Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109013468/sf3103sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109013468/sf3103Isup2.hkl |
CCDC reference: 729601
To a THF solution of 2-bromomethoxylbenzene (0.94 g, 5 mmol) was added a hexane solution of n-butyl lithium (2.0 ml, 5 mmol) at 195 K under a nitrogen atmosphere. The mixture was stirred for half an hour. An excess of octafluorocyclopentene (1.5 ml, 10 mmol) was added and stirring was continued for another two hours at this temperature. The reaction was then quenched by the addition of water. The product, 3,3,4,4,5,5-heptafluoro-(2-methoxylpheny)cyclopent-1-ene (1.43 g, 4.75 mmol), was collected and dried (yield 90%). This compound (1.43 g, 4.75 mmol) was reacted with 3-bromo-2-methyl-5-(4-methoxylphenyl)thiophene (0.94 g, 5 mmol; Perters et al., 2003) in the presence of n-butyl lithium (2.0 ml, 5 mmol) at 195 K under a nitrogen atmosphere. After an hour, the reaction was quenced by the addition of water. The solid product was purified by column chromatography on silica with petroleum ether as the eluant to give the title compound (1.50 g, 3.10 mmol, 65% yield; m.p. 384–390 K). Analysis calculated for C24H18F6O2S: C 59.50, H 3.75%; found: C 59.22, H 3.80%. 1H NMR (400 MHz, CDCl3, TMS): δ 1.87 (s, 3H, –CH3), 3.50 (s, 3H, –OCH3), 3.84 (s, 3H, –OCH3), 6.83, 6.85 (d, J = 8.0 Hz, 1H, aromatic H), 6.90, 6.92 (d, J = 8.0 Hz, 2H, aromatic H), 6.99 (t, J = 8.0 Hz, 1H, aromatic H), 7.11 (s, 1H, thienyl H), 7.37 (t, J = 8.0 Hz, 2H, aromatic H), 7.44, 7.46 (d, J = 8.0 Hz, 2H, aromatic H) p.p.m. 13C NMR (100 MHz, CDCl3): δ 14.03, 55.22, 55.39, 111.48, 114.36, 117.50, 120.80, 121.92, 126.79, 129.97, 131.73, 138.76, 141.07, 157.13, 159.32 p.p.m.
All H atoms were positioned geometrically and treated as riding [C—H = 0.96 Å (methyl) or 0.93 Å (aromatic), and Uiso(H) = 1.2Ueq(Caromatic) or 1.5Ueq(Cmethyl).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).
Fig. 1. A displacement ellipsoid plot (Barbour, 2001) of (I). Ellipsoids are drawn at the 50% probability level. | |
Fig. 2. Photochromic interconvertion of (I). |
C24H18F6O2S | Z = 2 |
Mr = 484.44 | F(000) = 496 |
Triclinic, P1 | Dx = 1.458 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.477 (1) Å | Cell parameters from 4266 reflections |
b = 10.398 (1) Å | θ = 2.6–28.1° |
c = 11.4573 (1) Å | µ = 0.22 mm−1 |
α = 90.259 (1)° | T = 291 K |
β = 101.436 (1)° | Block, colorless |
γ = 94.055 (1)° | 0.43 × 0.35 × 0.27 mm |
V = 1103.7 (2) Å3 |
Bruker SMART area-detector diffractometer | 4979 independent reflections |
Radiation source: fine-focus sealed tube | 4028 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→12 |
Tmin = 0.913, Tmax = 0.944 | k = −13→13 |
9784 measured reflections | l = −14→14 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0706P)2 + 0.2768P] where P = (Fo2 + 2Fc2)/3 |
4979 reflections | (Δ/σ)max = 0.001 |
301 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C24H18F6O2S | γ = 94.055 (1)° |
Mr = 484.44 | V = 1103.7 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.477 (1) Å | Mo Kα radiation |
b = 10.398 (1) Å | µ = 0.22 mm−1 |
c = 11.4573 (1) Å | T = 291 K |
α = 90.259 (1)° | 0.43 × 0.35 × 0.27 mm |
β = 101.436 (1)° |
Bruker SMART area-detector diffractometer | 4979 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4028 reflections with I > 2σ(I) |
Tmin = 0.913, Tmax = 0.944 | Rint = 0.012 |
9784 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.42 e Å−3 |
4979 reflections | Δρmin = −0.27 e Å−3 |
301 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.35767 (5) | 0.62175 (4) | 0.50957 (4) | 0.04695 (15) | |
F1 | 0.84196 (17) | 0.83930 (15) | 1.03918 (12) | 0.0849 (5) | |
F2 | 0.96010 (13) | 0.88468 (13) | 0.90055 (16) | 0.0858 (5) | |
F3 | 0.95213 (17) | 0.62311 (14) | 1.03354 (13) | 0.0862 (5) | |
F4 | 0.99110 (15) | 0.65263 (15) | 0.85574 (16) | 0.0847 (5) | |
F5 | 0.69068 (16) | 0.53213 (15) | 0.95267 (14) | 0.0867 (5) | |
F6 | 0.77693 (16) | 0.49067 (12) | 0.79713 (13) | 0.0813 (5) | |
O1 | 0.44100 (15) | 0.82927 (15) | 0.87811 (15) | 0.0646 (4) | |
O2 | −0.11648 (17) | 0.11781 (15) | 0.54858 (14) | 0.0669 (4) | |
C1 | 0.5029 (2) | 0.93844 (19) | 0.83981 (16) | 0.0500 (4) | |
C2 | 0.4398 (3) | 1.0558 (3) | 0.8238 (2) | 0.0704 (7) | |
H2 | 0.3473 | 1.0628 | 0.8378 | 0.084* | |
C3 | 0.5152 (4) | 1.1620 (2) | 0.7870 (2) | 0.0808 (8) | |
H3 | 0.4722 | 1.2399 | 0.7764 | 0.097* | |
C4 | 0.6514 (3) | 1.1550 (2) | 0.7658 (2) | 0.0746 (7) | |
H4 | 0.7003 | 1.2272 | 0.7409 | 0.089* | |
C5 | 0.7158 (2) | 1.03886 (18) | 0.78183 (18) | 0.0551 (5) | |
H5 | 0.8087 | 1.0338 | 0.7679 | 0.066* | |
C6 | 0.64338 (19) | 0.92958 (16) | 0.81847 (15) | 0.0417 (4) | |
C7 | 0.2991 (2) | 0.8299 (4) | 0.9020 (2) | 0.0876 (9) | |
H7A | 0.2978 | 0.8940 | 0.9623 | 0.131* | |
H7B | 0.2709 | 0.7466 | 0.9292 | 0.131* | |
H7C | 0.2329 | 0.8495 | 0.8305 | 0.131* | |
C8 | 0.71278 (17) | 0.80721 (16) | 0.84067 (14) | 0.0376 (3) | |
C9 | 0.8542 (2) | 0.80428 (18) | 0.92724 (17) | 0.0487 (4) | |
C10 | 0.8935 (2) | 0.66381 (19) | 0.92636 (18) | 0.0507 (4) | |
C11 | 0.7535 (2) | 0.58817 (17) | 0.86666 (17) | 0.0490 (4) | |
C12 | 0.66143 (17) | 0.68728 (16) | 0.80123 (14) | 0.0383 (3) | |
C13 | 0.50794 (18) | 0.70038 (16) | 0.59793 (15) | 0.0405 (4) | |
C14 | 0.53461 (18) | 0.64722 (15) | 0.70866 (15) | 0.0382 (3) | |
C15 | 0.43241 (18) | 0.54275 (16) | 0.72156 (16) | 0.0424 (4) | |
H15 | 0.4364 | 0.4963 | 0.7912 | 0.051* | |
C16 | 0.32821 (18) | 0.51795 (16) | 0.62128 (15) | 0.0407 (4) | |
C17 | 0.5883 (2) | 0.80790 (19) | 0.54656 (17) | 0.0519 (5) | |
H17A | 0.5456 | 0.8874 | 0.5558 | 0.078* | |
H17B | 0.5836 | 0.7904 | 0.4635 | 0.078* | |
H17C | 0.6874 | 0.8149 | 0.5875 | 0.078* | |
C18 | 0.20679 (18) | 0.41865 (16) | 0.60024 (15) | 0.0414 (4) | |
C19 | 0.1658 (2) | 0.3508 (2) | 0.69379 (18) | 0.0584 (5) | |
H19 | 0.2119 | 0.3724 | 0.7715 | 0.070* | |
C20 | 0.0578 (2) | 0.2520 (2) | 0.67377 (19) | 0.0662 (6) | |
H20 | 0.0328 | 0.2074 | 0.7378 | 0.079* | |
C21 | −0.0134 (2) | 0.21922 (19) | 0.55872 (17) | 0.0491 (4) | |
C22 | 0.0214 (2) | 0.28777 (19) | 0.46465 (17) | 0.0510 (4) | |
H22 | −0.0281 | 0.2683 | 0.3874 | 0.061* | |
C23 | 0.1308 (2) | 0.38607 (19) | 0.48563 (17) | 0.0505 (4) | |
H23 | 0.1540 | 0.4315 | 0.4214 | 0.061* | |
C24 | −0.1867 (3) | 0.0760 (2) | 0.4314 (2) | 0.0674 (6) | |
H24A | −0.2409 | 0.1439 | 0.3927 | 0.101* | |
H24B | −0.2508 | 0.0014 | 0.4360 | 0.101* | |
H24C | −0.1157 | 0.0548 | 0.3866 | 0.101* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0456 (3) | 0.0474 (3) | 0.0423 (2) | −0.00456 (19) | −0.00182 (18) | 0.00416 (18) |
F1 | 0.0981 (11) | 0.0933 (10) | 0.0543 (8) | 0.0385 (9) | −0.0173 (7) | −0.0272 (7) |
F2 | 0.0436 (7) | 0.0618 (8) | 0.1404 (14) | −0.0125 (6) | −0.0047 (8) | 0.0113 (8) |
F3 | 0.0996 (11) | 0.0693 (8) | 0.0707 (9) | 0.0207 (8) | −0.0343 (8) | 0.0006 (7) |
F4 | 0.0596 (8) | 0.0831 (10) | 0.1170 (13) | 0.0075 (7) | 0.0305 (8) | −0.0217 (9) |
F5 | 0.0775 (9) | 0.0878 (10) | 0.0871 (10) | −0.0098 (8) | 0.0022 (8) | 0.0478 (8) |
F6 | 0.0921 (10) | 0.0483 (7) | 0.0893 (10) | 0.0241 (7) | −0.0223 (8) | −0.0198 (6) |
O1 | 0.0442 (7) | 0.0713 (10) | 0.0815 (11) | −0.0034 (7) | 0.0236 (7) | −0.0145 (8) |
O2 | 0.0623 (9) | 0.0681 (9) | 0.0609 (9) | −0.0297 (7) | 0.0018 (7) | 0.0053 (7) |
C1 | 0.0460 (10) | 0.0564 (11) | 0.0445 (10) | 0.0085 (8) | 0.0001 (7) | −0.0135 (8) |
C2 | 0.0656 (14) | 0.0808 (16) | 0.0607 (13) | 0.0338 (12) | −0.0066 (11) | −0.0190 (12) |
C3 | 0.112 (2) | 0.0588 (14) | 0.0659 (15) | 0.0401 (15) | −0.0073 (14) | −0.0043 (11) |
C4 | 0.116 (2) | 0.0439 (11) | 0.0608 (14) | 0.0116 (12) | 0.0081 (14) | 0.0066 (9) |
C5 | 0.0694 (13) | 0.0426 (10) | 0.0529 (11) | 0.0027 (9) | 0.0117 (9) | 0.0035 (8) |
C6 | 0.0457 (9) | 0.0388 (8) | 0.0385 (8) | 0.0040 (7) | 0.0032 (7) | −0.0040 (6) |
C7 | 0.0405 (11) | 0.151 (3) | 0.0719 (16) | −0.0008 (14) | 0.0158 (11) | −0.0157 (17) |
C8 | 0.0355 (8) | 0.0387 (8) | 0.0380 (8) | −0.0002 (6) | 0.0068 (6) | 0.0002 (6) |
C9 | 0.0419 (9) | 0.0468 (10) | 0.0524 (10) | 0.0009 (8) | −0.0019 (8) | −0.0072 (8) |
C10 | 0.0438 (10) | 0.0508 (10) | 0.0533 (11) | 0.0105 (8) | −0.0025 (8) | −0.0011 (8) |
C11 | 0.0552 (11) | 0.0377 (9) | 0.0495 (10) | 0.0014 (8) | −0.0002 (8) | 0.0030 (7) |
C12 | 0.0367 (8) | 0.0383 (8) | 0.0384 (8) | −0.0008 (6) | 0.0051 (6) | 0.0020 (6) |
C13 | 0.0392 (8) | 0.0369 (8) | 0.0432 (9) | 0.0005 (7) | 0.0038 (7) | −0.0001 (7) |
C14 | 0.0378 (8) | 0.0336 (8) | 0.0408 (8) | −0.0004 (6) | 0.0031 (6) | −0.0016 (6) |
C15 | 0.0435 (9) | 0.0383 (8) | 0.0426 (9) | −0.0020 (7) | 0.0033 (7) | 0.0022 (7) |
C16 | 0.0389 (8) | 0.0373 (8) | 0.0445 (9) | −0.0001 (7) | 0.0061 (7) | −0.0006 (7) |
C17 | 0.0555 (11) | 0.0509 (10) | 0.0463 (10) | −0.0072 (9) | 0.0070 (8) | 0.0074 (8) |
C18 | 0.0376 (8) | 0.0394 (9) | 0.0452 (9) | −0.0008 (7) | 0.0050 (7) | −0.0013 (7) |
C19 | 0.0554 (11) | 0.0721 (13) | 0.0411 (10) | −0.0191 (10) | 0.0025 (8) | 0.0000 (9) |
C20 | 0.0651 (13) | 0.0805 (15) | 0.0461 (11) | −0.0271 (11) | 0.0052 (9) | 0.0104 (10) |
C21 | 0.0418 (9) | 0.0494 (10) | 0.0523 (10) | −0.0091 (8) | 0.0044 (8) | 0.0010 (8) |
C22 | 0.0496 (10) | 0.0541 (11) | 0.0441 (10) | −0.0097 (8) | 0.0015 (8) | −0.0030 (8) |
C23 | 0.0514 (10) | 0.0525 (11) | 0.0434 (10) | −0.0106 (8) | 0.0043 (8) | 0.0024 (8) |
C24 | 0.0639 (13) | 0.0611 (13) | 0.0681 (14) | −0.0232 (11) | 0.0011 (10) | −0.0055 (10) |
S1—C13 | 1.726 (2) | C8—C9 | 1.503 (2) |
S1—C16 | 1.730 (2) | C9—C10 | 1.533 (3) |
F1—C9 | 1.361 (2) | C10—C11 | 1.528 (3) |
F2—C9 | 1.344 (2) | C11—C12 | 1.504 (2) |
F3—C10 | 1.328 (2) | C12—C14 | 1.471 (2) |
F4—C10 | 1.355 (2) | C13—C14 | 1.370 (2) |
F5—C11 | 1.362 (2) | C13—C17 | 1.497 (2) |
F6—C11 | 1.344 (2) | C14—C15 | 1.432 (2) |
O1—C1 | 1.356 (3) | C15—C16 | 1.369 (2) |
O1—C7 | 1.425 (3) | C15—H15 | 0.9300 |
O2—C21 | 1.374 (2) | C16—C18 | 1.472 (2) |
O2—C24 | 1.426 (3) | C17—H17A | 0.9600 |
C1—C2 | 1.393 (3) | C17—H17B | 0.9600 |
C1—C6 | 1.409 (3) | C17—H17C | 0.9600 |
C2—C3 | 1.386 (4) | C18—C19 | 1.390 (3) |
C2—H2 | 0.9300 | C18—C23 | 1.394 (2) |
C3—C4 | 1.366 (4) | C19—C20 | 1.383 (3) |
C3—H3 | 0.9300 | C19—H19 | 0.9300 |
C4—C5 | 1.388 (3) | C20—C21 | 1.386 (3) |
C4—H4 | 0.9300 | C20—H20 | 0.9300 |
C5—C6 | 1.395 (3) | C21—C22 | 1.376 (3) |
C5—H5 | 0.9300 | C22—C23 | 1.388 (3) |
C6—C8 | 1.474 (2) | C22—H22 | 0.9300 |
C7—H7A | 0.9600 | C23—H23 | 0.9300 |
C7—H7B | 0.9600 | C24—H24A | 0.9600 |
C7—H7C | 0.9600 | C24—H24B | 0.9600 |
C8—C12 | 1.348 (2) | C24—H24C | 0.9600 |
C13—S1—C16 | 93.16 (8) | C12—C11—C10 | 105.0 (1) |
C1—O1—C7 | 119.3 (2) | C8—C12—C14 | 129.0 (2) |
C21—O2—C24 | 117.4 (2) | C8—C12—C11 | 110.7 (2) |
O1—C1—C2 | 125.0 (2) | C14—C12—C11 | 120.4 (1) |
O1—C1—C6 | 115.6 (2) | C14—C13—C17 | 130.5 (2) |
C2—C1—C6 | 119.3 (2) | C14—C13—S1 | 110.4 (1) |
C3—C2—C1 | 119.9 (2) | C17—C13—S1 | 119.1 (1) |
C3—C2—H2 | 120.1 | C13—C14—C15 | 113.0 (2) |
C1—C2—H2 | 120.1 | C13—C14—C12 | 123.2 (2) |
C4—C3—C2 | 121.5 (2) | C15—C14—C12 | 123.6 (2) |
C4—C3—H3 | 119.2 | C16—C15—C14 | 113.3 (2) |
C2—C3—H3 | 119.2 | C16—C15—H15 | 123.3 |
C3—C4—C5 | 119.2 (2) | C14—C15—H15 | 123.3 |
C3—C4—H4 | 120.4 | C15—C16—C18 | 129.1 (2) |
C5—C4—H4 | 120.4 | C15—C16—S1 | 110.1 (1) |
C4—C5—C6 | 121.0 (2) | C18—C16—S1 | 120.8 (1) |
C4—C5—H5 | 119.5 | C13—C17—H17A | 109.5 |
C6—C5—H5 | 119.5 | C13—C17—H17B | 109.5 |
C5—C6—C1 | 119.0 (2) | H17A—C17—H17B | 109.5 |
C5—C6—C8 | 121.6 (2) | C13—C17—H17C | 109.5 |
C1—C6—C8 | 119.4 (2) | H17A—C17—H17C | 109.5 |
O1—C7—H7A | 109.5 | H17B—C17—H17C | 109.5 |
O1—C7—H7B | 109.5 | C19—C18—C23 | 117.2 (2) |
H7A—C7—H7B | 109.5 | C19—C18—C16 | 121.3 (2) |
O1—C7—H7C | 109.5 | C23—C18—C16 | 121.6 (2) |
H7A—C7—H7C | 109.5 | C20—C19—C18 | 121.4 (2) |
H7B—C7—H7C | 109.5 | C20—C19—H19 | 119.3 |
C12—C8—C6 | 128.9 (2) | C18—C19—H19 | 119.3 |
C12—C8—C9 | 110.9 (2) | C19—C20—C21 | 120.3 (2) |
C6—C8—C9 | 119.9 (2) | C19—C20—H20 | 119.9 |
F2—C9—F1 | 105.5 (2) | C21—C20—H20 | 119.9 |
F2—C9—C8 | 113.9 (2) | O2—C21—C22 | 124.9 (2) |
F1—C9—C8 | 111.6 (2) | O2—C21—C20 | 115.5 (2) |
F2—C9—C10 | 111.1 (2) | C22—C21—C20 | 119.6 (2) |
F1—C9—C10 | 109.5 (2) | C21—C22—C23 | 119.7 (2) |
C8—C9—C10 | 105.3 (1) | C21—C22—H22 | 120.2 |
F3—C10—F4 | 107.3 (2) | C23—C22—H22 | 120.2 |
F3—C10—C9 | 113.1 (2) | C22—C23—C18 | 121.9 (2) |
F4—C10—C9 | 109.0 (2) | C22—C23—H23 | 119.1 |
F3—C10—C11 | 114.8 (2) | C18—C23—H23 | 119.1 |
F4—C10—C11 | 107.8 (2) | O2—C24—H24A | 109.5 |
C9—C10—C11 | 104.6 (1) | O2—C24—H24B | 109.5 |
F6—C11—F5 | 105.7 (2) | H24A—C24—H24B | 109.5 |
F6—C11—C12 | 114.1 (2) | O2—C24—H24C | 109.5 |
F5—C11—C12 | 111.1 (2) | H24A—C24—H24C | 109.5 |
F6—C11—C10 | 112.3 (2) | H24B—C24—H24C | 109.5 |
F5—C11—C10 | 108.7 (2) | ||
C7—O1—C1—C2 | 1.6 (3) | C9—C8—C12—C14 | −173.9 (2) |
C7—O1—C1—C6 | 179.9 (2) | C6—C8—C12—C11 | −167.6 (2) |
O1—C1—C2—C3 | 178.4 (2) | C9—C8—C12—C11 | 6.3 (2) |
C6—C1—C2—C3 | 0.2 (3) | F6—C11—C12—C8 | −139.5 (2) |
C1—C2—C3—C4 | −0.1 (4) | F5—C11—C12—C8 | 101.2 (2) |
C2—C3—C4—C5 | −0.2 (4) | C10—C11—C12—C8 | −16.1 (2) |
C3—C4—C5—C6 | 0.4 (3) | F6—C11—C12—C14 | 40.7 (2) |
C4—C5—C6—C1 | −0.3 (3) | F5—C11—C12—C14 | −78.6 (2) |
C4—C5—C6—C8 | −177.4 (2) | C10—C11—C12—C14 | 164.1 (2) |
O1—C1—C6—C5 | −178.4 (2) | C16—S1—C13—C14 | 0.7 (1) |
C2—C1—C6—C5 | 0.0 (3) | C16—S1—C13—C17 | 179.3 (2) |
O1—C1—C6—C8 | −1.2 (2) | C17—C13—C14—C15 | −178.7 (2) |
C2—C1—C6—C8 | 177.2 (2) | S1—C13—C14—C15 | −0.2 (2) |
C5—C6—C8—C12 | −131.2 (2) | C17—C13—C14—C12 | −3.0 (3) |
C1—C6—C8—C12 | 51.7 (3) | S1—C13—C14—C12 | 175.5 (1) |
C5—C6—C8—C9 | 55.4 (2) | C8—C12—C14—C13 | 49.3 (3) |
C1—C6—C8—C9 | −121.7 (2) | C11—C12—C14—C13 | −130.9 (2) |
C12—C8—C9—F2 | 128.0 (2) | C8—C12—C14—C15 | −135.4 (2) |
C6—C8—C9—F2 | −57.5 (2) | C11—C12—C14—C15 | 44.3 (2) |
C12—C8—C9—F1 | −112.6 (2) | C13—C14—C15—C16 | −0.6 (2) |
C6—C8—C9—F1 | 61.9 (2) | C12—C14—C15—C16 | −176.2 (2) |
C12—C8—C9—C10 | 6.1 (2) | C14—C15—C16—C18 | 179.5 (2) |
C6—C8—C9—C10 | −179.4 (2) | C14—C15—C16—S1 | 1.0 (2) |
F2—C9—C10—F3 | 95.2 (2) | C13—S1—C16—C15 | −1.0 (1) |
F1—C9—C10—F3 | −21.0 (2) | C13—S1—C16—C18 | −179.6 (1) |
C8—C9—C10—F3 | −141.0 (2) | C15—C16—C18—C19 | 13.6 (3) |
F2—C9—C10—F4 | −24.1 (2) | S1—C16—C18—C19 | −168.0 (1) |
F1—C9—C10—F4 | −140.3 (2) | C15—C16—C18—C23 | −164.5 (2) |
C8—C9—C10—F4 | 99.7 (2) | S1—C16—C18—C23 | 13.8 (2) |
F2—C9—C10—C11 | −139.2 (2) | C23—C18—C19—C20 | 2.4 (3) |
F1—C9—C10—C11 | 104.7 (2) | C16—C18—C19—C20 | −175.9 (2) |
C8—C9—C10—C11 | −15.4 (2) | C18—C19—C20—C21 | −0.7 (4) |
F3—C10—C11—F6 | −92.2 (2) | C24—O2—C21—C22 | 3.7 (3) |
F4—C10—C11—F6 | 27.3 (2) | C24—O2—C21—C20 | −176.5 (2) |
C9—C10—C11—F6 | 143.3 (2) | C19—C20—C21—O2 | 178.6 (2) |
F3—C10—C11—F5 | 24.4 (2) | C19—C20—C21—C22 | −1.6 (4) |
F4—C10—C11—F5 | 143.9 (2) | O2—C21—C22—C23 | −178.1 (2) |
C9—C10—C11—F5 | −100.2 (2) | C20—C21—C22—C23 | 2.2 (3) |
F3—C10—C11—C12 | 143.3 (2) | C21—C22—C23—C18 | −0.4 (3) |
F4—C10—C11—C12 | −97.2 (2) | C19—C18—C23—C22 | −1.8 (3) |
C9—C10—C11—C12 | 18.8 (2) | C16—C18—C23—C22 | 176.4 (2) |
C6—C8—C12—C14 | 12.2 (3) |
Experimental details
Crystal data | |
Chemical formula | C24H18F6O2S |
Mr | 484.44 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 291 |
a, b, c (Å) | 9.477 (1), 10.398 (1), 11.4573 (1) |
α, β, γ (°) | 90.259 (1), 101.436 (1), 94.055 (1) |
V (Å3) | 1103.7 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.22 |
Crystal size (mm) | 0.43 × 0.35 × 0.27 |
Data collection | |
Diffractometer | Bruker SMART area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.913, 0.944 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9784, 4979, 4028 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.135, 1.06 |
No. of reflections | 4979 |
No. of parameters | 301 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.27 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).
Photochromic diarylethenes find possible applications in optical memory-storage devices and as optical switches (Irie, 2000; Tian & Yang, 2004). In our own studies, we have found that central to photochromic activity of the class of perfluorocyclopentenes is a pendant five-membered heterocyclic ring (Fan et al., 2008), a feature that is displayed by the title compound, (I).
The envelope-shaped cyclopentenyl ring [the r.m.s.deviation of the constituent C atoms is 0.08 Å] has a substituent thienyl group and an anisyl group on opposing ends of the C═C double bond (Fig. 1). Steric hindrance is avoided by twisting of these rings [the dihedral angles being 51.2 (1)° for the phenylene ring and 51.3 (1)° for the thienyl ring], but the avoidance of crowding places the aliphatic ring substituents on opposites sides of the mean cyclopentenyl plane. This configuration is crucial for the manifestation of photochromism and other photo-induced properties (Woodward & Hoffmann, 1970). More importantly, the C═C double bond of the cyclopentenyl ring can, theoretically, change to a C—C single bond. Such a reduction in bond order would accompany the formation of a new C—C bond between the C atom of the phenylene group bearing the methoxy unit and the C atom of the thienyl group bearing the methyl substituent (Fig. 2).
As the distance between these two C atoms is 3.717 (2) Å, the compound can be expected to exhibit photochromism (Fig. 2). It is known that photochromic activity in similar compounds is usually present when this distance is less than 4.2 Å (Kobatake & Irie, 2004; Ramamurthy & Venkatesan, 1987). We have been able to verify this experimentally. Upon irradiation with 365 nm radiation, the colorless crystals turned blue rapidly, but if the UV light is removed, the blue color returns to colorless immediately. In hexane, the irradiated compound showed an absorption maximum at 592 nm. Upon irradiation using a wavelength of more than 510 nm, the blue hexane solution was rendered colorless and showed an absorption maximum at 287 nm. In a poly(methyl methacylate) amorphous film, the title diarylethene also demonstrates photochromism. Yamamoto et al. (2003) have tested photocyclization of a photochromic diarylethene derivative in single crystals. The result showed a photogenerated closed-ring diarylethene whose occupancy was estimated to be roughly 9%. In order to prove that the diarylethene crystals structure is change by UV light, we hope to design an experiment where a continually irradiated crystal can be subjected to X-ray crystallographic analysis to see if changes in the intensities and the unit cell can be observed and interpreted.