Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101010988/fr1332sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101010988/fr1332Isup2.hkl |
CCDC reference: 173396
For the preparation of 5,6-diphenylthieno[2,3-d][1,3]dithiole-2-thione, (IX), a solution of 1,8-diketone (VII) (0.5 g, 0.85 mmol) and Lawesson's reagent, (I) (0.4 g, 0.99 mmol), in dry toluene (25 ml) was refluxed overnight under a nitrogen atmosphere. The solvent was evaporated and the residue purified by column chromatography, eluting with hexane–dichloromethane (2:1) (m.p. 429–430 K; 0.087 g, 30%). 1H NMR (200 MHz, CDCl3): δ 7.5 (10H, m); 13C NMR (50.32 Hz, CDCl3): δ 207 (C═S), 143.8, 140.7, 133.9, 132.6, 129.06, 129, 128.9, 128.8, 128.7, 128.6, 128.5, 128.4; m/z (EI): 342 (M+); m/z (HRMS): 341.9665, C17H10S4 requires 341.9684; UV (CH3CN, nm) 392.
Ring H atoms were placed geometrically 0.93 Å from their parent atoms. For all H atoms, a riding model was used with Ueq(H) = 1.3Ueq(C).
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1993); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1965); software used to prepare material for publication: PLATON (Spek, 1990).
Fig. 1. ORTEP (Johnson, 1965) drawing of the asymmetric unit, showing the atomic numbering scheme and displacement ellipsoids at the 40% probability level. |
C17H10S4 | Z = 8 |
Mr = 342.53 | Dx = 1.475 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 23.441 (3) Å | θ = 11–18° |
b = 10.1303 (14) Å | µ = 0.60 mm−1 |
c = 13.5222 (17) Å | T = 295 K |
β = 73.822 (10)° | Prismatic, yellow |
V = 3083.9 (7) Å3 | 0.45 × 0.24 × 0.15 mm |
Enraf-Nonius CAD-4 diffractometer | θmax = 27.9° |
ω/2θ scans | h = −29→30 |
Absorption correction: ψ scans ? | k = −13→0 |
Tmin = 0.840, Tmax = 0.913 | l = 0→17 |
7317 measured reflections | 3 standard reflections every 120 min |
7013 independent reflections | intensity decay: 1% |
Rint = 0.052 |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.033 | w = 1/[σ2(Fo2) + (0.0555P)2 + 0.6458P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.099 | (Δ/σ)max = 0.001 |
S = 1.07 | Δρmax = 0.25 e Å−3 |
5657 reflections | Δρmin = −0.36 e Å−3 |
379 parameters |
C17H10S4 | V = 3083.9 (7) Å3 |
Mr = 342.53 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 23.441 (3) Å | µ = 0.60 mm−1 |
b = 10.1303 (14) Å | T = 295 K |
c = 13.5222 (17) Å | 0.45 × 0.24 × 0.15 mm |
β = 73.822 (10)° |
Enraf-Nonius CAD-4 diffractometer | 7013 independent reflections |
Absorption correction: ψ scans ? | Rint = 0.052 |
Tmin = 0.840, Tmax = 0.913 | 3 standard reflections every 120 min |
7317 measured reflections | intensity decay: 1% |
R[F2 > 2σ(F2)] = 0.033 | 379 parameters |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.25 e Å−3 |
5657 reflections | Δρmin = −0.36 e Å−3 |
x | y | z | Uiso*/Ueq | ||
S1B | 0.50369 (3) | 0.53071 (5) | 0.86838 (4) | 0.04845 (13) | |
S2B | 0.57143 (2) | 0.59604 (4) | 0.65119 (3) | 0.04058 (11) | |
S3B | 0.50855 (2) | 0.34501 (5) | 0.69854 (3) | 0.04335 (12) | |
S4B | 0.55851 (2) | 0.27183 (5) | 0.46669 (4) | 0.04114 (12) | |
C1B | 0.52733 (8) | 0.49398 (18) | 0.74491 (13) | 0.0379 (4) | |
C2B | 0.57625 (7) | 0.49098 (17) | 0.54740 (13) | 0.0348 (3) | |
C3B | 0.54640 (8) | 0.37370 (17) | 0.57138 (13) | 0.0371 (4) | |
C4B | 0.61036 (7) | 0.50075 (17) | 0.44220 (13) | 0.0344 (3) | |
C5B | 0.60535 (8) | 0.38760 (17) | 0.38906 (13) | 0.0362 (4) | |
C6B | 0.63262 (8) | 0.35034 (19) | 0.28076 (14) | 0.0399 (4) | |
C7B | 0.63742 (9) | 0.4395 (2) | 0.20093 (15) | 0.0520 (5) | |
C8B | 0.66253 (11) | 0.4001 (3) | 0.09952 (17) | 0.0712 (8) | |
C9B | 0.68258 (11) | 0.2717 (4) | 0.0778 (2) | 0.0805 (9) | |
C10B | 0.67725 (10) | 0.1837 (3) | 0.1558 (2) | 0.0732 (8) | |
C11B | 0.65316 (9) | 0.2219 (2) | 0.25695 (18) | 0.0549 (5) | |
C12B | 0.64641 (8) | 0.61904 (17) | 0.40010 (13) | 0.0370 (4) | |
C13B | 0.62091 (9) | 0.74387 (19) | 0.41810 (16) | 0.0476 (4) | |
C14B | 0.65410 (12) | 0.8545 (2) | 0.3772 (2) | 0.0626 (6) | |
C15B | 0.71170 (12) | 0.8422 (2) | 0.31945 (18) | 0.0657 (7) | |
C16B | 0.73771 (10) | 0.7195 (3) | 0.30280 (17) | 0.0604 (6) | |
C17B | 0.70551 (9) | 0.6074 (2) | 0.34248 (15) | 0.0475 (5) | |
S1A | 0.99807 (2) | 0.52535 (5) | 0.87090 (4) | 0.04715 (13) | |
S2A | 0.92916 (2) | 0.59254 (4) | 0.72136 (4) | 0.04177 (12) | |
S3A | 0.98892 (2) | 0.33786 (5) | 0.70942 (4) | 0.04403 (12) | |
S4A | 0.93756 (2) | 0.26740 (5) | 0.52675 (4) | 0.04269 (12) | |
C1A | 0.97276 (8) | 0.48848 (18) | 0.77214 (13) | 0.0379 (4) | |
C2A | 0.92288 (8) | 0.48705 (17) | 0.62322 (13) | 0.0357 (4) | |
C3A | 0.95101 (8) | 0.36829 (18) | 0.61904 (14) | 0.0383 (4) | |
C4A | 0.88889 (7) | 0.50013 (17) | 0.55104 (13) | 0.0356 (4) | |
C5A | 0.89233 (8) | 0.38637 (17) | 0.49395 (14) | 0.0372 (4) | |
C6A | 0.86478 (8) | 0.35182 (19) | 0.41155 (14) | 0.0395 (4) | |
C7A | 0.86338 (9) | 0.4415 (2) | 0.33425 (15) | 0.0485 (5) | |
C8A | 0.83780 (11) | 0.4050 (3) | 0.25713 (17) | 0.0648 (7) | |
C9A | 0.81401 (10) | 0.2808 (3) | 0.2562 (2) | 0.0733 (8) | |
C10A | 0.81575 (11) | 0.1919 (3) | 0.3316 (2) | 0.0719 (7) | |
C11A | 0.84075 (10) | 0.2267 (2) | 0.40930 (19) | 0.0566 (5) | |
C12A | 0.85495 (8) | 0.62124 (17) | 0.54314 (13) | 0.0359 (4) | |
C13A | 0.79560 (8) | 0.6164 (2) | 0.54386 (16) | 0.0457 (4) | |
C14A | 0.76500 (9) | 0.7322 (3) | 0.53773 (17) | 0.0575 (6) | |
C15A | 0.79301 (11) | 0.8517 (2) | 0.52922 (18) | 0.0599 (6) | |
C16A | 0.85175 (11) | 0.8584 (2) | 0.52745 (18) | 0.0566 (5) | |
C17A | 0.88251 (8) | 0.74364 (19) | 0.53548 (16) | 0.0442 (4) | |
H7B | 0.6239 | 0.5256 | 0.2152 | 0.062* | |
H8B | 0.6659 | 0.4601 | 0.0461 | 0.085* | |
H9B | 0.6997 | 0.2458 | 0.0100 | 0.097* | |
H10B | 0.6899 | 0.0971 | 0.1409 | 0.088* | |
H11B | 0.6506 | 0.1613 | 0.3097 | 0.066* | |
H13B | 0.5817 | 0.7532 | 0.4575 | 0.057* | |
H14B | 0.6369 | 0.9378 | 0.3892 | 0.075* | |
H15B | 0.7334 | 0.9168 | 0.2914 | 0.079* | |
H16B | 0.7772 | 0.7116 | 0.2646 | 0.073* | |
H17B | 0.7233 | 0.5247 | 0.3306 | 0.057* | |
H7A | 0.8795 | 0.5254 | 0.3342 | 0.058* | |
H8A | 0.8367 | 0.4650 | 0.2056 | 0.078* | |
H9A | 0.7968 | 0.2574 | 0.2045 | 0.088* | |
H10A | 0.8001 | 0.1078 | 0.3306 | 0.086* | |
H11A | 0.8415 | 0.1659 | 0.4605 | 0.068* | |
H13A | 0.7763 | 0.5354 | 0.5485 | 0.055* | |
H14A | 0.7251 | 0.7284 | 0.5394 | 0.069* | |
H15A | 0.7722 | 0.9286 | 0.5246 | 0.072* | |
H16A | 0.8709 | 0.9396 | 0.5209 | 0.068* | |
H17A | 0.9221 | 0.7488 | 0.5357 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1B | 0.0433 (9) | 0.0329 (8) | 0.0373 (9) | 0.0007 (7) | −0.0108 (7) | 0.0038 (7) |
C2B | 0.0395 (9) | 0.0283 (8) | 0.0359 (8) | −0.0021 (7) | −0.0096 (7) | 0.0010 (7) |
C3B | 0.0412 (9) | 0.0329 (8) | 0.0353 (8) | −0.0004 (7) | −0.0077 (7) | −0.0043 (7) |
C4B | 0.0356 (8) | 0.0298 (8) | 0.0372 (8) | 0.0012 (7) | −0.0091 (7) | 0.0007 (7) |
C5B | 0.0384 (9) | 0.0329 (9) | 0.0373 (9) | 0.0015 (7) | −0.0102 (7) | −0.0015 (7) |
C6B | 0.0361 (9) | 0.0439 (10) | 0.0398 (9) | −0.0051 (8) | −0.0105 (7) | −0.0059 (7) |
C7B | 0.0532 (11) | 0.0619 (13) | 0.0428 (10) | 0.0021 (9) | −0.0165 (9) | −0.0090 (10) |
C8B | 0.0641 (14) | 0.109 (2) | 0.0409 (11) | 0.0038 (13) | −0.0156 (10) | −0.0283 (15) |
C9B | 0.0546 (14) | 0.127 (3) | 0.0511 (14) | −0.0361 (16) | 0.0005 (11) | −0.0231 (16) |
C10B | 0.0508 (12) | 0.0800 (18) | 0.0786 (17) | −0.0392 (15) | −0.0014 (12) | −0.0019 (12) |
C11B | 0.0503 (11) | 0.0504 (12) | 0.0588 (13) | −0.0135 (10) | −0.0065 (10) | 0.0014 (9) |
C12B | 0.0432 (9) | 0.0335 (9) | 0.0355 (8) | 0.0026 (7) | −0.0128 (7) | −0.0060 (7) |
C13B | 0.0529 (11) | 0.0360 (10) | 0.0554 (12) | 0.0054 (8) | −0.0178 (9) | −0.0023 (8) |
C14B | 0.0859 (17) | 0.0368 (11) | 0.0727 (15) | 0.0117 (10) | −0.0346 (13) | −0.0134 (11) |
C15B | 0.0864 (17) | 0.0590 (15) | 0.0557 (13) | 0.0169 (11) | −0.0262 (12) | −0.0389 (13) |
C16B | 0.0550 (12) | 0.0750 (16) | 0.0465 (11) | 0.0014 (11) | −0.0061 (9) | −0.0261 (12) |
C17B | 0.0460 (10) | 0.0499 (11) | 0.0446 (10) | −0.0055 (9) | −0.0092 (8) | −0.0081 (9) |
S1B | 0.0676 (3) | 0.0414 (3) | 0.0342 (2) | −0.00136 (19) | −0.0107 (2) | 0.0042 (2) |
S2B | 0.0507 (3) | 0.0296 (2) | 0.0388 (2) | −0.00354 (17) | −0.00803 (19) | −0.00255 (18) |
S3B | 0.0531 (3) | 0.0361 (2) | 0.0366 (2) | 0.00123 (18) | −0.00529 (19) | −0.0094 (2) |
S4B | 0.0496 (3) | 0.0326 (2) | 0.0391 (2) | −0.00266 (17) | −0.00897 (19) | −0.00859 (18) |
C1A | 0.0428 (9) | 0.0328 (9) | 0.0406 (9) | 0.0021 (7) | −0.0159 (7) | −0.0027 (7) |
C2A | 0.0408 (9) | 0.0283 (8) | 0.0414 (9) | −0.0005 (7) | −0.0172 (7) | −0.0007 (7) |
C3A | 0.0435 (9) | 0.0331 (8) | 0.0431 (9) | −0.0030 (7) | −0.0200 (8) | 0.0034 (7) |
C4A | 0.0365 (8) | 0.0314 (8) | 0.0411 (9) | 0.0009 (7) | −0.0147 (7) | −0.0019 (7) |
C5A | 0.0388 (9) | 0.0324 (9) | 0.0431 (9) | −0.0007 (7) | −0.0162 (7) | 0.0006 (7) |
C6A | 0.0364 (9) | 0.0418 (10) | 0.0416 (9) | −0.0089 (8) | −0.0127 (7) | 0.0017 (7) |
C7A | 0.0482 (10) | 0.0553 (12) | 0.0430 (10) | −0.0020 (9) | −0.0144 (8) | 0.0030 (9) |
C8A | 0.0587 (13) | 0.094 (2) | 0.0452 (12) | −0.0089 (12) | −0.0206 (10) | 0.0163 (13) |
C9A | 0.0543 (13) | 0.110 (2) | 0.0621 (15) | −0.0371 (16) | −0.0272 (11) | 0.0067 (14) |
C10A | 0.0614 (14) | 0.0755 (17) | 0.0821 (18) | −0.0310 (15) | −0.0254 (13) | −0.0113 (13) |
C11A | 0.0599 (13) | 0.0499 (12) | 0.0643 (14) | −0.0083 (10) | −0.0242 (11) | −0.0070 (10) |
C12A | 0.0401 (9) | 0.0341 (9) | 0.0351 (8) | 0.0002 (7) | −0.0132 (7) | 0.0035 (7) |
C13A | 0.0411 (9) | 0.0499 (11) | 0.0487 (11) | −0.0061 (9) | −0.0164 (8) | 0.0027 (8) |
C14A | 0.0462 (11) | 0.0772 (16) | 0.0544 (12) | −0.0111 (11) | −0.0231 (9) | 0.0203 (11) |
C15A | 0.0698 (14) | 0.0534 (13) | 0.0595 (13) | −0.0013 (10) | −0.0232 (11) | 0.0268 (11) |
C16A | 0.0683 (14) | 0.0353 (10) | 0.0642 (14) | 0.0050 (9) | −0.0154 (11) | 0.0082 (10) |
C17A | 0.0434 (10) | 0.0349 (9) | 0.0551 (11) | 0.0031 (8) | −0.0151 (8) | 0.0015 (8) |
S1A | 0.0638 (3) | 0.0412 (3) | 0.0447 (3) | 0.0017 (2) | −0.0287 (2) | −0.0038 (2) |
S2A | 0.0531 (3) | 0.0295 (2) | 0.0502 (3) | −0.00560 (18) | −0.0267 (2) | 0.00322 (19) |
S3A | 0.0552 (3) | 0.0345 (2) | 0.0506 (3) | −0.00347 (19) | −0.0283 (2) | 0.0091 (2) |
S4A | 0.0529 (3) | 0.0320 (2) | 0.0487 (3) | −0.00797 (19) | −0.0231 (2) | 0.00772 (19) |
C1A—S1A | 1.6482 (18) | C1B—S1B | 1.6485 (18) |
C1A—S2A | 1.7374 (18) | C1B—S2B | 1.7359 (18) |
C1A—S3A | 1.7355 (19) | C1B—S3B | 1.7373 (19) |
C2A—S2A | 1.7417 (17) | C2B—S2B | 1.7398 (17) |
C2A—C3A | 1.365 (2) | C2B—C3B | 1.371 (2) |
C2A—C4A | 1.428 (2) | C2B—C4B | 1.428 (2) |
C3A—S3A | 1.7274 (18) | C3B—S3B | 1.7257 (18) |
C3A—S4A | 1.7090 (18) | C3B—S4B | 1.7104 (18) |
C4A—C5A | 1.377 (2) | C4B—C5B | 1.375 (2) |
C5A—S4A | 1.7420 (18) | C5B—S4B | 1.7437 (18) |
C4A—C12A | 1.482 (2) | C4B—C12B | 1.485 (2) |
C5A—C6A | 1.477 (2) | C5B—C6B | 1.474 (2) |
C6A—C11A | 1.390 (3) | C6B—C7B | 1.388 (3) |
C6A—C7A | 1.392 (3) | C6B—C11B | 1.393 (3) |
C7A—C8A | 1.390 (3) | C7B—C8B | 1.392 (3) |
C7A—H7A | 0.9300 | C7B—H7B | 0.9300 |
C8A—C9A | 1.377 (4) | C8B—C9B | 1.387 (4) |
C8A—H8A | 0.9300 | C8B—H8B | 0.9300 |
C9A—C10A | 1.369 (4) | C9B—C10B | 1.359 (4) |
C9A—H9A | 0.9300 | C9B—H9B | 0.9300 |
C10A—C11A | 1.384 (3) | C10B—C11B | 1.382 (3) |
C10A—H10A | 0.9300 | C10B—H10B | 0.9300 |
C11A—H11A | 0.9300 | C11B—H11B | 0.9300 |
C12A—C17A | 1.389 (3) | C12B—C13B | 1.391 (3) |
C12A—C13A | 1.389 (3) | C12B—C17B | 1.392 (3) |
C13A—C14A | 1.390 (3) | C13B—C14B | 1.389 (3) |
C13A—H13A | 0.9300 | C13B—H13B | 0.9300 |
C14A—C15A | 1.367 (4) | C14B—C15B | 1.364 (4) |
C14A—H14A | 0.9300 | C14B—H14B | 0.9300 |
C15A—C16A | 1.372 (3) | C15B—C16B | 1.375 (4) |
C15A—H15A | 0.9300 | C15B—H15B | 0.9300 |
C16A—C17A | 1.388 (3) | C16B—C17B | 1.386 (3) |
C16A—H16A | 0.9300 | C16B—H16B | 0.9300 |
C17A—H17A | 0.9300 | C17B—H17B | 0.9300 |
S1A—C1A—S3A | 121.08 (11) | S1B—C1B—S2B | 124.66 (11) |
S1A—C1A—S2A | 124.54 (11) | S1B—C1B—S3B | 120.93 (11) |
S2A—C1A—S3A | 114.37 (10) | S2B—C1B—S3B | 114.40 (10) |
C3A—C2A—C4A | 114.11 (15) | C3B—C2B—C4B | 113.76 (15) |
C3A—C2A—S2A | 115.45 (13) | C3B—C2B—S2B | 115.17 (13) |
C4A—C2A—S2A | 130.22 (13) | C4B—C2B—S2B | 130.82 (13) |
C2A—C3A—S4A | 111.83 (13) | C2B—C3B—S4B | 111.78 (13) |
C2A—C3A—S3A | 117.75 (14) | C2B—C3B—S3B | 117.93 (13) |
S4A—C3A—S3A | 130.24 (11) | S4B—C3B—S3B | 130.07 (11) |
C5A—C4A—C2A | 110.42 (15) | C5B—C4B—C2B | 110.92 (15) |
C5A—C4A—C12A | 126.95 (16) | C5B—C4B—C12B | 126.48 (15) |
C2A—C4A—C12A | 122.62 (15) | C2B—C4B—C12B | 122.59 (15) |
C4A—C5A—C6A | 130.66 (16) | C4B—C5B—C6B | 130.99 (16) |
C4A—C5A—S4A | 112.40 (13) | C4B—C5B—S4B | 112.16 (13) |
C6A—C5A—S4A | 116.94 (13) | C6B—C5B—S4B | 116.85 (13) |
C11A—C6A—C7A | 118.93 (18) | C7B—C6B—C11B | 118.68 (19) |
C5A—C6A—C11A | 119.82 (18) | C7B—C6B—C5B | 121.65 (18) |
C7A—C6A—C5A | 121.23 (17) | C5B—C6B—C11B | 119.65 (18) |
C8A—C7A—C6A | 119.7 (2) | C6B—C7B—C8B | 120.0 (2) |
C8A—C7A—H7A | 120.2 | C6B—C7B—H7B | 120.0 |
C6A—C7A—H7A | 120.2 | C8B—C7B—H7B | 120.0 |
C7A—C8A—C9A | 120.6 (2) | C7B—C8B—C9B | 120.2 (2) |
C9A—C8A—H8A | 119.7 | C9B—C8B—H8B | 119.9 |
C7A—C8A—H8A | 119.7 | C7B—C8B—H8B | 119.9 |
C10A—C9A—C8A | 119.9 (2) | C10B—C9B—C8B | 119.9 (2) |
C10A—C9A—H9A | 120.1 | C10B—C9B—H9B | 120.0 |
C8A—C9A—H9A | 120.1 | C8B—C9B—H9B | 120.0 |
C9A—C10A—C11A | 120.3 (2) | C9B—C10B—C11B | 120.5 (3) |
C9A—C10A—H10A | 119.8 | C9B—C10B—H10B | 119.7 |
C11A—C10A—H10A | 119.8 | C11B—C10B—H10B | 119.7 |
C10A—C11A—C6A | 120.6 (2) | C10B—C11B—C6B | 120.6 (2) |
C10A—C11A—H11A | 119.7 | C10B—C11B—H11B | 119.7 |
C6A—C11A—H11A | 119.7 | C6B—C11B—H11B | 119.7 |
C17A—C12A—C13A | 118.45 (17) | C13B—C12B—C17B | 119.13 (17) |
C17A—C12A—C4A | 119.77 (15) | C13B—C12B—C4B | 119.70 (16) |
C13A—C12A—C4A | 121.78 (17) | C17B—C12B—C4B | 121.16 (17) |
C14A—C13A—C12A | 120.13 (19) | C12B—C13B—C14B | 119.9 (2) |
C14A—C13A—H13A | 119.9 | C12B—C13B—H13B | 120.1 |
C12A—C13A—H13A | 119.9 | C14B—C13B—H13B | 120.1 |
C15A—C14A—C13A | 120.62 (19) | C15B—C14B—C13B | 120.6 (2) |
C15A—C14A—H14A | 119.7 | C15B—C14B—H14B | 119.7 |
C13A—C14A—H14A | 119.7 | C13B—C14B—H14B | 119.7 |
C14A—C15A—C16A | 120.07 (19) | C14B—C15B—C16B | 119.9 (2) |
C14A—C15A—H15A | 120.0 | C14B—C15B—H15B | 120.0 |
C16A—C15A—H15A | 120.0 | C16B—C15B—H15B | 120.0 |
C15A—C16A—C17A | 119.9 (2) | C15B—C16B—C17B | 120.6 (2) |
C15A—C16A—H16A | 120.1 | C15B—C16B—H16B | 119.7 |
C17A—C16A—H16A | 120.1 | C17B—C16B—H16B | 119.7 |
C12A—C17A—C16A | 120.82 (18) | C16B—C17B—C12B | 119.8 (2) |
C12A—C17A—H17A | 119.6 | C16B—C17B—H17B | 120.1 |
C16A—C17A—H17A | 119.6 | C12B—C17B—H17B | 120.1 |
C1A—S2A—C2A | 96.47 (8) | C1B—S2B—C2B | 96.67 (8) |
C1A—S3A—C3A | 95.95 (8) | C1B—S3B—C3B | 95.84 (8) |
C3A—S4A—C5A | 91.22 (8) | C3B—S4B—C5B | 91.37 (8) |
C4B—C2B—C3B—S4B | −0.3 (2) | C4A—C2A—C3A—S4A | 0.2 (2) |
S2B—C2B—C3B—S4B | −175.14 (9) | S2A—C2A—C3A—S4A | 175.37 (10) |
C4B—C2B—C3B—S3B | 174.82 (13) | C4A—C2A—C3A—S3A | −175.41 (13) |
S2B—C2B—C3B—S3B | 0.0 (2) | S2A—C2A—C3A—S3A | −0.3 (2) |
C3B—C2B—C4B—C5B | −0.4 (2) | C3A—C2A—C4A—C5A | 0.6 (2) |
S2B—C2B—C4B—C5B | 173.40 (14) | S2A—C2A—C4A—C5A | −173.65 (14) |
C3B—C2B—C4B—C12B | −179.56 (16) | C3A—C2A—C4A—C12A | 179.94 (16) |
S2B—C2B—C4B—C12B | −5.8 (3) | S2A—C2A—C4A—C12A | 5.7 (3) |
C2B—C4B—C5B—C6B | −178.87 (18) | C2A—C4A—C5A—C6A | 179.35 (18) |
C12B—C4B—C5B—C6B | 0.3 (3) | C12A—C4A—C5A—C6A | 0.1 (3) |
C2B—C4B—C5B—S4B | 0.92 (19) | C2A—C4A—C5A—S4A | −1.16 (19) |
C12B—C4B—C5B—S4B | −179.96 (14) | C12A—C4A—C5A—S4A | 179.56 (14) |
C4B—C5B—C6B—C7B | −41.6 (3) | C4A—C5A—C6A—C11A | −138.1 (2) |
S4B—C5B—C6B—C7B | 138.63 (16) | S4A—C5A—C6A—C11A | 42.4 (2) |
C4B—C5B—C6B—C11B | 139.7 (2) | C4A—C5A—C6A—C7A | 43.2 (3) |
S4B—C5B—C6B—C11B | −40.1 (2) | S4A—C5A—C6A—C7A | −136.28 (16) |
C11B—C6B—C7B—C8B | −0.2 (3) | C11A—C6A—C7A—C8A | 0.4 (3) |
C5B—C6B—C7B—C8B | −178.93 (19) | C5A—C6A—C7A—C8A | 179.13 (18) |
C6B—C7B—C8B—C9B | 0.3 (3) | C6A—C7A—C8A—C9A | −0.2 (3) |
C7B—C8B—C9B—C10B | 0.5 (4) | C7A—C8A—C9A—C10A | −0.3 (4) |
C8B—C9B—C10B—C11B | −1.4 (4) | C8A—C9A—C10A—C11A | 0.7 (4) |
C9B—C10B—C11B—C6B | 1.5 (4) | C9A—C10A—C11A—C6A | −0.5 (4) |
C7B—C6B—C11B—C10B | −0.7 (3) | C7A—C6A—C11A—C10A | −0.1 (3) |
C5B—C6B—C11B—C10B | 178.06 (19) | C5A—C6A—C11A—C10A | −178.8 (2) |
C5B—C4B—C12B—C13B | 131.2 (2) | C5A—C4A—C12A—C17A | −130.8 (2) |
C2B—C4B—C12B—C13B | −49.8 (2) | C2A—C4A—C12A—C17A | 49.9 (3) |
C5B—C4B—C12B—C17B | −48.7 (3) | C5A—C4A—C12A—C13A | 49.6 (3) |
C2B—C4B—C12B—C17B | 130.33 (19) | C2A—C4A—C12A—C13A | −129.60 (19) |
C17B—C12B—C13B—C14B | 1.1 (3) | C17A—C12A—C13A—C14A | −0.4 (3) |
C4B—C12B—C13B—C14B | −178.71 (19) | C4A—C12A—C13A—C14A | 179.11 (18) |
C12B—C13B—C14B—C15B | −0.2 (3) | C12A—C13A—C14A—C15A | 1.1 (3) |
C13B—C14B—C15B—C16B | −1.1 (4) | C13A—C14A—C15A—C16A | −0.5 (4) |
C14B—C15B—C16B—C17B | 1.3 (4) | C14A—C15A—C16A—C17A | −0.7 (4) |
C15B—C16B—C17B—C12B | −0.3 (3) | C13A—C12A—C17A—C16A | −0.8 (3) |
C13B—C12B—C17B—C16B | −0.9 (3) | C4A—C12A—C17A—C16A | 179.66 (19) |
C4B—C12B—C17B—C16B | 178.94 (18) | C15A—C16A—C17A—C12A | 1.4 (3) |
S1B—C1B—S2B—C2B | −179.91 (12) | S1A—C1A—S2A—C2A | 179.07 (12) |
S3B—C1B—S2B—C2B | −0.26 (12) | S3A—C1A—S2A—C2A | −0.56 (12) |
C3B—C2B—S2B—C1B | 0.16 (15) | C3A—C2A—S2A—C1A | 0.49 (16) |
C4B—C2B—S2B—C1B | −173.57 (17) | C4A—C2A—S2A—C1A | 174.70 (17) |
C2B—C3B—S3B—C1B | −0.16 (16) | C2A—C3A—S3A—C1A | −0.12 (17) |
S4B—C3B—S3B—C1B | 173.94 (14) | S4A—C3A—S3A—C1A | −174.80 (14) |
S1B—C1B—S3B—C3B | 179.92 (12) | S1A—C1A—S3A—C3A | −179.20 (12) |
S2B—C1B—S3B—C3B | 0.26 (12) | S2A—C1A—S3A—C3A | 0.45 (12) |
C2B—C3B—S4B—C5B | 0.71 (15) | C2A—C3A—S4A—C5A | −0.73 (15) |
S3B—C3B—S4B—C5B | −173.68 (14) | S3A—C3A—S4A—C5A | 174.19 (15) |
C4B—C5B—S4B—C3B | −0.95 (15) | C4A—C5A—S4A—C3A | 1.10 (15) |
C6B—C5B—S4B—C3B | 178.87 (14) | C6A—C5A—S4A—C3A | −179.33 (15) |
Experimental details
Crystal data | |
Chemical formula | C17H10S4 |
Mr | 342.53 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 23.441 (3), 10.1303 (14), 13.5222 (17) |
β (°) | 73.822 (10) |
V (Å3) | 3083.9 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.60 |
Crystal size (mm) | 0.45 × 0.24 × 0.15 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scans |
Tmin, Tmax | 0.840, 0.913 |
No. of measured, independent and observed (?) reflections | 7317, 7013, 5657 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.099, 1.07 |
No. of reflections | 5657 |
No. of parameters | 379 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.36 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1993), MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP (Johnson, 1965), PLATON (Spek, 1990).
C1A—S1A | 1.6482 (18) | C1B—S1B | 1.6485 (18) |
C1A—S2A | 1.7374 (18) | C1B—S2B | 1.7359 (18) |
C1A—S3A | 1.7355 (19) | C1B—S3B | 1.7373 (19) |
C2A—S2A | 1.7417 (17) | C2B—S2B | 1.7398 (17) |
C2A—C3A | 1.365 (2) | C2B—C3B | 1.371 (2) |
C2A—C4A | 1.428 (2) | C2B—C4B | 1.428 (2) |
C3A—S3A | 1.7274 (18) | C3B—S3B | 1.7257 (18) |
C3A—S4A | 1.7090 (18) | C3B—S4B | 1.7104 (18) |
C4A—C5A | 1.377 (2) | C4B—C5B | 1.375 (2) |
C5A—S4A | 1.7420 (18) | C5B—S4B | 1.7437 (18) |
S2A—C1A—S3A | 114.37 (10) | S2B—C1B—S3B | 114.40 (10) |
C2A—C3A—S3A | 117.75 (14) | C2B—C3B—S3B | 117.93 (13) |
C2A—C4A—C12A | 122.62 (15) | C2B—C4B—C12B | 122.59 (15) |
C4A—C5A—C6A | 130.66 (16) | C4B—C5B—C6B | 130.99 (16) |
C4A—C5A—S4A | 112.40 (13) | C4B—C5B—S4B | 112.16 (13) |
C5A—C6A—C11A | 119.82 (18) | C5B—C6B—C11B | 119.65 (18) |
C7A—C8A—C9A | 120.6 (2) | C7B—C8B—C9B | 120.2 (2) |
C9A—C10A—C11A | 120.3 (2) | C9B—C10B—C11B | 120.5 (3) |
C1A—S2A—C2A | 96.47 (8) | C1B—S2B—C2B | 96.67 (8) |
C1A—S3A—C3A | 95.95 (8) | C1B—S3B—C3B | 95.84 (8) |
C3A—S4A—C5A | 91.22 (8) | C3B—S4B—C5B | 91.37 (8) |
It has recently been discovered that Lawesson's reagent (LR), (I), could be used to construct 1,4-dithiine (III) and/or thiophene heterocycles from 1,8-diketones (II) (Öztürk, 1996). The possible mechanism of this reaction involves a nine-membered-ring intermediate which then rearranges to the six-membered dithiine ring. In-situ loss of an S atom from the 1,4-dithiine ring leads to the formation of a thiophene. The dithiine/thiophene ratio depends on the electron-withdrawing or electron-releasing nature of the aromatic (Ar) substituent. While electron-donating groups make the loss of the S atom easier, electron-withdrawing groups make it harder.
Our previous and ongoing studies indicated that when the corresponding 1,8-diketone is treated with LR, dithiine (V) is obtained as a minor product (Öztürk, 1996; Öztürk & Türksoy,1999). On the other hand, when the phenyl group of the 1,8-diketone is replaced by para-methoxyphenyl, thiophene rather than dithiine becomes a major product (Öztürk & Wallis, 1996).
In an effort to obtain new diphenyl-substituted dithiine (VIII) and thiophene (IX) heterocycles, which are useful building blocks for organic conducting/superconducting materials, the tetraphenyl-1,8-diketone (VII) was reacted overnight with LR in refluxing toluene under a nitrogen atmosphere. In accordance with the results obtained previously (Lee et al., 1998), no product containing dithiine ring (VIII) was obtained. Diphenylthiophene (IX) was isolated as the sole product and its the X-ray crystal structure is reported here.
Compound (IX) crystallizes in P21/c and has two crystallographically independent molecules in the asymmetric unit, labelled A and B (Fig. 1). Interatomic distances and angles are very similar in both molecules. The fused heterocyle in the molecules is nearly planar; the best planes of the two five-membered rings (thiophene and dithiole) form dihedral angles of 4.77 (8)° in molecule A and 5.35 (8)° in molecule B. These values are comparable with those found in 6-(4-methoxyphenyl)thieno[2,3-d][1,3]dithiole-2-thione [4.2 (1)°; Öztürk & Wallis, 1996]. The phenyl groups in (IX) are essentially planar, the maximum deviations being 0.007 (2) Å (C17A in molecule A) and -0.008 (3) Å (C15B in molecule B). The dihedral angles between the phenyl groups (C6—C11 and C12—C17) and the fused heterocycle are 42.88 (9) and 52.79 (8)°, while the dihedral angle between these two phenyl rings is 55.05 (11)° for molecule A; these values are slightly less, 40.62 (9), 52.28 (8) and 52.75 (11)°, respectively, for molecule B. The terminal C═S double bond [mean 1.648 (2) Å] is quite similar to that of other structures including 1,3-thiole-2-thione (Öztürk & Wallis, 1996; Parvez et al., 1996; Lee & Noh, 1998). There is a marked asymmetry in the thiophene and dithiole rings. The S4—C5 bond distance [1.742 (2) in molecule A and 1.744 (2) Å in molecule B] is longer than the S4—C3 bond distance [1.709 (2) and 1.710 (2) Å for molecules A and B, respectively]. The mean bond angle at the S4 atom, 91.29 (8)°, is significantly smaller than the angles at the S2 and S3 atoms, which have mean values of 96.57 (8) and 95.89 (8)°, respectively.
As usual in this type of compound, packing appears to be governed by S···S interactions. Some intermolecular S···S contact distances are S1A···S3Ai 3.333 (1), S1A···S4Ai 3.372 (1), S1A···S1Aii 3.555 (1), S2A···S3Ai 3.427 (1), S1B···S3Biii 3.344 (1), S1B···S4Biii 3.355 (1), S1B···S1Biv 3.570 (1) and S2B···S3Biii 3.447 (1) Å and contribute to the formation of chains along the b direction [symmetry codes: (i) 2 - x, 1/2 + y, 3/2 - z; (ii) 2 - x, 1 - y, 2 - z; (iii) 1 - x, 1/2 + y, 3/2 - z; (iv) 1 - x, 1 - y, 2 - z]. These chains, in turn, are held together by van der Waals interactions.