Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007116/wn6142sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007116/wn6142Isup2.hkl |
CCDC reference: 214591
A mixture of Pd(PPh3)4 (91.3 mg, 0.079 mmol), CuI (15.0 mg, 0.079 mmol), 2-bromo-5-(phenylethylyne)thiophene (500 mg, 1.90 mmol), (R)-2,2'-ethynyl-1,1'-binaphthyl (240 mg, 0.791 mmol) and iPr2NH (3 ml) in toluene (20 ml) was heated under an argon atmosphere at 318 K for 15 h. After the usual work-up with NH4Cl/CHCl3, the organic layer was dried over MgSO4, and the solvents were removed under reduced pressure. The resulting residue was purified by chromatography on silica gel (hexane–CH2Cl2 4:1, RF = 0.23) to give 429.3 mg of the title compound, (I), as a yellow solid (81% yield); 1H NMR (300 MHz, CDCl3): δ 6.51 (d, J = 3.8 Hz, 2H), 6.94 (d, J = 3.8 Hz, 2H), 7.40–7.30 (m, 10H), 7.48–7.46 (m, 4H), 7.54–7.51 (m, 2H), 7.76 (d, J = 8.2 Hz, 2H), 7.99 (dd, J = 8.2, J = 6.7 Hz, 4H); 13C NMR (125 MHz, CDCl3): δ 82.4, 86.4, 93.9, 94.2, 121.1, 122. 6, 124.4, 124.5, 126.5, 126.8, 127.0, 127.6, 128.1, 128.2, 128.3, 128.6, 131.4, 131.5, 131.6, 132.5, 133.1, 140.0; elemental analysis calculated (%) for C48H26S2: C 86.45, H 3.93, found: C 86.29 H 3.66.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: TEXSAN (Rigaku, 1999); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Molecular Structure Corporation and Rigaku, 2001).
Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
C48H26S2 | F(000) = 692.00 |
Mr = 666.85 | Dx = 1.272 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.7107 Å |
a = 12.2484 (1) Å | Cell parameters from 3933 reflections |
b = 12.6553 (1) Å | θ = 2.3–25.0° |
c = 11.5031 (9) Å | µ = 0.19 mm−1 |
β = 102.407 (5)° | T = 123 K |
V = 1741.4 (1) Å3 | Cube, yellow |
Z = 2 | 0.30 × 0.20 × 0.20 mm |
Rigaku RAXIS-IV diffractometer | 3501 reflections with F2 > 2σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.022 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −15→15 |
Tmin = 0.963, Tmax = 1.000 | k = −16→15 |
6879 measured reflections | l = −14→14 |
3505 independent reflections |
Refinement on F2 | w = 1/[0.0016Fo2 + σ2(Fo) + 0.5]/(4Fo2) |
R[F2 > 2σ(F2)] = 0.030 | (Δ/σ)max < 0.001 |
wR(F2) = 0.094 | Δρmax = 0.33 e Å−3 |
S = 1.18 | Δρmin = −0.44 e Å−3 |
2081 reflections | Absolute structure: Flack (1983), 1592 Friedel pairs |
240 parameters | Absolute structure parameter: 0.07 (4) |
All H-atom parameters refined |
C48H26S2 | V = 1741.4 (1) Å3 |
Mr = 666.85 | Z = 2 |
Monoclinic, C2 | Mo Kα radiation |
a = 12.2484 (1) Å | µ = 0.19 mm−1 |
b = 12.6553 (1) Å | T = 123 K |
c = 11.5031 (9) Å | 0.30 × 0.20 × 0.20 mm |
β = 102.407 (5)° |
Rigaku RAXIS-IV diffractometer | 3505 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3501 reflections with F2 > 2σ(F2) |
Tmin = 0.963, Tmax = 1.000 | Rint = 0.022 |
6879 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | All H-atom parameters refined |
wR(F2) = 0.094 | Δρmax = 0.33 e Å−3 |
S = 1.18 | Δρmin = −0.44 e Å−3 |
2081 reflections | Absolute structure: Flack (1983), 1592 Friedel pairs |
240 parameters | Absolute structure parameter: 0.07 (4) |
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY |
Refinement. Refinement using reflections with F2 > −10.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
S1 | −0.37680 (3) | −0.42883 (3) | −0.32626 (2) | 0.02704 (8) | |
C12 | −0.1920 (1) | −0.5298 (1) | −0.1934 (1) | 0.0200 (3) | |
C2 | 0.14344 (9) | −0.72572 (9) | −0.0161 (1) | 0.0166 (2) | |
C13 | −0.3049 (1) | −0.49753 (9) | −0.2037 (1) | 0.0215 (3) | |
C11 | −0.0985 (1) | −0.5642 (1) | −0.1776 (1) | 0.0191 (3) | |
C3 | 0.1777 (1) | −0.78498 (9) | 0.0896 (1) | 0.0198 (3) | |
C5 | 0.3524 (1) | −0.8286 (1) | 0.0333 (1) | 0.0313 (3) | |
C16 | −0.4972 (1) | −0.4273 (1) | −0.2708 (1) | 0.0278 (3) | |
C4 | 0.2798 (1) | −0.8360 (1) | 0.1143 (1) | 0.0269 (3) | |
C1 | 0.03821 (9) | −0.67186 (9) | −0.04333 (9) | 0.0149 (2) | |
C7 | 0.2165 (1) | −0.7201 (1) | −0.0982 (1) | 0.0218 (3) | |
C9 | 0.0812 (1) | −0.6121 (1) | −0.2315 (1) | 0.0239 (3) | |
C19 | −0.7758 (1) | −0.3014 (1) | −0.4801 (1) | 0.0309 (3) | |
C17 | −0.5960 (1) | −0.3808 (1) | −0.3401 (1) | 0.0334 (3) | |
C10 | 0.0077 (1) | −0.61592 (9) | −0.1495 (1) | 0.0178 (2) | |
C15 | −0.4822 (1) | −0.4775 (1) | −0.1623 (1) | 0.0328 (3) | |
C22 | −0.9587 (1) | −0.2154 (1) | −0.6403 (1) | 0.0353 (3) | |
C6 | 0.3218 (1) | −0.7734 (1) | −0.0690 (1) | 0.0293 (3) | |
C21 | −0.8836 (1) | −0.1502 (1) | −0.5637 (1) | 0.0369 (4) | |
C8 | 0.1828 (1) | −0.6617 (1) | −0.2053 (1) | 0.0269 (3) | |
C23 | −0.9422 (1) | −0.3223 (1) | −0.6358 (1) | 0.0357 (4) | |
C20 | −0.7927 (1) | −0.1918 (1) | −0.4848 (1) | 0.0338 (3) | |
C24 | −0.8515 (1) | −0.3667 (1) | −0.5558 (1) | 0.0365 (4) | |
C18 | −0.6790 (1) | −0.3447 (1) | −0.4024 (1) | 0.0353 (3) | |
C14 | −0.3719 (1) | −0.5174 (1) | −0.1242 (1) | 0.0275 (3) | |
H6 | 0.0676 (1) | −0.5699 (1) | −0.2937 (1) | 0.029 (1)* | |
H1 | 0.1330 (1) | −0.78611 (9) | 0.1537 (1) | 0.024 (1)* | |
H2 | 0.2909 (1) | −0.8782 (1) | 0.1878 (1) | 0.032 (1)* | |
H8 | −0.5358 (1) | −0.4780 (1) | −0.1081 (1) | 0.040 (1)* | |
H7 | −0.3413 (1) | −0.5591 (1) | −0.0447 (1) | 0.033 (1)* | |
H13 | −0.8367 (1) | −0.4368 (1) | −0.5564 (1) | 0.041 (1)* | |
H12 | −0.9922 (1) | −0.3616 (1) | −0.6866 (1) | 0.041 (1)* | |
H11 | −1.0232 (1) | −0.1810 (1) | −0.6976 (1) | 0.041 (1)* | |
H10 | −0.8952 (1) | −0.0720 (1) | −0.5746 (1) | 0.043 (1)* | |
H9 | −0.7423 (1) | −0.1466 (1) | −0.4241 (1) | 0.039 (1)* | |
H5 | 0.2373 (1) | −0.6537 (1) | −0.2581 (1) | 0.033 (1)* | |
H4 | 0.3660 (1) | −0.7750 (1) | −0.1299 (1) | 0.036 (1)* | |
H3 | 0.4217 (1) | −0.8716 (1) | 0.0526 (1) | 0.038 (1)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0280 (2) | 0.0312 (2) | 0.0183 (1) | 0.0138 (1) | −0.0030 (1) | 0.0012 (1) |
C12 | 0.0211 (6) | 0.0209 (5) | 0.0167 (5) | 0.0034 (5) | 0.0006 (4) | 0.0003 (4) |
C2 | 0.0116 (5) | 0.0193 (5) | 0.0183 (5) | −0.0015 (4) | 0.0020 (4) | −0.0049 (4) |
C13 | 0.0204 (6) | 0.0228 (6) | 0.0180 (5) | 0.0076 (5) | −0.0030 (4) | −0.0014 (4) |
C11 | 0.0209 (5) | 0.0208 (5) | 0.0153 (5) | 0.0017 (5) | 0.0032 (4) | 0.0018 (4) |
C3 | 0.0143 (5) | 0.0214 (5) | 0.0227 (5) | 0.0002 (4) | 0.0015 (4) | −0.0007 (4) |
C5 | 0.0128 (5) | 0.0413 (7) | 0.0374 (7) | 0.0087 (6) | −0.0002 (5) | −0.0101 (6) |
C16 | 0.0244 (6) | 0.0330 (6) | 0.0216 (5) | 0.0154 (6) | −0.0052 (4) | −0.0096 (5) |
C4 | 0.0202 (6) | 0.0297 (6) | 0.0276 (6) | 0.0048 (5) | −0.0019 (5) | −0.0008 (5) |
C1 | 0.0102 (4) | 0.0186 (5) | 0.0165 (5) | −0.0011 (4) | 0.0039 (4) | −0.0028 (4) |
C7 | 0.0123 (5) | 0.0319 (6) | 0.0220 (5) | −0.0009 (5) | 0.0053 (4) | −0.0095 (5) |
C9 | 0.0231 (6) | 0.0332 (6) | 0.0169 (5) | −0.0015 (5) | 0.0075 (4) | 0.0033 (4) |
C19 | 0.0255 (6) | 0.0395 (8) | 0.0231 (6) | 0.0180 (6) | −0.0052 (5) | −0.0098 (5) |
C17 | 0.0303 (7) | 0.0411 (7) | 0.0232 (6) | 0.0175 (6) | −0.0064 (5) | −0.0122 (5) |
C10 | 0.0148 (5) | 0.0211 (5) | 0.0174 (5) | −0.0006 (4) | 0.0034 (4) | −0.0005 (4) |
C15 | 0.0251 (7) | 0.0463 (8) | 0.0251 (6) | 0.0146 (6) | 0.0017 (5) | −0.0038 (5) |
C22 | 0.0270 (6) | 0.0531 (9) | 0.0222 (6) | 0.0194 (7) | −0.0027 (5) | 0.0021 (6) |
C6 | 0.0136 (5) | 0.0440 (8) | 0.0319 (6) | 0.0019 (6) | 0.0081 (5) | −0.0126 (6) |
C21 | 0.0342 (7) | 0.0381 (8) | 0.0347 (7) | 0.0167 (7) | −0.0005 (6) | 0.0015 (6) |
C8 | 0.0184 (5) | 0.0421 (7) | 0.0225 (6) | −0.0019 (6) | 0.0095 (4) | −0.0046 (5) |
C23 | 0.0270 (7) | 0.0465 (9) | 0.0271 (7) | 0.0129 (6) | −0.0084 (6) | −0.0096 (6) |
C20 | 0.0321 (7) | 0.0353 (7) | 0.0285 (6) | 0.0118 (6) | −0.0056 (5) | −0.0081 (5) |
C24 | 0.0331 (7) | 0.0373 (8) | 0.0321 (7) | 0.0174 (6) | −0.0083 (6) | −0.0106 (6) |
C18 | 0.0329 (7) | 0.0419 (8) | 0.0250 (6) | 0.0186 (7) | −0.0072 (5) | −0.0127 (6) |
C14 | 0.0229 (6) | 0.0369 (7) | 0.0207 (5) | 0.0098 (6) | 0.0001 (5) | 0.0003 (5) |
S1—C13 | 1.7274 (12) | C7—C6 | 1.4303 (17) |
S1—C16 | 1.7282 (13) | C7—C8 | 1.4202 (18) |
C10—C11 | 1.4302 (17) | C9—C10 | 1.4379 (14) |
C11—C12 | 1.2018 (17) | C9—C8 | 1.3675 (18) |
C12—C13 | 1.4220 (16) | C9—H6 | 0.880 (2) |
C13—C14 | 1.3768 (18) | C19—C20 | 1.401 (2) |
C14—C15 | 1.4206 (18) | C19—C24 | 1.398 (2) |
C15—C16 | 1.377 (2) | C15—H8 | 0.998 (2) |
C16—C17 | 1.4252 (17) | C22—C21 | 1.398 (2) |
C17—C18 | 1.201 (2) | C22—C23 | 1.368 (2) |
C18—C19 | 1.4314 (18) | C22—H11 | 1.012 (3) |
C2—C3 | 1.4134 (16) | C6—H4 | 0.973 (2) |
C2—C1 | 1.4321 (15) | C21—C20 | 1.381 (2) |
C2—C7 | 1.4358 (13) | C21—H10 | 1.004 (2) |
C3—C4 | 1.3808 (16) | C8—H5 | 1.000 (2) |
C3—H1 | 1.008 (2) | C23—C24 | 1.3986 (19) |
C5—C4 | 1.4226 (19) | C23—H12 | 0.901 (3) |
C5—C6 | 1.350 (2) | C20—H9 | 1.006 (3) |
C5—H3 | 0.992 (2) | C24—H13 | 0.905 (2) |
C4—H2 | 0.985 (2) | C14—H7 | 1.053 (2) |
C1—C10 | 1.3910 (15) | ||
S1···C12 | 2.7578 (13) | C1···C8 | 2.8354 (14) |
S1···C13 | 1.7274 (12) | C1···H6 | 3.2450 (15) |
S1···C16 | 1.7282 (13) | C1···H1 | 2.7284 (15) |
S1···C19i | 3.5846 (13) | C1···H1iv | 2.6375 (17) |
S1···C17 | 2.7243 (15) | C7···C9 | 2.4235 (18) |
S1···C15 | 2.5782 (16) | C7···C10 | 2.8250 (17) |
S1···C24i | 3.4501 (16) | C7···C6 | 1.4303 (17) |
S1···C18i | 3.5018 (14) | C7···C8 | 1.4202 (18) |
S1···C14 | 2.5691 (14) | C7···H6 | 3.1992 (18) |
S1···H8 | 3.5459 (15) | C7···H1 | 3.3777 (17) |
S1···H7 | 3.5761 (14) | C7···H7iv | 2.8483 (17) |
S1···H13i | 3.1920 (17) | C7···H5 | 2.0870 (17) |
S1···H11ii | 3.4508 (17) | C7···H4 | 2.0628 (16) |
S1···H10iii | 3.3492 (16) | C7···H3 | 3.3348 (19) |
S1···H10ii | 3.3184 (15) | C9···C10 | 1.4379 (14) |
S1···H9iii | 3.5169 (14) | C9···C8 | 1.3675 (18) |
C12···C2iv | 3.4191 (17) | C9···H6 | 0.880 (2) |
C12···C13 | 1.4220 (16) | C9···H2vi | 3.3374 (19) |
C12···C11 | 1.2018 (17) | C9···H12i | 3.418 (2) |
C12···C3iv | 3.4342 (17) | C9···H5 | 2.0679 (17) |
C12···C1 | 3.4743 (17) | C19···C17 | 2.6320 (19) |
C12···C1iv | 3.4628 (16) | C19···C22 | 2.797 (2) |
C12···C10 | 2.6261 (17) | C19···C21 | 2.405 (2) |
C12···C6v | 3.5349 (18) | C19···C23 | 2.4209 (17) |
C12···C14 | 2.5029 (18) | C19···C20 | 1.401 (2) |
C12···H1iv | 3.3331 (17) | C19···C24 | 1.398 (2) |
C12···H7 | 2.7834 (17) | C19···C18 | 1.4314 (18) |
C12···H13i | 3.1987 (19) | C19···H2x | 3.542 (2) |
C12···H12i | 3.5868 (19) | C19···H13 | 1.995 (2) |
C12···H9iii | 2.9838 (18) | C19···H12 | 3.2479 (18) |
C12···H4v | 3.3490 (19) | C19···H10 | 3.327 (2) |
C12···H3v | 3.5017 (19) | C19···H9 | 2.076 (2) |
C2···C11iv | 3.1579 (15) | C17···C15 | 2.530 (2) |
C2···C3 | 1.4134 (16) | C17···C21ii | 3.577 (2) |
C2···C5 | 2.8179 (16) | C17···C20 | 3.545 (2) |
C2···C4 | 2.4307 (16) | C17···C24 | 3.556 (2) |
C2···C1 | 1.4321 (15) | C17···C18 | 1.201 (2) |
C2···C1iv | 2.5564 (15) | C17···H1x | 2.5800 (17) |
C2···C7 | 1.4358 (13) | C17···H2x | 3.249 (2) |
C2···C9 | 2.8238 (18) | C17···H8 | 2.887 (2) |
C2···C10 | 2.4398 (16) | C17···H13 | 3.497 (2) |
C2···C10iv | 3.2402 (15) | C17···H10ii | 2.605 (2) |
C2···C6 | 2.4663 (15) | C17···H9 | 3.491 (2) |
C2···C8 | 2.4650 (15) | C10···C8 | 2.4366 (16) |
C2···H1 | 2.1260 (16) | C10···H6 | 2.0374 (14) |
C2···H1iv | 3.5005 (17) | C10···H1iv | 2.7526 (17) |
C2···H2 | 3.2656 (16) | C10···H5 | 3.3476 (15) |
C2···H7iv | 3.1751 (17) | C10···H3vi | 3.337 (2) |
C2···H5 | 3.3581 (15) | C15···C14 | 1.4206 (18) |
C2···H4 | 3.3271 (15) | C15···H1x | 3.0611 (18) |
C13···C11 | 2.6203 (17) | C15···H8 | 0.998 (2) |
C13···C16 | 2.4808 (17) | C15···H8xi | 3.072 (3) |
C13···C15 | 2.3348 (18) | C15···H7 | 2.2072 (18) |
C13···C6v | 3.4379 (19) | C15···H11ii | 3.046 (2) |
C13···C14 | 1.3768 (18) | C15···H10ii | 3.299 (2) |
C13···H8 | 3.2563 (19) | C22···C21 | 1.398 (2) |
C13···H7 | 2.1218 (17) | C22···C21xii | 3.444 (2) |
C13···H11ii | 3.176 (2) | C22···C23 | 1.368 (2) |
C13···H9iii | 3.3769 (18) | C22···C20 | 2.420 (2) |
C13···H4v | 3.5034 (19) | C22···C24 | 2.406 (2) |
C11···C3iv | 3.1931 (17) | C22···H13 | 3.224 (2) |
C11···C1 | 2.4362 (15) | C22···H12 | 1.946 (3) |
C11···C1iv | 2.8380 (16) | C22···H11 | 1.0115 (1) |
C11···C9 | 2.4869 (16) | C22···H10 | 2.053 (2) |
C11···C10 | 1.4302 (17) | C22···H9 | 3.337 (2) |
C11···C14 | 3.5808 (18) | C22···H5xiii | 3.270 (2) |
C11···H6 | 2.6635 (16) | C22···H4xiii | 3.184 (2) |
C11···H1iv | 2.8624 (17) | C6···C8 | 2.4923 (19) |
C11···H13i | 3.3987 (18) | C6···H2 | 3.3337 (19) |
C11···H12i | 3.3151 (18) | C6···H7iv | 2.999 (2) |
C11···H9iii | 3.1754 (19) | C6···H5 | 2.6704 (19) |
C11···H3v | 3.5683 (18) | C6···H4 | 0.973 (2) |
C11···H3vi | 3.3708 (19) | C6···H3 | 2.064 (2) |
C3···C5 | 2.4279 (17) | C6···H3ix | 3.3457 (19) |
C3···C4 | 1.3808 (16) | C21···C23 | 2.385 (2) |
C3···C1 | 2.4871 (15) | C21···C20 | 1.381 (2) |
C3···C1iv | 2.9535 (16) | C21···C24 | 2.767 (2) |
C3···C7 | 2.4510 (17) | C21···H12 | 3.182 (2) |
C3···C17vii | 3.4656 (18) | C21···H11 | 2.077 (2) |
C3···C10iv | 3.2988 (16) | C21···H11xii | 3.459 (2) |
C3···C6 | 2.8021 (16) | C21···H10 | 1.004 |
C3···H1 | 1.0080 (1) | C21···H10xii | 3.564 (3) |
C3···H2 | 1.9784 (17) | C21···H9 | 2.093 (2) |
C3···H8vii | 3.0326 (18) | C21···H5xiii | 2.999 (2) |
C3···H7iv | 3.5915 (18) | C8···H6 | 1.9380 (19) |
C3···H3 | 3.2946 (16) | C8···H7iv | 3.3654 (18) |
C5···C4 | 1.4226 (19) | C8···H5 | 1.000 (2) |
C5···C7 | 2.4203 (19) | C8···H4 | 2.6478 (18) |
C5···C6 | 1.350 (2) | C23···C20 | 2.780 (2) |
C5···H1 | 3.3198 (17) | C23···C24 | 1.3986 (19) |
C5···H2 | 2.167 (2) | C23···H6i | 3.508 (2) |
C5···H7iv | 3.418 (2) | C23···H2xiv | 3.5300 (19) |
C5···H12viii | 3.398 (2) | C23···H13 | 2.023 (2) |
C5···H4 | 2.036 (2) | C23···H12 | 0.901 (3) |
C5···H4ix | 3.4563 (19) | C23···H11 | 2.094 (2) |
C5···H3 | 0.992 (2) | C23···H10 | 3.269 (2) |
C5···H3ix | 3.180 (3) | C23···H4xiii | 3.095 (2) |
C16···C17 | 1.4252 (17) | C20···C24 | 2.414 (2) |
C16···C15 | 1.377 (2) | C20···C18 | 2.452 (2) |
C16···C21ii | 3.538 (2) | C20···H13 | 3.223 (2) |
C16···C18 | 2.6253 (18) | C20···H13xv | 3.582 (2) |
C16···C14 | 2.3216 (17) | C20···H11 | 3.318 (2) |
C16···H1x | 2.9558 (16) | C20···H11xii | 3.397 (2) |
C16···H8 | 2.126 (2) | C20···H10 | 2.095 (2) |
C16···H7 | 3.3259 (17) | C20···H9 | 1.0060 (1) |
C16···H11ii | 3.248 (2) | C20···H5xiii | 3.2099 (19) |
C16···H10ii | 2.692 (2) | C24···C18 | 2.460 (2) |
C4···C7 | 2.8125 (19) | C24···H13 | 0.905 (2) |
C4···C6 | 2.4097 (19) | C24···H12 | 2.0313 (19) |
C4···H1 | 2.0452 (17) | C24···H11 | 3.336 (2) |
C4···H2 | 0.985 (2) | C24···H9 | 3.313 (2) |
C4···H8vii | 3.475 (2) | C18···H1x | 2.8913 (18) |
C4···H7iii | 3.514 (2) | C18···H2x | 3.098 (2) |
C4···H12viii | 3.2251 (18) | C18···H13 | 2.599 (2) |
C4···H11viii | 3.480 (2) | C18···H10ii | 3.045 (2) |
C4···H4 | 3.2982 (18) | C18···H9 | 2.620 (2) |
C4···H3 | 2.0632 (18) | C14···H8 | 2.1146 (19) |
C1···C7 | 2.4767 (14) | C14···H8xi | 3.1576 (19) |
C1···C9 | 2.4539 (14) | C14···H7 | 1.0525 (1) |
C1···C10 | 1.3910 (15) | C14···H11ii | 3.002 (2) |
C1···C10iv | 2.5042 (15) | ||
S1—C13—C12 | 121.95 (9) | C2—C7—C8 | 119.3 (1) |
S1—C13—C14 | 111.21 (9) | C6—C7—C8 | 121.9 (1) |
C13—S1—C16 | 91.76 (6) | C10—C9—C8 | 120.55 (11) |
S1—C16—C17 | 119.22 (11) | C10—C9—H6 | 121.2 (2) |
S1—C16—C15 | 111.74 (9) | C8—C9—H6 | 117.5 (2) |
C9—C10—C11 | 120.24 (11) | C20—C19—C24 | 119.23 (13) |
C10—C11—C12 | 172.28 (13) | C16—C15—H8 | 126.3 (2) |
C11—C12—C13 | 173.98 (13) | C14—C15—H8 | 121.0 (2) |
C12—C13—C14 | 126.82 (11) | C21—C22—C23 | 119.22 (13) |
C13—C14—C15 | 113.15 (12) | C21—C22—H11 | 118.2 (2) |
C14—C15—C16 | 112.13 (12) | C23—C22—H11 | 122.5 (2) |
C15—C16—C17 | 128.99 (13) | C5—C6—C7 | 120.99 (11) |
C16—C17—C18 | 177.12 (13) | C5—C6—H4 | 121.6 (2) |
C17—C18—C19 | 177.94 (17) | C7—C6—H4 | 117.0 (2) |
C18—C19—C20 | 119.91 (14) | C22—C21—C20 | 121.14 (15) |
C18—C19—C24 | 120.79 (13) | C22—C21—H10 | 116.5 (2) |
C1—C10—C9 | 120.3 (1) | C20—C21—H10 | 122.1 (2) |
C1—C10—C11 | 119.4 (1) | C7—C8—C9 | 120.8 (1) |
C3—C2—C1 | 121.87 (9) | C7—C8—H5 | 118.1 (1) |
C3—C2—C7 | 118.7 (1) | C9—C8—H5 | 121.0 (1) |
C1—C2—C7 | 119.4 (1) | C22—C23—C24 | 120.84 (14) |
C2—C3—C4 | 120.90 (11) | C22—C23—H12 | 116.6 (2) |
C2—C3—H1 | 121.9 (1) | C24—C23—H12 | 122.6 (2) |
C4—C3—H1 | 116.9 (1) | C19—C20—C21 | 119.66 (14) |
C4—C5—C6 | 120.68 (12) | C19—C20—H9 | 118.2 (2) |
C4—C5—H3 | 116.2 (2) | C21—C20—H9 | 121.8 (2) |
C6—C5—H3 | 122.8 (2) | C19—C24—C23 | 119.91 (14) |
C3—C4—C5 | 120.00 (12) | C19—C24—H13 | 118.5 (2) |
C3—C4—H2 | 112.4 (1) | C23—C24—H13 | 121.4 (2) |
C5—C4—H2 | 127.5 (2) | C13—C14—H7 | 121.1 (1) |
C2—C1—C10 | 119.59 (9) | C15—C14—H7 | 125.7 (2) |
C2—C7—C6 | 118.74 (11) | ||
C16—S1—C13—C12 | 178.1 (1) | C1—C2—C7—C6 | 179.3 (1) |
C16—S1—C13—C14 | −0.2 (1) | C1—C2—C7—C8 | −0.3 (2) |
C13—S1—C16—C17 | −177.6 (1) | C2—C3—C4—C5 | 0.5 (2) |
C13—S1—C16—C15 | 0.1 (1) | C6—C5—C4—C3 | −1.1 (2) |
S1—C13—C14—C15 | 0.3 (1) | C4—C5—C6—C7 | 0.7 (2) |
C12—C13—C14—C15 | −177.9 (1) | C2—C1—C10—C9 | 0.0 (2) |
S1—C16—C15—C14 | 0.1 (1) | C2—C7—C6—C5 | 0.3 (2) |
C17—C16—C15—C14 | 177.5 (2) | C8—C7—C6—C5 | 180.0 (1) |
C2—C1—C10—C11 | 178.6 (1) | C2—C7—C8—C9 | −0.9 (2) |
C8—C9—C10—C11 | −179.8 (1) | C6—C7—C8—C9 | 179.5 (1) |
C8—C9—C10—C1 | −1.3 (2) | C10—C9—C8—C7 | 1.7 (2) |
C18—C19—C20—C21 | 177.2 (1) | C24—C19—C20—C21 | 0.2 (2) |
C16—C15—C14—C13 | −0.3 (2) | C20—C19—C24—C23 | 0.5 (2) |
C1—C2—C3—C4 | −179.8 (1) | C18—C19—C24—C23 | −176.5 (1) |
C7—C2—C3—C4 | 0.5 (2) | C23—C22—C21—C20 | 0.8 (2) |
C3—C2—C1—C10 | −179.0 (1) | C21—C22—C23—C24 | −0.1 (2) |
C7—C2—C1—C10 | 0.7 (2) | C22—C21—C20—C19 | −0.8 (2) |
C3—C2—C7—C6 | −0.9 (2) | C22—C23—C24—C19 | −0.6 (2) |
C3—C2—C7—C8 | 179.4 (1) |
Symmetry codes: (i) −x−1, y, −z−1; (ii) −x−3/2, y−1/2, −z−1; (iii) x+1/2, y−1/2, z; (iv) −x, y, −z; (v) x−1/2, y+1/2, z; (vi) −x+1/2, y+1/2, −z; (vii) −x−1/2, y−1/2, −z; (viii) x+3/2, y−1/2, z+1; (ix) −x+1, y, −z; (x) −x−1/2, y+1/2, −z; (xi) −x−1, y, −z; (xii) −x−2, y, −z−1; (xiii) −x−1/2, y+1/2, −z−1; (xiv) x−3/2, y+1/2, z−1; (xv) −x−3/2, y+1/2, −z−1. |
Experimental details
Crystal data | |
Chemical formula | C48H26S2 |
Mr | 666.85 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 123 |
a, b, c (Å) | 12.2484 (1), 12.6553 (1), 11.5031 (9) |
β (°) | 102.407 (5) |
V (Å3) | 1741.4 (1) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku RAXIS-IV diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.963, 1.000 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 6879, 3505, 3501 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.094, 1.18 |
No. of reflections | 2081 |
No. of parameters | 240 |
No. of restraints | ? |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.33, −0.44 |
Absolute structure | Flack (1983), 1592 Friedel pairs |
Absolute structure parameter | 0.07 (4) |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, TEXSAN (Rigaku, 1999), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), CrystalStructure (Molecular Structure Corporation and Rigaku, 2001).
S1—C13 | 1.7274 (12) | C14—C15 | 1.4206 (18) |
S1—C16 | 1.7282 (13) | C15—C16 | 1.377 (2) |
C10—C11 | 1.4302 (17) | C16—C17 | 1.4252 (17) |
C11—C12 | 1.2018 (17) | C17—C18 | 1.201 (2) |
C12—C13 | 1.4220 (16) | C18—C19 | 1.4314 (18) |
C13—C14 | 1.3768 (18) | ||
S1—C13—C12 | 121.95 (9) | C13—C14—C15 | 113.15 (12) |
S1—C13—C14 | 111.21 (9) | C14—C15—C16 | 112.13 (12) |
C13—S1—C16 | 91.76 (6) | C15—C16—C17 | 128.99 (13) |
S1—C16—C17 | 119.22 (11) | C16—C17—C18 | 177.12 (13) |
S1—C16—C15 | 111.74 (9) | C17—C18—C19 | 177.94 (17) |
C9—C10—C11 | 120.24 (11) | C18—C19—C20 | 119.91 (14) |
C10—C11—C12 | 172.28 (13) | C18—C19—C24 | 120.79 (13) |
C11—C12—C13 | 173.98 (13) | C1—C10—C9 | 120.3 (1) |
C12—C13—C14 | 126.82 (11) | C1—C10—C11 | 119.4 (1) |
C16—S1—C13—C12 | 178.1 (1) | C17—C16—C15—C14 | 177.5 (2) |
C16—S1—C13—C14 | −0.2 (1) | C2—C1—C10—C11 | 178.6 (1) |
C13—S1—C16—C17 | −177.6 (1) | C8—C9—C10—C11 | −179.8 (1) |
C13—S1—C16—C15 | 0.1 (1) | C8—C9—C10—C1 | −1.3 (2) |
S1—C13—C14—C15 | 0.3 (1) | C18—C19—C20—C21 | 177.2 (1) |
C12—C13—C14—C15 | −177.9 (1) | C16—C15—C14—C13 | −0.3 (2) |
S1—C16—C15—C14 | 0.1 (1) |
Phenylene–ethynylenes have received great attention as organic photoluminescent (Kokil et al., 2002) and electroluminescent compounds (Kraft et al., 1998) and a number of phenylene–ethynylenes have been prepared (Bunz et al., 2001). We have been intrigued by such features of phenylene–ethynylenes, and we have successfully prepared acetylenes bearing various substituents (Orita et al., 1999), a highly strained acetylenic cyclophane (Orita, Hasegawa, Nakano & Otera, 2002) and optically active acetylenic cyclophanes (Orita, Hasegawa, An et al., 2002). Furthermore, it is recognized that thiophene derivatives serve as conducting organic materials and various types of oligo- and polythiophenes have been reported (Miller & Mann, 1996). We have prepared an optically active phenylene–ethynylene-bearing thiophenylene, (I), in expectation of a new function of phenylene–ethynylene derivatives as a new category of photo- and electroluminescent compounds. We describe here the structural features of (I) in the solid state.
(R)-1,1'-Binaphthyl was employed as a chiral center and, in the crystal structure, the dihedral angle between the two naphthyl groups is 69.3 (3)°. The title compound shows C2 symmetry, the crystallographic twofold axis passing through the mid-point of the C1—C1' bond (Fig. 1). The two arylene–ethynylenes are oriented in opposite directions, showing no intramolecular interaction with each other. Although both types of acetylenes are conjugated to arenes, the bond lengths C17—C18 and C11—C12, 1.201 (2) and 1.2018 (17) Å, respectively, are in good agreement with values observed in cyclic acetylenes which we have prepared earlier (Orita, Jiang et al., 2002). The dihedral angles between phenyl and thienylene and between thienylene and naphthylene are 83.2 (3) and 8.7 (3)°, respectively, showing that the three aromatic ring systems are not completely conjugated.