Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104005815/fr1446sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104005815/fr1446Isup2.hkl |
CCDC reference: 200593
The novel diarylethene (Ia) was prepared by the reduction of 1,2-bis(2-methyl-5-formyl-thien-3-yl)perfluorocyclopentene (BMFTP; Gilat et al., 1993; Shou-Zhi et al., 2002) with lithium aluminium hydride (see scheme below). To a stirred solution of LiAlH4 (0.1723 g, 4 mmol) in anhydrous ether (50 ml) at room temperature was added dropwise a solution of BMFTP (0.8486 g, 2 mmol) in ether (20 ml), and stirring was continued for 1 h at room temperature. Aqueous sodium potassium tartrate (30%, 5 ml) was then added. The mixture was filtered after stirring for a few minutes and dried over anhydrous MgSO4. The solvent was removed. Column chromatography (silica gel, ethyl acetate/hexane 1:1) afforded diarylethene (Ia) (0.8131 g, 95%) as colorless crystals. The structure of (Ia) was confirmed by melting point, NMR and mass spectrometry (m.p. 398 K). 1HNMR (500 MHz, CDCl3): δ 2.06 (s, 6H), 2.99 (s, 4H), 4.72 (s, 2H), 6.99 (s, 2H); MS m/z (M+): 428.
H atoms of hydroxy groups were found in a difference Fourier map and refined individually. The other H atoms were placed at idealized postions and treated as riding on their parent atoms, with C—H distances of 0.93 Å for aryl, 0.96 Å for methylene and 0.97 Å for methyl H atoms. The Uiso(H) values were set to 1.2Ueq of the parent atoms for aryl and methylene H atoms, and 1.5Ueq for methyl atoms.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The structure of (Ia), with 35% probability displacement ellipsoids and the atom-numbering scheme. | |
Fig. 2. A packing view along the a direction, showing the hydrogen bonding. |
C17H14F6O2S2 | F(000) = 872 |
Mr = 428.40 | Dx = 1.553 Mg m−3 |
Monoclinic, P21/c | Melting point: 125 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 13.5688 (10) Å | Cell parameters from 6248 reflections |
b = 7.5506 (6) Å | θ = 2.2–32.8° |
c = 18.0929 (14) Å | µ = 0.36 mm−1 |
β = 98.728 (2)° | T = 296 K |
V = 1832.2 (2) Å3 | Prism, colorless |
Z = 4 | 0.5 × 0.3 × 0.2 mm |
Bruker SMART APEX CCD diffractometer | 5308 independent reflections |
Radiation source: fine-focus sealed tube | 4075 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 15µm x 15µm pixels mm-1 | θmax = 30.0°, θmin = 2.3° |
ω scans | h = −19→19 |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | k = −7→10 |
Tmin = 0.79, Tmax = 0.93 | l = −25→25 |
14143 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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.001P)2 + 2.5P] where P = (Fo2 + 2Fc2)/3 |
5308 reflections | (Δ/σ)max = 0.001 |
254 parameters | Δρmax = 0.75 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
C17H14F6O2S2 | V = 1832.2 (2) Å3 |
Mr = 428.40 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.5688 (10) Å | µ = 0.36 mm−1 |
b = 7.5506 (6) Å | T = 296 K |
c = 18.0929 (14) Å | 0.5 × 0.3 × 0.2 mm |
β = 98.728 (2)° |
Bruker SMART APEX CCD diffractometer | 5308 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 4075 reflections with I > 2σ(I) |
Tmin = 0.79, Tmax = 0.93 | Rint = 0.024 |
14143 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.75 e Å−3 |
5308 reflections | Δρmin = −0.58 e Å−3 |
254 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. |
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 | 0.81011 (5) | 0.21514 (9) | 0.31531 (4) | 0.05078 (17) | |
S2 | 0.94117 (4) | 0.71452 (11) | 0.55645 (4) | 0.05488 (19) | |
F1 | 0.47722 (14) | 0.5078 (3) | 0.33811 (14) | 0.1013 (8) | |
F2 | 0.53390 (15) | 0.7091 (4) | 0.27370 (9) | 0.0993 (8) | |
F3 | 0.41204 (13) | 0.7631 (5) | 0.40481 (13) | 0.1546 (16) | |
F4 | 0.5060 (3) | 0.9465 (4) | 0.36292 (13) | 0.1499 (14) | |
F5 | 0.60270 (13) | 0.9431 (3) | 0.49155 (12) | 0.0819 (6) | |
F6 | 0.53627 (12) | 0.7024 (3) | 0.51934 (10) | 0.0805 (6) | |
O1 | 0.90629 (13) | 0.2981 (3) | 0.17097 (10) | 0.0476 (4) | |
H1A | 0.936 (2) | 0.368 (4) | 0.1968 (15) | 0.047 (8)* | |
O2 | 0.96538 (14) | 0.5359 (3) | 0.71925 (11) | 0.0552 (5) | |
H2A | 0.949 (2) | 0.442 (4) | 0.7019 (17) | 0.060 (10)* | |
C1 | 0.66526 (15) | 0.6799 (3) | 0.44564 (12) | 0.0362 (5) | |
C2 | 0.64256 (16) | 0.6003 (3) | 0.37909 (12) | 0.0387 (5) | |
C3 | 0.53859 (19) | 0.6482 (4) | 0.34276 (14) | 0.0547 (7) | |
C4 | 0.5029 (2) | 0.7873 (5) | 0.39384 (16) | 0.0647 (9) | |
C5 | 0.57794 (17) | 0.7824 (4) | 0.46518 (13) | 0.0444 (6) | |
C6 | 0.74911 (18) | 0.3309 (3) | 0.37647 (13) | 0.0434 (5) | |
C7 | 0.70144 (16) | 0.4748 (3) | 0.34218 (12) | 0.0394 (5) | |
C8 | 0.71514 (17) | 0.4898 (3) | 0.26529 (12) | 0.0415 (5) | |
H8A | 0.6872 | 0.5801 | 0.2339 | 0.050* | |
C9 | 0.77224 (16) | 0.3607 (3) | 0.24294 (12) | 0.0410 (5) | |
C10 | 0.80267 (17) | 0.3339 (4) | 0.16752 (13) | 0.0459 (6) | |
H10A | 0.7649 | 0.2361 | 0.1427 | 0.055* | |
H10B | 0.7860 | 0.4394 | 0.1376 | 0.055* | |
C11 | 0.7547 (3) | 0.2661 (4) | 0.45555 (15) | 0.0637 (8) | |
H11A | 0.6938 | 0.2946 | 0.4738 | 0.095* | |
H11B | 0.8096 | 0.3223 | 0.4865 | 0.095* | |
H11C | 0.7643 | 0.1401 | 0.4569 | 0.095* | |
C12 | 0.85060 (16) | 0.7146 (4) | 0.47856 (13) | 0.0424 (5) | |
C13 | 0.75881 (15) | 0.6829 (3) | 0.49816 (12) | 0.0356 (5) | |
C14 | 0.76317 (17) | 0.6596 (3) | 0.57709 (12) | 0.0399 (5) | |
H14A | 0.7072 | 0.6379 | 0.5996 | 0.048* | |
C15 | 0.85610 (18) | 0.6721 (3) | 0.61577 (13) | 0.0431 (5) | |
C16 | 0.8871 (2) | 0.6582 (4) | 0.69854 (14) | 0.0530 (7) | |
H16A | 0.9082 | 0.7740 | 0.7181 | 0.064* | |
H16B | 0.8300 | 0.6228 | 0.7214 | 0.064* | |
C17 | 0.8797 (2) | 0.7490 (5) | 0.40331 (15) | 0.0611 (8) | |
H17A | 0.8248 | 0.8026 | 0.3714 | 0.092* | |
H17B | 0.8968 | 0.6392 | 0.3818 | 0.092* | |
H17C | 0.9361 | 0.8273 | 0.4085 | 0.092* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0599 (4) | 0.0473 (4) | 0.0472 (3) | 0.0136 (3) | 0.0147 (3) | −0.0016 (3) |
S2 | 0.0327 (3) | 0.0748 (5) | 0.0545 (4) | −0.0039 (3) | −0.0020 (3) | 0.0038 (4) |
F1 | 0.0522 (10) | 0.1049 (17) | 0.1378 (19) | −0.0078 (11) | −0.0142 (11) | −0.0386 (15) |
F2 | 0.0903 (14) | 0.164 (2) | 0.0412 (9) | 0.0702 (15) | 0.0033 (9) | 0.0113 (12) |
F3 | 0.0368 (9) | 0.320 (5) | 0.1032 (17) | 0.0186 (17) | −0.0022 (10) | −0.108 (2) |
F4 | 0.268 (4) | 0.0968 (19) | 0.0698 (14) | 0.097 (2) | −0.0232 (18) | −0.0005 (13) |
F5 | 0.0536 (10) | 0.0660 (12) | 0.1222 (16) | 0.0136 (9) | 0.0007 (10) | −0.0415 (12) |
F6 | 0.0538 (9) | 0.1296 (18) | 0.0640 (11) | 0.0213 (11) | 0.0284 (8) | 0.0190 (11) |
O1 | 0.0358 (8) | 0.0616 (12) | 0.0456 (10) | 0.0029 (8) | 0.0070 (7) | −0.0106 (9) |
O2 | 0.0499 (11) | 0.0549 (12) | 0.0537 (11) | −0.0027 (10) | −0.0153 (8) | 0.0036 (10) |
C1 | 0.0310 (10) | 0.0421 (12) | 0.0354 (10) | 0.0048 (9) | 0.0052 (8) | 0.0011 (9) |
C2 | 0.0341 (10) | 0.0463 (13) | 0.0355 (11) | 0.0063 (10) | 0.0048 (8) | 0.0001 (10) |
C3 | 0.0412 (13) | 0.078 (2) | 0.0418 (13) | 0.0142 (13) | −0.0037 (10) | −0.0124 (13) |
C4 | 0.0464 (14) | 0.092 (2) | 0.0516 (15) | 0.0318 (16) | −0.0060 (12) | −0.0145 (16) |
C5 | 0.0351 (11) | 0.0547 (15) | 0.0424 (12) | 0.0071 (11) | 0.0030 (9) | −0.0098 (11) |
C6 | 0.0484 (13) | 0.0428 (13) | 0.0415 (12) | 0.0037 (11) | 0.0143 (10) | −0.0021 (10) |
C7 | 0.0355 (11) | 0.0461 (13) | 0.0366 (11) | 0.0038 (10) | 0.0057 (9) | −0.0051 (10) |
C8 | 0.0382 (11) | 0.0499 (14) | 0.0356 (11) | 0.0064 (10) | 0.0027 (9) | −0.0023 (10) |
C9 | 0.0349 (11) | 0.0510 (14) | 0.0365 (11) | 0.0019 (10) | 0.0031 (9) | −0.0059 (10) |
C10 | 0.0372 (11) | 0.0621 (16) | 0.0374 (11) | 0.0074 (11) | 0.0026 (9) | −0.0088 (11) |
C11 | 0.091 (2) | 0.0527 (17) | 0.0520 (16) | 0.0125 (16) | 0.0276 (15) | 0.0105 (13) |
C12 | 0.0342 (11) | 0.0510 (14) | 0.0411 (12) | 0.0014 (10) | 0.0027 (9) | 0.0045 (11) |
C13 | 0.0314 (10) | 0.0397 (12) | 0.0349 (10) | 0.0034 (9) | 0.0026 (8) | −0.0018 (9) |
C14 | 0.0371 (11) | 0.0456 (13) | 0.0371 (11) | 0.0018 (10) | 0.0056 (9) | −0.0017 (10) |
C15 | 0.0433 (12) | 0.0442 (13) | 0.0395 (12) | 0.0023 (11) | −0.0008 (9) | −0.0009 (10) |
C16 | 0.0567 (15) | 0.0565 (16) | 0.0407 (13) | 0.0040 (13) | −0.0088 (11) | −0.0024 (12) |
C17 | 0.0488 (14) | 0.083 (2) | 0.0542 (16) | −0.0072 (15) | 0.0153 (12) | 0.0099 (15) |
S1—C6 | 1.718 (2) | C6—C11 | 1.503 (3) |
S1—C9 | 1.727 (3) | C7—C8 | 1.436 (3) |
S2—C15 | 1.721 (3) | C8—C9 | 1.345 (3) |
S2—C12 | 1.724 (2) | C8—H8A | 0.9300 |
F1—C3 | 1.343 (4) | C9—C10 | 1.498 (3) |
F2—C3 | 1.324 (3) | C10—H10A | 0.9700 |
F3—C4 | 1.291 (4) | C10—H10B | 0.9700 |
F4—C4 | 1.329 (4) | C11—H11A | 0.9600 |
F5—C5 | 1.328 (3) | C11—H11B | 0.9600 |
F6—C5 | 1.347 (3) | C11—H11C | 0.9600 |
O1—C10 | 1.424 (3) | C12—C13 | 1.367 (3) |
O1—H1A | 0.78 (3) | C12—C17 | 1.497 (3) |
O2—C16 | 1.414 (3) | C13—C14 | 1.431 (3) |
O2—H2A | 0.79 (3) | C14—C15 | 1.349 (3) |
C1—C2 | 1.339 (3) | C14—H14A | 0.9300 |
C1—C13 | 1.466 (3) | C15—C16 | 1.496 (3) |
C1—C5 | 1.502 (3) | C16—H16A | 0.9700 |
C2—C7 | 1.464 (3) | C16—H16B | 0.9700 |
C2—C3 | 1.507 (3) | C17—H17A | 0.9600 |
C3—C4 | 1.525 (4) | C17—H17B | 0.9600 |
C4—C5 | 1.518 (3) | C17—H17C | 0.9600 |
C6—C7 | 1.365 (3) | ||
C6—S1—C9 | 92.73 (12) | C8—C9—S1 | 110.60 (18) |
C15—S2—C12 | 92.72 (11) | C10—C9—S1 | 120.89 (19) |
C10—O1—H1A | 109 (2) | O1—C10—C9 | 113.12 (19) |
C16—O2—H2A | 109 (2) | O1—C10—H10A | 109.0 |
C2—C1—C13 | 130.4 (2) | C9—C10—H10A | 109.0 |
C2—C1—C5 | 111.15 (19) | O1—C10—H10B | 109.0 |
C13—C1—C5 | 118.43 (19) | C9—C10—H10B | 109.0 |
C1—C2—C7 | 129.3 (2) | H10A—C10—H10B | 107.8 |
C1—C2—C3 | 110.9 (2) | C6—C11—H11A | 109.5 |
C7—C2—C3 | 119.7 (2) | C6—C11—H11B | 109.5 |
F2—C3—F1 | 105.9 (2) | H11A—C11—H11B | 109.5 |
F2—C3—C2 | 113.7 (2) | C6—C11—H11C | 109.5 |
F1—C3—C2 | 111.6 (2) | H11A—C11—H11C | 109.5 |
F2—C3—C4 | 111.0 (3) | H11B—C11—H11C | 109.5 |
F1—C3—C4 | 109.3 (3) | C13—C12—C17 | 130.0 (2) |
C2—C3—C4 | 105.3 (2) | C13—C12—S2 | 110.65 (17) |
F3—C4—F4 | 106.6 (3) | C17—C12—S2 | 119.35 (18) |
F3—C4—C5 | 113.5 (3) | C13—C12—C6 | 72.50 (14) |
F4—C4—C5 | 108.6 (3) | C17—C12—C6 | 78.80 (17) |
F3—C4—C3 | 113.2 (3) | S2—C12—C6 | 126.13 (13) |
F4—C4—C3 | 109.5 (3) | C12—C13—C14 | 112.28 (19) |
C5—C4—C3 | 105.3 (2) | C12—C13—C1 | 124.6 (2) |
F5—C5—F6 | 105.1 (2) | C14—C13—C1 | 123.05 (19) |
F5—C5—C1 | 112.9 (2) | C15—C14—C13 | 113.7 (2) |
F6—C5—C1 | 111.9 (2) | C15—C14—H14A | 123.1 |
F5—C5—C4 | 112.6 (2) | C13—C14—H14A | 123.1 |
F6—C5—C4 | 109.2 (2) | C14—C15—C16 | 127.8 (2) |
C1—C5—C4 | 105.29 (19) | C14—C15—S2 | 110.60 (18) |
C7—C6—C11 | 130.1 (2) | C16—C15—S2 | 121.58 (19) |
C7—C6—S1 | 110.72 (17) | O2—C16—C15 | 113.4 (2) |
C11—C6—S1 | 119.20 (19) | O2—C16—H16A | 108.9 |
C7—C6—C12 | 73.14 (15) | C15—C16—H16A | 108.9 |
C11—C6—C12 | 79.23 (16) | O2—C16—H16B | 108.9 |
S1—C6—C12 | 123.80 (12) | C15—C16—H16B | 108.9 |
C6—C7—C8 | 112.4 (2) | H16A—C16—H16B | 107.7 |
C6—C7—C2 | 124.2 (2) | C12—C17—H17A | 109.5 |
C8—C7—C2 | 123.4 (2) | C12—C17—H17B | 109.5 |
C9—C8—C7 | 113.6 (2) | H17A—C17—H17B | 109.5 |
C9—C8—H8A | 123.2 | C12—C17—H17C | 109.5 |
C7—C8—H8A | 123.2 | H17A—C17—H17C | 109.5 |
C8—C9—C10 | 128.5 (2) | H17B—C17—H17C | 109.5 |
C13—C1—C2—C7 | 7.8 (4) | C1—C2—C7—C6 | 47.1 (4) |
C5—C1—C2—C7 | −173.4 (2) | C3—C2—C7—C6 | −129.7 (3) |
C13—C1—C2—C3 | −175.2 (3) | C1—C2—C7—C8 | −133.1 (3) |
C5—C1—C2—C3 | 3.6 (3) | C3—C2—C7—C8 | 50.2 (4) |
C1—C2—C3—F2 | 127.5 (3) | C6—C7—C8—C9 | −0.4 (3) |
C7—C2—C3—F2 | −55.1 (4) | C2—C7—C8—C9 | 179.8 (2) |
C1—C2—C3—F1 | −112.7 (3) | C7—C8—C9—C10 | −179.7 (2) |
C7—C2—C3—F1 | 64.6 (3) | C7—C8—C9—S1 | 0.6 (3) |
C1—C2—C3—C4 | 5.8 (3) | C6—S1—C9—C8 | −0.5 (2) |
C7—C2—C3—C4 | −176.9 (3) | C6—S1—C9—C10 | 179.8 (2) |
F2—C3—C4—F3 | 99.6 (4) | C8—C9—C10—O1 | 132.9 (3) |
F1—C3—C4—F3 | −16.9 (4) | S1—C9—C10—O1 | −47.4 (3) |
C2—C3—C4—F3 | −136.9 (3) | C15—S2—C12—C13 | 0.0 (2) |
F2—C3—C4—F4 | −19.2 (4) | C15—S2—C12—C17 | 179.3 (2) |
F1—C3—C4—F4 | −135.7 (3) | C15—S2—C12—C6 | −82.99 (14) |
C2—C3—C4—F4 | 104.3 (3) | C7—C6—C12—C13 | 76.21 (19) |
F2—C3—C4—C5 | −135.9 (3) | C11—C6—C12—C13 | −61.7 (2) |
F1—C3—C4—C5 | 107.6 (3) | S1—C6—C12—C13 | −179.79 (18) |
C2—C3—C4—C5 | −12.3 (3) | C7—C6—C12—C17 | −62.34 (19) |
C2—C1—C5—F5 | −134.7 (2) | C11—C6—C12—C17 | 159.7 (2) |
C13—C1—C5—F5 | 44.3 (3) | S1—C6—C12—C17 | 41.7 (2) |
C2—C1—C5—F6 | 107.0 (2) | C7—C6—C12—S2 | 179.36 (18) |
C13—C1—C5—F6 | −74.0 (3) | C11—C6—C12—S2 | 41.4 (2) |
C2—C1—C5—C4 | −11.4 (3) | S1—C6—C12—S2 | −76.64 (19) |
C13—C1—C5—C4 | 167.5 (2) | C17—C12—C13—C14 | −178.9 (3) |
F3—C4—C5—F5 | −97.9 (4) | S2—C12—C13—C14 | 0.3 (3) |
F4—C4—C5—F5 | 20.4 (3) | C6—C12—C13—C14 | 123.1 (2) |
C3—C4—C5—F5 | 137.7 (3) | C17—C12—C13—C1 | −1.3 (5) |
F3—C4—C5—F6 | 18.3 (4) | S2—C12—C13—C1 | 177.92 (19) |
F4—C4—C5—F6 | 136.7 (3) | C6—C12—C13—C1 | −59.3 (2) |
C3—C4—C5—F6 | −106.1 (3) | C2—C1—C13—C12 | 46.8 (4) |
F3—C4—C5—C1 | 138.7 (3) | C5—C1—C13—C12 | −131.9 (3) |
F4—C4—C5—C1 | −103.0 (3) | C2—C1—C13—C14 | −135.8 (3) |
C3—C4—C5—C1 | 14.3 (3) | C5—C1—C13—C14 | 45.5 (3) |
C9—S1—C6—C7 | 0.2 (2) | C12—C13—C14—C15 | −0.5 (3) |
C9—S1—C6—C11 | −179.6 (2) | C1—C13—C14—C15 | −178.2 (2) |
C9—S1—C6—C12 | −82.87 (14) | C13—C14—C15—C16 | 178.7 (2) |
C11—C6—C7—C8 | 179.8 (3) | C13—C14—C15—S2 | 0.4 (3) |
S1—C6—C7—C8 | 0.0 (3) | C12—S2—C15—C14 | −0.2 (2) |
C12—C6—C7—C8 | 120.5 (2) | C12—S2—C15—C16 | −178.6 (2) |
C11—C6—C7—C2 | −0.3 (4) | C14—C15—C16—O2 | 128.7 (3) |
S1—C6—C7—C2 | 179.87 (19) | S2—C15—C16—O2 | −53.2 (3) |
C12—C6—C7—C2 | −59.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2i | 0.78 (3) | 2.00 (3) | 2.738 (3) | 159 (3) |
O2—H2A···O1ii | 0.79 (3) | 1.96 (3) | 2.748 (3) | 173 (3) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C17H14F6O2S2 |
Mr | 428.40 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 13.5688 (10), 7.5506 (6), 18.0929 (14) |
β (°) | 98.728 (2) |
V (Å3) | 1832.2 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.36 |
Crystal size (mm) | 0.5 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.79, 0.93 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14143, 5308, 4075 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.118, 1.05 |
No. of reflections | 5308 |
No. of parameters | 254 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.75, −0.58 |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXTL (Bruker, 1997), SHELXTL.
S1—C6 | 1.718 (2) | O1—C10 | 1.424 (3) |
S1—C9 | 1.727 (3) | C12—C13 | 1.367 (3) |
F1—C3 | 1.343 (4) | C12—C17 | 1.497 (3) |
C6—S1—C9 | 92.73 (12) | F1—C3—C2 | 111.6 (2) |
C2—C1—C13 | 130.4 (2) | C2—C3—C4 | 105.3 (2) |
C2—C1—C5 | 111.15 (19) | C5—C4—C3 | 105.3 (2) |
C13—C1—C5 | 118.43 (19) | C1—C5—C4 | 105.29 (19) |
F2—C3—F1 | 105.9 (2) | C8—C9—C10 | 128.5 (2) |
F2—C3—C2 | 113.7 (2) | O1—C10—C9 | 113.12 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2i | 0.78 (3) | 2.00 (3) | 2.738 (3) | 159 (3) |
O2—H2A···O1ii | 0.79 (3) | 1.96 (3) | 2.748 (3) | 173 (3) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+1/2, z+1/2. |
Photochromic diarylethene derivatives have attracted much attention as the most promising materials for optical memories and other optoelectronic devices because of their good thermal stability, high sensitivity and multiplexed recording (Hao-Bo et al., 2003; Irie, 2000). A diarylethene with five-membered heterocyclic rings has two conformations, with the two rings in mirror symmetry (parallel conformation) and in C2 symmetry (antiparallel conformation; Irie & Mohri, 1988; Uchida et al., 1990). According to the Woodward–Hoffmann rule, photoinduced cyclization and cycloreversion reactions can proceed in a conrotatory mode by alternate irradiation with UV and visible light only from the antiparallel conformation (Woodward & Hoffmann, 1970; Irie, 2000). In a previous paper, we have reported the allomorphism of a diarylethene compound and discussed its photochromic properties both in solution and in the single crystalline phase (Shou-Zhi et al., 2003). This compound is a good example for validating the rule exactly. In the present work, a novel photochromic diarylethene compound, (Ia), was synthesized in high yield by a simple method. The structure of this compound is presented here.
The molecular structure of (Ia) is shown in Fig. 1 and a packing diagram is shown in Fig. 2. In the perfluorocyclopentene ring, the C1—C2 bond is clearly a double bond, significantly shorter than the C1—C5 and C2—C3 single bonds. The distance between the reactive C atoms C6 and C12 is 3.596 (4) Å; this distance is short enough for the reaction theoretically to take place in the crystalline phase (Ramamurthy & Venkatesan, 1987). The dihedral angles between the perfluorocyclopentene ring and adjacent thiophene rings are 46.4 (1) and 49.5 (1)°, respectively. In addition, there exist intermolecular hydrogen-bonding interactions between molecules. There are two independent hydrogen bonds; the O1—H···O2 interaction connects two molecules into a dimer, and the O2—H···O1 interaction enables the dimers to form two-dimensional layer parallel to the (100) plane.
The molecule has approximate C2 symmetry (antiparallel conformation) and can therefore undergo a photocyclization reaction (Yamada et al., 2000). The photochromism is shown in the scheme above. On irradiation with 254 nm UV light, the colorless single-crystal of (Ia) turned red immediately. When observed under polarized light, the red color intensity changed on rotation of the crystalline sample. This phenomenon suggests that the closed-ring isomers are regularly packed in the crystal. When the red crystal was dissolved in ethanol, the solution turned red; the absorption maximum was observed at 514 nm, as it is for the closed-ring form, (Ib), shown in the scheme above. Unfortunately, the single-crystal diffraction pattern of (Ib) could not be obtained because it was very unstable under the experimental conditions. The red color disappeared rapidly upon irradiation with 450 nm light or daylight, and the absorption spectrum of the solution containing the colorless crystal is the same as that of the open-ring form, (Ia).