −0.1465 | 0.2501 | −0.0953 | 0.069* | |
| C18 | 0.6894 (3) | −0.0855 (4) | −0.3767 (3) | 0.0604 (8) | |
| H18A | 0.7095 | −0.1838 | −0.3314 | 0.073* | |
| H18B | 0.6131 | −0.0752 | −0.4380 | 0.073* | |
| C19 | −0.1626 (4) | 0.3311 (4) | −0.2807 (3) | 0.0680 (9) | |
| H19A | −0.2477 | 0.4233 | −0.2623 | 0.102* | |
| H19B | −0.2019 | 0.2571 | −0.3085 | 0.102* | |
| H19C | −0.0936 | 0.3526 | −0.3464 | 0.102* | |
| C20 | 0.8373 (5) | −0.0823 (6) | −0.4465 (4) | 0.0866 (13) | |
| H20A | 0.8747 | −0.1641 | −0.5037 | 0.130* | |
| H20B | 0.9140 | −0.0944 | −0.3866 | 0.130* | |
| H20C | 0.8177 | 0.0135 | −0.4937 | 0.130* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0432 (4) | 0.0556 (4) | 0.0568 (5) | −0.0203 (3) | 0.0164 (3) | −0.0206 (3) |
| C1 | 0.0576 (17) | 0.080 (2) | 0.070 (2) | −0.0398 (16) | 0.0352 (15) | −0.0323 (17) |
| C2 | 0.0596 (17) | 0.0696 (18) | 0.0622 (18) | −0.0334 (15) | 0.0336 (14) | −0.0329 (15) |
| C3 | 0.0314 (11) | 0.0457 (12) | 0.0341 (11) | −0.0071 (9) | 0.0110 (9) | −0.0058 (9) |
| C4 | 0.0615 (18) | 0.088 (2) | 0.090 (2) | −0.0447 (18) | 0.0481 (18) | −0.055 (2) |
| C5 | 0.068 (2) | 0.090 (2) | 0.097 (3) | −0.0424 (19) | 0.054 (2) | −0.062 (2) |
| C6 | 0.0326 (11) | 0.0505 (14) | 0.0415 (13) | −0.0084 (10) | 0.0130 (10) | −0.0066 (10) |
| C7 | 0.0395 (13) | 0.0532 (14) | 0.0433 (14) | −0.0099 (11) | 0.0122 (11) | −0.0087 (11) |
| C8 | 0.0372 (12) | 0.0506 (14) | 0.0393 (13) | −0.0113 (11) | 0.0109 (10) | −0.0059 (10) |
| C9 | 0.0326 (11) | 0.0477 (13) | 0.0404 (12) | −0.0116 (10) | 0.0126 (10) | −0.0065 (10) |
| C10 | 0.0321 (11) | 0.0443 (12) | 0.0366 (12) | −0.0116 (9) | 0.0080 (9) | −0.0025 (9) |
| C11 | 0.0315 (11) | 0.0488 (13) | 0.0406 (13) | −0.0098 (10) | 0.0118 (9) | −0.0082 (10) |
| C12 | 0.0360 (12) | 0.0596 (15) | 0.0526 (15) | −0.0182 (11) | 0.0201 (11) | −0.0148 (12) |
| C13 | 0.0430 (13) | 0.0452 (13) | 0.0514 (14) | −0.0190 (11) | 0.0110 (11) | −0.0048 (11) |
| C14 | 0.0385 (13) | 0.0582 (16) | 0.0552 (16) | −0.0142 (12) | 0.0173 (11) | −0.0212 (13) |
| C15 | 0.0452 (13) | 0.0580 (15) | 0.0509 (15) | −0.0225 (12) | 0.0100 (11) | −0.0140 (12) |
| C16 | 0.0374 (13) | 0.0617 (16) | 0.0442 (14) | −0.0113 (12) | 0.0149 (11) | −0.0129 (12) |
| C17 | 0.0475 (15) | 0.0641 (18) | 0.0589 (17) | −0.0165 (13) | 0.0028 (13) | −0.0116 (14) |
| C18 | 0.0478 (15) | 0.077 (2) | 0.0428 (15) | −0.0039 (14) | 0.0070 (12) | −0.0187 (14) |
| C19 | 0.0546 (18) | 0.080 (2) | 0.068 (2) | −0.0214 (17) | −0.0071 (15) | −0.0038 (17) |
| C20 | 0.063 (2) | 0.111 (3) | 0.061 (2) | −0.003 (2) | 0.0313 (17) | −0.018 (2) |
| S1—C12 | 1.702 (3) | C13—H13A | 0.9700 |
| S1—C9 | 1.735 (3) | C13—H13B | 0.9700 |
| C1—C6 | 1.385 (4) | C14—C16 | 1.507 (3) |
| C1—C2 | 1.387 (4) | C14—H14A | 0.9700 |
| C1—H1A | 0.9300 | C14—H14B | 0.9700 |
| C2—C3 | 1.375 (4) | C15—C17 | 1.511 (4) |
| C2—H2A | 0.9300 | C15—H15A | 0.9700 |
| C3—C4 | 1.382 (4) | C15—H15B | 0.9700 |
| C3—C3i | 1.490 (4) | C16—C18 | 1.527 (4) |
| C4—C5 | 1.387 (4) | C16—H16A | 0.9700 |
| C4—H4A | 0.9300 | C16—H16B | 0.9700 |
| C5—C6 | 1.377 (4) | C17—C19 | 1.519 (5) |
| C5—H5A | 0.9300 | C17—H17A | 0.9700 |
| C6—C7 | 1.435 (3) | C17—H17B | 0.9700 |
| C7—C8 | 1.193 (3) | C18—C20 | 1.502 (5) |
| C8—C9 | 1.414 (3) | C18—H18A | 0.9700 |
| C9—C10 | 1.382 (3) | C18—H18B | 0.9700 |
| C10—C11 | 1.428 (3) | C19—H19A | 0.9600 |
| C10—C13 | 1.507 (4) | C19—H19B | 0.9600 |
| C11—C12 | 1.369 (4) | C19—H19C | 0.9600 |
| C11—C14 | 1.514 (3) | C20—H20A | 0.9600 |
| C12—H12 | 0.9300 | C20—H20B | 0.9600 |
| C13—C15 | 1.539 (4) | C20—H20C | 0.9600 |
| C12—S1—C9 | 91.29 (12) | C11—C14—H14A | 108.5 |
| C6—C1—C2 | 120.7 (3) | C16—C14—H14B | 108.5 |
| C6—C1—H1A | 119.7 | C11—C14—H14B | 108.5 |
| C2—C1—H1A | 119.7 | H14A—C14—H14B | 107.5 |
| C3—C2—C1 | 122.4 (3) | C17—C15—C13 | 113.7 (2) |
| C3—C2—H2A | 118.8 | C17—C15—H15A | 108.8 |
| C1—C2—H2A | 118.8 | C13—C15—H15A | 108.8 |
| C2—C3—C4 | 116.4 (2) | C17—C15—H15B | 108.8 |
| C2—C3—C3i | 122.1 (3) | C13—C15—H15B | 108.8 |
| C4—C3—C3i | 121.5 (3) | H15A—C15—H15B | 107.7 |
| C3—C4—C5 | 122.0 (3) | C14—C16—C18 | 112.4 (2) |
| C3—C4—H4A | 119.0 | C14—C16—H16A | 109.1 |
| C5—C4—H4A | 119.0 | C18—C16—H16A | 109.1 |
| C6—C5—C4 | 121.1 (3) | C14—C16—H16B | 109.1 |
| C6—C5—H5A | 119.5 | C18—C16—H16B | 109.1 |
| C4—C5—H5A | 119.5 | H16A—C16—H16B | 107.9 |
| C5—C6—C1 | 117.5 (2) | C15—C17—C19 | 114.3 (3) |
| C5—C6—C7 | 121.7 (2) | C15—C17—H17A | 108.7 |
| C1—C6—C7 | 120.8 (2) | C19—C17—H17A | 108.7 |
| C8—C7—C6 | 179.8 (4) | C15—C17—H17B | 108.7 |
| C7—C8—C9 | 178.8 (3) | C19—C17—H17B | 108.7 |
| C10—C9—C8 | 126.9 (2) | H17A—C17—H17B | 107.6 |
| C10—C9—S1 | 111.52 (17) | C20—C18—C16 | 113.2 (3) |
| C8—C9—S1 | 121.6 (2) | C20—C18—H18A | 108.9 |
| C9—C10—C11 | 112.0 (2) | C16—C18—H18A | 108.9 |
| C9—C10—C13 | 123.8 (2) | C20—C18—H18B | 108.9 |
| C11—C10—C13 | 124.2 (2) | C16—C18—H18B | 108.9 |
| C12—C11—C10 | 111.9 (2) | H18A—C18—H18B | 107.7 |
| C12—C11—C14 | 126.0 (2) | C17—C19—H19A | 109.5 |
| C10—C11—C14 | 122.0 (2) | C17—C19—H19B | 109.5 |
| C11—C12—S1 | 113.24 (18) | H19A—C19—H19B | 109.5 |
| C11—C12—H12 | 123.4 | C17—C19—H19C | 109.5 |
| S1—C12—H12 | 123.4 | H19A—C19—H19C | 109.5 |
| C10—C13—C15 | 112.8 (2) | H19B—C19—H19C | 109.5 |
| C10—C13—H13A | 109.0 | C18—C20—H20A | 109.5 |
| C15—C13—H13A | 109.0 | C18—C20—H20B | 109.5 |
| C10—C13—H13B | 109.0 | H20A—C20—H20B | 109.5 |
| C15—C13—H13B | 109.0 | C18—C20—H20C | 109.5 |
| H13A—C13—H13B | 107.8 | H20A—C20—H20C | 109.5 |
| C16—C14—C11 | 115.3 (2) | H20B—C20—H20C | 109.5 |
| C16—C14—H14A | 108.5 | ||
| C12—C11—C10—C9 | −0.6 (4) | C4—C5—C6—C1 | −1.5 (1) |
| C12—S1—C9—C10 | 0.1 (8) | C1—C2—C3—C4 | −1.6 (0) |
| C10—C11—C12—S1 | 0.5 (1) | C5—C4—C3—C2 | 1.5 (0) |
| C11—C12—S1—C9 | −0.2 (0) | C5—C6—C1—C2 | 1.4 (2) |
| C11—C10—C9—S1 | 0.4 (9) | C9—C8—C7—C6 | 93.5 (2) |
| C11—C10—C9—C8 | −179.9 (8) | C10—C9—C8—C7 | 24.6 (9) |
| C12—S1—C9—C8 | −179.7 (4) | S1—C9—C8—C7 | −155.8 (2) |
| C7—C6—C5—C4 | 177.9 (5) | C5—C6—C7—C8 | −117.5 (4) |
| C7—C6—C1—C2 | −178.0 (5) | C1—C6—C7—C8 | 61.9 (0) |
| C6—C5—C4—C3 | 0.0 (4) | C4—C3—C3—C4 | 90.0 (0) |
| C6—C1—C2—C3 | 0.1 (5) |
| Symmetry codes: (i) −x−1, −y+1, −z+1. |
The present research work was financially supported by the National Natural Science Foundation of China (grant No. 20572113), Hebei Natural Science Foundation, and the Hebei University of Science and Technology Project for Young Scientists Fund.
Baudour, J. L. (1972). Acta Cryst. B28, 1649–1656.
Brad Wan, W., Brand, S. C., Park, J. J. & Haley, M. (2000). Chem. Eur. J. 6, 2044–2052.
Charbonneau, G. P. & Delugeard, Y. (1977). Acta Cryst. B33, 1586–1588.
Cornil, J., Calbert, J. P. & Bredas, J. L. (2001). J. Am. Chem. Soc. 123, 1250–1251.
Domenicano, A., Vaciago, A. & Coulson, C. A. (1975). Acta Cryst. B31, 221–234.
Grosshenny, V., Romero, F. M. & Ziessel, R. (1997). J. Org. Chem. 62, 1491–1500.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Please check added reference
Huang, S. & Tour, J. M. (1998). Polym. Prepr. 39, 525–526.
Liu, L., Liu, Z. X., Xu, W., Xu, H., Zhang, D. Q. & Zhu, D. B. (2005). Tetrahedron, 61, 3813–3817.
Rigaku (2001). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
Robertson, G. B. (1961). Nature (London), 191, 593–594.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Tour, J. M. (1996). Chem. Rev. 96, 537–553.
The synthesis and characterization of nanometer-sized conjugated molecules of precise length and constitution are of widespread interest, which is due to their electroconductive, magnetic, and optical properties (Tour, 1996; Huang & Tour, 1998; Grosshenny et al., 1997; Brad Wan et al., 2000). Generally, crystal structure of a molecule is important for better understanding of its properties. Therefore, structures of oligothiophene single crystals have been reported. The field of molecular organic semiconductors is being revolutionized by the availability of ultrahigh purity single crystals that have allowed the demonstration of phenomena long thought to be restricted to inorganic semiconductors (Cornil et al., 2001).
The molecule of the title compound (Fig. 1) is centrosymmetric. An asymmetric unit comprises a half on the molecule. The inversion centre is located in the middle of C3—C3i bond. Conjugated molecular skeleton is nearly planar; mean deviation from the best least-square plane is 0.041 Å. The endocyclic bond angles on the long molecular axis are less than the normal 120° value (they vary from 116.42–117.52°) whereas that situated out of this long molecular axis are greater than 120° (in the range 120.73–122.43°). This result agrees with those obtained for polyphenyls (Robertson, 1961; Baudour, 1972; Domenicano et al., 1975; Charbonneau & Delugeard, 1977). The two thiophene rings, phenyl rings and C≡C are coplanar. The crystal packing is dominated by van der Waals interactions.