Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105005251/av1231sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105005251/av1231IIIsup2.hkl |
CCDC reference: 275537
Compound (III) was prepared as follows. To a solution of 3,4-dibromothiophene (0.96 g, 4 mmol) in dry ether (30 ml) was added n-BuLi (1.6 ml, 4 mmol, 2.5 M) by syringe at 351 K under a nitrogen atmosphere. The solution was stirred for 5 min and elemental sulfur (Quantity?) was added portionwise. The solution was then stirred for 15 min and the addition of n-BuLi and elemental S was repeated in the same ratios at the same temperature (351 K). The final solution was stirred for a further 30 min, then 2-bromo-4-methoxyacetophenone (2 g, 9 mmol) was added portionwise and the solution was allowed to come to room temperature. After the addition of ice, the mixture was extracted with ether (3 × 20 ml). The organic layer was dried over MgSO4, filtered and the solvent evaporated under reduced pressure. The crude product was purified by column chromatography, eluting with hexane–ethyl acetate (5:1), to yield the title compound (m.p. 387–388 K, yield 1 g, 58%). 1H NMR (200 MHz, CDCl3, δ, p.p.m.): 7.86 (4H, d, J = 8.3 Hz, Ph), 7.25 (2H, s, thiophene), 6.87 (4H, d, J = 8.3 Hz, Ph), 4.18 (4H, s, SCH2), 3.83 (6H, s, OCH3); 13C NMR (67.8 MHz, CDCl3, δ, p.p.m.): 192.7 (C ═O), 163.7 (q, C), 132 (q, C), 130.1 (CH), 128.5 (q, C), 127.2 (CH), 113.8 (CH), 55.4 (OCH3), 40.9 (SCH2); m/z (EI): 444 M+.
All H atoms were placed in idealized positions and refined using a riding model, with Uiso(H) = 1.3Ueq(C), and with fixed C—H distances of 0.93 (aromatic), 0.96 (methyl) and 0.97 Å (ethyl).
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 1990); software used to prepare material for publication: WinGX (Farrugia, 1999).
C22H20O4S3 | F(000) = 928 |
Mr = 444.56 | Dx = 1.427 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 10.4682 (12) Å | θ = 9.7–18.1° |
b = 10.9027 (12) Å | µ = 0.39 mm−1 |
c = 18.4929 (12) Å | T = 293 K |
β = 101.390 (7)° | Prism, yellow |
V = 2069.1 (4) Å3 | 0.6 × 0.6 × 0.48 mm |
Z = 4 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.026 |
non–profiled ω scans | θmax = 26.3°, θmin = 2.5° |
Absorption correction: ψ scan (North et al., 1968) | h = 0→13 |
Tmin = 0.802, Tmax = 0.837 | k = 0→13 |
4417 measured reflections | l = −23→22 |
4191 independent reflections | 3 standard reflections every 120 min |
3279 reflections with I > 2σ(I) | intensity decay: 8% |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + (0.0507P)2 + 0.5012P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.100 | (Δ/σ)max = 0.001 |
S = 1.05 | Δρmax = 0.18 e Å−3 |
4191 reflections | Δρmin = −0.26 e Å−3 |
270 parameters |
C22H20O4S3 | V = 2069.1 (4) Å3 |
Mr = 444.56 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.4682 (12) Å | µ = 0.39 mm−1 |
b = 10.9027 (12) Å | T = 293 K |
c = 18.4929 (12) Å | 0.6 × 0.6 × 0.48 mm |
β = 101.390 (7)° |
Enraf-Nonius CAD-4 diffractometer | 3279 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.026 |
Tmin = 0.802, Tmax = 0.837 | 3 standard reflections every 120 min |
4417 measured reflections | intensity decay: 8% |
4191 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.18 e Å−3 |
4191 reflections | Δρmin = −0.26 e Å−3 |
270 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.62116 (18) | −0.11830 (19) | −0.02545 (11) | 0.0472 (5) | |
H1 | 0.5435 | −0.1378 | −0.0574 | 0.057* | |
C1' | 0.81939 (19) | −0.10864 (19) | 0.06986 (11) | 0.0472 (5) | |
H1' | 0.8894 | −0.1212 | 0.1087 | 0.057* | |
C2 | 0.68510 (17) | −0.01027 (17) | −0.02715 (10) | 0.0393 (4) | |
C2' | 0.80141 (17) | −0.00459 (17) | 0.02923 (10) | 0.0386 (4) | |
C3' | 1.02794 (17) | 0.08251 (17) | 0.11217 (10) | 0.0413 (4) | |
H3'A | 0.9901 | 0.067 | 0.1551 | 0.05* | |
H3'B | 1.07 | 0.0078 | 0.1005 | 0.05* | |
C3 | 0.50187 (17) | 0.05237 (17) | −0.14744 (10) | 0.0415 (4) | |
H3A | 0.521 | −0.0262 | −0.1675 | 0.05* | |
H3B | 0.4345 | 0.0401 | −0.1189 | 0.05* | |
C4' | 1.12737 (18) | 0.18475 (17) | 0.12864 (10) | 0.0410 (4) | |
C4 | 0.45493 (18) | 0.14131 (17) | −0.20929 (10) | 0.0411 (4) | |
C5' | 1.24001 (17) | 0.16556 (17) | 0.19009 (10) | 0.0384 (4) | |
C5 | 0.33199 (18) | 0.11468 (17) | −0.26222 (10) | 0.0405 (4) | |
C6' | 1.24802 (18) | 0.06766 (18) | 0.23869 (10) | 0.0424 (4) | |
H6' | 1.1824 | 0.0089 | 0.2313 | 0.051* | |
C6 | 0.25499 (19) | 0.01326 (18) | −0.25711 (11) | 0.0474 (5) | |
H6 | 0.2801 | −0.0418 | −0.2185 | 0.057* | |
C7 | 0.14117 (19) | −0.00821 (18) | −0.30825 (11) | 0.0473 (5) | |
H7 | 0.0904 | −0.0767 | −0.3039 | 0.057* | |
C7' | 1.35104 (18) | 0.05527 (18) | 0.29776 (10) | 0.0436 (4) | |
H7' | 1.3538 | −0.0102 | 0.3303 | 0.052* | |
C8 | 0.10404 (18) | 0.07341 (19) | −0.36584 (10) | 0.0433 (4) | |
C8' | 1.45044 (18) | 0.14174 (17) | 0.30797 (10) | 0.0412 (4) | |
C9' | 1.44698 (19) | 0.23751 (18) | 0.25786 (11) | 0.0458 (5) | |
H9' | 1.5153 | 0.2934 | 0.2634 | 0.055* | |
C10' | 1.34270 (19) | 0.24943 (17) | 0.20021 (10) | 0.0425 (4) | |
H10' | 1.3405 | 0.3144 | 0.1674 | 0.051* | |
C10 | 0.29290 (19) | 0.19500 (19) | −0.32089 (11) | 0.0475 (5) | |
H10 | 0.3434 | 0.2637 | −0.3254 | 0.057* | |
C11' | 1.5535 (2) | 0.0554 (2) | 0.42306 (12) | 0.0679 (7) | |
H11'A | 1.633 | 0.0627 | 0.459 | 0.102* | |
H11'B | 1.5453 | −0.0268 | 0.4041 | 0.102* | |
H11'C | 1.4809 | 0.0738 | 0.4458 | 0.102* | |
C11 | −0.0839 (2) | −0.0439 (2) | −0.41892 (13) | 0.0631 (6) | |
H11C | −0.158 | −0.0392 | −0.4588 | 0.095* | |
H11B | −0.113 | −0.0496 | −0.3729 | 0.095* | |
H11A | −0.0332 | −0.1151 | −0.4251 | 0.095* | |
C9 | 0.1813 (2) | 0.1746 (2) | −0.37212 (11) | 0.0504 (5) | |
H9 | 0.1572 | 0.2289 | −0.4112 | 0.061* | |
O1' | 1.11355 (15) | 0.27892 (13) | 0.09311 (8) | 0.0564 (4) | |
O1 | 0.51783 (14) | 0.23349 (13) | −0.21523 (8) | 0.0559 (4) | |
O2 | −0.00581 (13) | 0.06345 (14) | −0.41881 (8) | 0.0553 (4) | |
O2' | 1.55554 (14) | 0.13925 (13) | 0.36415 (7) | 0.0539 (4) | |
S1 | 0.69923 (5) | −0.21429 (5) | 0.04195 (3) | 0.05294 (16) | |
S2' | 0.90191 (5) | 0.12607 (4) | 0.03525 (3) | 0.04417 (14) | |
S2 | 0.64629 (5) | 0.11260 (5) | −0.08911 (3) | 0.04645 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0338 (10) | 0.0548 (12) | 0.0488 (11) | 0.0020 (9) | −0.0019 (8) | 0.0034 (9) |
C1' | 0.0390 (10) | 0.0532 (12) | 0.0446 (10) | 0.0046 (9) | −0.0030 (8) | 0.0031 (9) |
C2 | 0.0317 (9) | 0.0433 (10) | 0.0402 (9) | 0.0074 (8) | 0.0010 (7) | −0.0006 (8) |
C2' | 0.0311 (9) | 0.0462 (10) | 0.0362 (9) | 0.0079 (8) | 0.0011 (7) | −0.0033 (8) |
C3' | 0.0355 (9) | 0.0439 (10) | 0.0402 (10) | 0.0066 (8) | −0.0032 (8) | −0.0035 (8) |
C3 | 0.0352 (9) | 0.0429 (10) | 0.0421 (10) | 0.0042 (8) | −0.0029 (8) | −0.0021 (8) |
C4' | 0.0408 (10) | 0.0408 (10) | 0.0388 (10) | 0.0059 (8) | 0.0015 (8) | −0.0037 (8) |
C4 | 0.0354 (10) | 0.0417 (10) | 0.0432 (10) | 0.0038 (8) | −0.0001 (8) | −0.0011 (8) |
C5' | 0.0364 (9) | 0.0382 (9) | 0.0382 (9) | 0.0009 (8) | 0.0019 (7) | −0.0032 (8) |
C5 | 0.0367 (9) | 0.0417 (10) | 0.0402 (10) | 0.0033 (8) | 0.0004 (8) | 0.0014 (8) |
C6' | 0.0350 (9) | 0.0434 (10) | 0.0460 (11) | −0.0071 (8) | 0.0009 (8) | 0.0025 (8) |
C6 | 0.0489 (11) | 0.0440 (11) | 0.0434 (10) | −0.0012 (9) | −0.0058 (8) | 0.0084 (8) |
C7 | 0.0441 (11) | 0.0451 (11) | 0.0477 (11) | −0.0054 (9) | −0.0030 (9) | 0.0014 (9) |
C7' | 0.0404 (10) | 0.0437 (10) | 0.0432 (10) | −0.0052 (8) | −0.0004 (8) | 0.0057 (8) |
C8 | 0.0353 (9) | 0.0525 (11) | 0.0381 (10) | 0.0055 (8) | −0.0022 (8) | −0.0035 (8) |
C8' | 0.0391 (10) | 0.0442 (10) | 0.0370 (9) | −0.0028 (8) | −0.0007 (8) | −0.0045 (8) |
C9' | 0.0463 (11) | 0.0429 (10) | 0.0444 (10) | −0.0133 (9) | −0.0001 (8) | −0.0019 (8) |
C10' | 0.0494 (11) | 0.0358 (9) | 0.0396 (10) | −0.0035 (8) | 0.0023 (8) | 0.0010 (8) |
C10 | 0.0430 (11) | 0.0473 (11) | 0.0488 (11) | −0.0024 (9) | 0.0004 (9) | 0.0074 (9) |
C11' | 0.0706 (15) | 0.0718 (15) | 0.0484 (12) | −0.0162 (12) | −0.0197 (11) | 0.0138 (11) |
C11 | 0.0432 (12) | 0.0805 (16) | 0.0590 (13) | −0.0087 (11) | −0.0057 (10) | −0.0072 (12) |
C9 | 0.0472 (11) | 0.0540 (12) | 0.0453 (11) | 0.0031 (9) | −0.0026 (9) | 0.0129 (9) |
O1' | 0.0605 (9) | 0.0450 (8) | 0.0553 (9) | 0.0030 (7) | −0.0092 (7) | 0.0067 (7) |
O1 | 0.0468 (8) | 0.0508 (8) | 0.0634 (9) | −0.0075 (7) | −0.0057 (7) | 0.0077 (7) |
O2 | 0.0427 (8) | 0.0661 (9) | 0.0489 (8) | −0.0009 (7) | −0.0110 (6) | 0.0022 (7) |
O2' | 0.0500 (8) | 0.0587 (9) | 0.0439 (8) | −0.0151 (7) | −0.0129 (6) | 0.0048 (6) |
S1 | 0.0443 (3) | 0.0519 (3) | 0.0593 (3) | 0.0009 (2) | 0.0022 (2) | 0.0108 (2) |
S2' | 0.0399 (3) | 0.0430 (3) | 0.0429 (3) | 0.0044 (2) | −0.0082 (2) | −0.0024 (2) |
S2 | 0.0374 (3) | 0.0450 (3) | 0.0493 (3) | 0.0016 (2) | −0.0099 (2) | 0.0033 (2) |
C1—C2 | 1.358 (3) | C6'—H6' | 0.93 |
C1—S1 | 1.707 (2) | C6—C7 | 1.387 (3) |
C1—H1 | 0.93 | C6—H6 | 0.93 |
C1'—C2' | 1.353 (3) | C7—C8 | 1.383 (3) |
C1'—S1 | 1.708 (2) | C7—H7 | 0.93 |
C1'—H1' | 0.93 | C7'—C8' | 1.389 (3) |
C2—C2' | 1.439 (2) | C7'—H7' | 0.93 |
C2—S2 | 1.7575 (19) | C8—O2 | 1.360 (2) |
C2'—S2' | 1.761 (2) | C8—C9 | 1.386 (3) |
C3'—C4' | 1.514 (3) | C8'—O2' | 1.356 (2) |
C3'—S2' | 1.8024 (17) | C8'—C9' | 1.392 (3) |
C3'—H3'A | 0.97 | C9'—C10' | 1.373 (3) |
C3'—H3'B | 0.97 | C9'—H9' | 0.93 |
C3—C4 | 1.506 (3) | C10'—H10' | 0.93 |
C3—S2 | 1.7989 (18) | C10—C9 | 1.369 (3) |
C3—H3A | 0.97 | C10—H10 | 0.93 |
C3—H3B | 0.97 | C11'—O2' | 1.426 (3) |
C4'—O1' | 1.212 (2) | C11'—H11'A | 0.96 |
C4'—C5' | 1.482 (2) | C11'—H11'B | 0.96 |
C4—O1 | 1.218 (2) | C11'—H11'C | 0.96 |
C4—C5 | 1.484 (2) | C11—O2 | 1.427 (3) |
C5'—C6' | 1.387 (3) | C11—H11C | 0.96 |
C5'—C10' | 1.395 (3) | C11—H11B | 0.96 |
C5—C6 | 1.382 (3) | C11—H11A | 0.96 |
C5—C10 | 1.391 (3) | C9—H9 | 0.93 |
C6'—C7' | 1.382 (2) | ||
C2—C1—S1 | 112.43 (14) | C8—C7—C6 | 119.29 (18) |
C2—C1—H1 | 123.8 | C8—C7—H7 | 120.4 |
S1—C1—H1 | 123.8 | C6—C7—H7 | 120.4 |
C2'—C1'—S1 | 112.59 (14) | C6'—C7'—C8' | 119.19 (17) |
C2'—C1'—H1' | 123.7 | C6'—C7'—H7' | 120.4 |
S1—C1'—H1' | 123.7 | C8'—C7'—H7' | 120.4 |
C1—C2—C2' | 111.76 (17) | O2—C8—C7 | 124.91 (18) |
C1—C2—S2 | 128.65 (14) | O2—C8—C9 | 115.31 (17) |
C2'—C2—S2 | 119.54 (14) | C7—C8—C9 | 119.78 (17) |
C1'—C2'—C2 | 111.79 (17) | O2'—C8'—C7' | 124.27 (17) |
C1'—C2'—S2' | 128.84 (14) | O2'—C8'—C9' | 115.82 (16) |
C2—C2'—S2' | 119.33 (14) | C7'—C8'—C9' | 119.90 (17) |
C4'—C3'—S2' | 109.37 (13) | C10'—C9'—C8' | 120.01 (17) |
C4'—C3'—H3'A | 109.8 | C10'—C9'—H9' | 120 |
S2'—C3'—H3'A | 109.8 | C8'—C9'—H9' | 120 |
C4'—C3'—H3'B | 109.8 | C9'—C10'—C5' | 121.02 (17) |
S2'—C3'—H3'B | 109.8 | C9'—C10'—H10' | 119.5 |
H3'A—C3'—H3'B | 108.2 | C5'—C10'—H10' | 119.5 |
C4—C3—S2 | 109.26 (13) | C9—C10—C5 | 121.12 (19) |
C4—C3—H3A | 109.8 | C9—C10—H10 | 119.4 |
S2—C3—H3A | 109.8 | C5—C10—H10 | 119.4 |
C4—C3—H3B | 109.8 | O2'—C11'—H11'A | 109.5 |
S2—C3—H3B | 109.8 | O2'—C11'—H11'B | 109.5 |
H3A—C3—H3B | 108.3 | H11'A—C11'—H11'B | 109.5 |
O1'—C4'—C5' | 121.80 (17) | O2'—C11'—H11'C | 109.5 |
O1'—C4'—C3' | 120.71 (16) | H11'A—C11'—H11'C | 109.5 |
C5'—C4'—C3' | 117.48 (16) | H11'B—C11'—H11'C | 109.5 |
O1—C4—C5 | 121.05 (17) | O2—C11—H11C | 109.5 |
O1—C4—C3 | 119.90 (17) | O2—C11—H11B | 109.5 |
C5—C4—C3 | 119.04 (16) | H11C—C11—H11B | 109.5 |
C6'—C5'—C10' | 118.09 (16) | O2—C11—H11A | 109.5 |
C6'—C5'—C4' | 122.86 (17) | H11C—C11—H11A | 109.5 |
C10'—C5'—C4' | 119.05 (17) | H11B—C11—H11A | 109.5 |
C6—C5—C10 | 118.10 (17) | C10—C9—C8 | 120.21 (18) |
C6—C5—C4 | 123.57 (17) | C10—C9—H9 | 119.9 |
C10—C5—C4 | 118.32 (17) | C8—C9—H9 | 119.9 |
C7'—C6'—C5' | 121.69 (17) | C8—O2—C11 | 117.97 (16) |
C7'—C6'—H6' | 119.2 | C8'—O2'—C11' | 117.77 (16) |
C5'—C6'—H6' | 119.2 | C1—S1—C1' | 91.43 (10) |
C5—C6—C7 | 121.49 (18) | C2'—S2'—C3' | 99.89 (9) |
C5—C6—H6 | 119.3 | C2—S2—C3 | 99.87 (9) |
C7—C6—H6 | 119.3 | ||
S1—C1—C2—C2' | −0.8 (2) | C6—C7—C8—O2 | −179.13 (19) |
S1—C1—C2—S2 | 176.74 (12) | C6—C7—C8—C9 | 0.6 (3) |
S1—C1'—C2'—C2 | 0.0 (2) | C6'—C7'—C8'—O2' | 179.53 (18) |
S1—C1'—C2'—S2' | −177.40 (11) | C6'—C7'—C8'—C9' | −1.7 (3) |
C1—C2—C2'—C1' | 0.5 (2) | O2'—C8'—C9'—C10' | −178.32 (18) |
S2—C2—C2'—C1' | −177.28 (14) | C7'—C8'—C9'—C10' | 2.8 (3) |
C1—C2—C2'—S2' | 178.19 (14) | C8'—C9'—C10'—C5' | −1.0 (3) |
S2—C2—C2'—S2' | 0.4 (2) | C6'—C5'—C10'—C9' | −1.9 (3) |
S2'—C3'—C4'—O1' | 1.4 (2) | C4'—C5'—C10'—C9' | 177.83 (17) |
S2'—C3'—C4'—C5' | −179.45 (13) | C6—C5—C10—C9 | 0.1 (3) |
S2—C3—C4—O1 | 3.6 (2) | C4—C5—C10—C9 | 179.17 (19) |
S2—C3—C4—C5 | −176.38 (14) | C5—C10—C9—C8 | 0.7 (3) |
O1'—C4'—C5'—C6' | 169.74 (19) | O2—C8—C9—C10 | 178.70 (19) |
C3'—C4'—C5'—C6' | −9.4 (3) | C7—C8—C9—C10 | −1.0 (3) |
O1'—C4'—C5'—C10' | −9.9 (3) | C7—C8—O2—C11 | −5.3 (3) |
C3'—C4'—C5'—C10' | 170.94 (17) | C9—C8—O2—C11 | 174.98 (19) |
O1—C4—C5—C6 | −178.31 (19) | C7'—C8'—O2'—C11' | −11.0 (3) |
C3—C4—C5—C6 | 1.7 (3) | C9'—C8'—O2'—C11' | 170.12 (19) |
O1—C4—C5—C10 | 2.7 (3) | C2—C1—S1—C1' | 0.68 (17) |
C3—C4—C5—C10 | −177.26 (17) | C2'—C1'—S1—C1 | −0.39 (17) |
C10'—C5'—C6'—C7' | 3.0 (3) | C1'—C2'—S2'—C3' | −2.3 (2) |
C4'—C5'—C6'—C7' | −176.67 (18) | C2—C2'—S2'—C3' | −179.54 (14) |
C10—C5—C6—C7 | −0.6 (3) | C4'—C3'—S2'—C2' | −179.19 (13) |
C4—C5—C6—C7 | −179.57 (18) | C1—C2—S2—C3 | −0.3 (2) |
C5—C6—C7—C8 | 0.2 (3) | C2'—C2—S2—C3 | 177.04 (14) |
C5'—C6'—C7'—C8' | −1.3 (3) | C4—C3—S2—C2 | −176.36 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O1 | 0.93 | 2.47 | 2.778 (2) | 99 |
C10′—H10′···O1′ | 0.93 | 2.53 | 2.811 (2) | 98 |
C7—H7···O1i | 0.93 | 2.42 | 3.343 (2) | 173 |
Symmetry code: (i) −x+1/2, y−1/2, −z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C22H20O4S3 |
Mr | 444.56 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 10.4682 (12), 10.9027 (12), 18.4929 (12) |
β (°) | 101.390 (7) |
V (Å3) | 2069.1 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.39 |
Crystal size (mm) | 0.6 × 0.6 × 0.48 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.802, 0.837 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4417, 4191, 3279 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.623 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.100, 1.05 |
No. of reflections | 4191 |
No. of parameters | 270 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.26 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 1990), WinGX (Farrugia, 1999).
C1—C2 | 1.358 (3) | C3—S2 | 1.7989 (18) |
C1—S1 | 1.707 (2) | C4'—O1' | 1.212 (2) |
C1'—C2' | 1.353 (3) | C4'—C5' | 1.482 (2) |
C1'—S1 | 1.708 (2) | C4—O1 | 1.218 (2) |
C2—C2' | 1.439 (2) | C4—C5 | 1.484 (2) |
C2—S2 | 1.7575 (19) | C8—O2 | 1.360 (2) |
C2'—S2' | 1.761 (2) | C8'—O2' | 1.356 (2) |
C3'—C4' | 1.514 (3) | C11'—O2' | 1.426 (3) |
C3'—S2' | 1.8024 (17) | C11—O2 | 1.427 (3) |
C3—C4 | 1.506 (3) | ||
C2—C1—S1 | 112.43 (14) | O2—C8—C9 | 115.31 (17) |
C2'—C1'—S1 | 112.59 (14) | O2'—C8'—C9' | 115.82 (16) |
C1—C2—S2 | 128.65 (14) | C8—O2—C11 | 117.97 (16) |
C1'—C2'—S2' | 128.84 (14) | C8'—O2'—C11' | 117.77 (16) |
C4'—C3'—S2' | 109.37 (13) | C1—S1—C1' | 91.43 (10) |
C4—C3—S2 | 109.26 (13) | C2'—S2'—C3' | 99.89 (9) |
C10'—C5'—C4' | 119.05 (17) | C2—S2—C3 | 99.87 (9) |
C10—C5—C4 | 118.32 (17) | ||
S2'—C3'—C4'—O1' | 1.4 (2) | C2—C2'—S2'—C3' | −179.54 (14) |
S2—C3—C4—O1 | 3.6 (2) | C4'—C3'—S2'—C2' | −179.19 (13) |
O1'—C4'—C5'—C6' | 169.74 (19) | C1—C2—S2—C3 | −0.3 (2) |
O1—C4—C5—C6 | −178.31 (19) | C2'—C2—S2—C3 | 177.04 (14) |
C1'—C2'—S2'—C3' | −2.3 (2) | C4—C3—S2—C2 | −176.36 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O1 | 0.93 | 2.47 | 2.778 (2) | 99 |
C10'—H10'···O1' | 0.93 | 2.53 | 2.811 (2) | 98 |
C7—H7···O1i | 0.93 | 2.42 | 3.343 (2) | 173 |
Symmetry code: (i) −x+1/2, y−1/2, −z−1/2. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Dithieno[3,2 − b;2',3'-d]thiophenes (DTT), which consist of three fused thiophene heterocycles, are important compounds for the synthesis of a wide variety of materials for electronics and optical applications (Kim et al., 2001, 1999; Osterod et al., 2001; Ventelon et al., 1999; Tsivgoulis & Lehn, 1995). Dimeric DTT systems, which have been employed in thin-film transistors, have been shown to have high mobilities and on/off ratios (Sirringhaus et al., 1997; Morrison et al., 1999; Li et al., 1998). Their oxidized dioxide forms demonstrate interesting fluorescence properties and this creates important application opportunities, such as their use as labelling agents in biological systems (Sotgiu et al. 2003; Barbarella, 2002; Barbarella et al., 2001), photovoltaic devices (Catellani et al., 2002) and light-emitting diodes (Gigli et al., 2001). Conducting polymers (Fujitsuka et al., 1996; Lazzaroni et al., 1989; Di Marco et al., 1985), and organic acceptor and donor molecules for the preparation of different cationic radical salts and charge-transfer complexes (Mazaki & Kabayashi, 1992; Yui et al., 1987; Hayashi et al., 1992; Bertinelli et al., 1984), have been prepared.
Although some methods have been developed for the synthesis of the DTT molecule (De Jong & Janssen, 1971; Mazaki & Kabayashi, 1989; Hellberg & Remonen, 1995; Schroth et al., 1997; Frey et al., 2002), new synthetic methods are still required, particularly to functionalize the system. Recently, we have reported an efficient and novel method (Ertas & Ozturk, 2004). During the application of this method to the synthesis of 3,5-di(4-methoxyphenyl)dithieno[3,2 − b;2',3'-d]thiophenes, (I), an intermediate was isolated, namely the title compound, (III), which was obtained in three steps starting from 3,4-dibromothiophene, (II) (scheme). We report here the X-ray single-crystal structure of (III), which has α-thioketones at the 3- and 4- positions of the thiophene ring.
The molecular structure and atom-numbering scheme of (III) are shown in Fig. 1, and the arrangement of the molecules in the unit cell is given in Fig. 2. Selected bond lengths and angles are listed in Table 1. Overall, the molecule is fairly flat; the dihedral angles between the essentially planar thiophene and phenyl rings (C5–C10 and C5'–C10') are 9.4 (1) and 10.6 (1)°, respectively, while the dihedral angle between these two phenyl rings is 2.4 (1)°. The thioketone moieties attached to atoms C2 and C2' of the thiophene ring adopt an extended conformation, with torsion angles close to 0 or 180°: C1—C2—S2—C3 − 0.3 (2) and C1'—C2'—S2'—C3' −2.3 (2)°, C2—S2—C3—C4 − 176.4 (1) and C2'—S2'—C3'—C4' −179.2 (1)°, S2—C3—C4—O1 3.7 (2) and S2'—C3'—C4'—O1' 1.4 (2)°, and C3—C4—C5—C6 1.7 (3) and C3'—C4'—C5'—C6' −9.4 (3)°. The angles between the least-squares planes formed by the thioketone groups (S2/C3/C4/O1 and S2'/C3'/C4'/O1') and the thiophene ring are 7.7 (1) and 0.7 (1)°, respectively. Thus, this part of the molecule is almost coplanar with the thiophene ring.
The S1—C1 and S1'—C1' bond lengths [1.709 (2) and 1.709 (2) Å] are in good agreement with those found for structures containing a thiophene ring (Kazak et al., 2000; Rodinovskaya et al., 2002). In the thioketone parts, the difference between the S2—C2/S2'—C2' bond lengths [1.758 (2) and 1.762 (2) Å, respectively] and the S2—C3/S2'—C3' bond lengths [1.799 (2) and 1.803 (2) Å, respectively] can be attributed to the different hybridization of the Csp3 and Csp2 atoms. Bonds C4—O1 and C4'—O1' are found to have normal double-bond lengths.
There are no intramolecular hydrogen bonds in (III), but the O atoms of the ketone groups are involved in short contacts, forming a five-membered ring-structure (Table 2). The interatomic distances S2···S2' [3.169 (1) Å], S2···O1 [2.783 (2) Å] and S2'···O1' [2.810 (2) Å] also indicate close contacts. There is a C—H···O-type intermolecular hydrogen bond between neighbouring molecules along the b axis. Molecules are stacked along the a direction at a mean interplanar distance of ≈ 3.45 Å; no hydrogen bonds are observed between these layers (Fig. 2).