Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680504033X/lh6558sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680504033X/lh6558Iasup2.hkl |
CCDC reference: 281126
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.007 Å
- Disorder in main residue
- R factor = 0.068
- wR factor = 0.143
- Data-to-parameter ratio = 12.9
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C32
Alert level C ABSTM02_ALERT_3_C The ratio of Tmax/Tmin expected RT(exp) is > 1.10 Absorption corrections should be applied. Tmin and Tmax expected: 0.845 0.944 RT(exp) = 1.117 PLAT057_ALERT_3_C Correction for Absorption Required RT(exp) ... 1.12 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.19 PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C25 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for S3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C23 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C30 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C50 PLAT301_ALERT_3_C Main Residue Disorder ......................... 3.00 Perc. PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 7 PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C11 - C12 ... 1.38 Ang. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C12 - C13 ... 1.36 Ang. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C22 - C23 ... 1.35 Ang. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C23 - C24 ... 1.33 Ang. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C38 - C39 ... 1.38 Ang. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C39 - C40 ... 1.34 Ang. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C49 - C50 ... 1.36 Ang. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C50 - C51 ... 1.36 Ang.
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 19 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 15 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion
The title compound was derived originally from 2-methylthiophene, (1). 3,5-Dibromo-2-methylthiophene, (2) (50.7 g, 198.1 mmol), in 81.2% yield was synthesized by bromizing (1) (24.0 g, 244.8 mmol) in acetic acid at 273 K. 3-Bromo- 2-methyl-5-thienylboronic acid, (3) (12.0 g, 54.3 mmol), was prepared in 85.5% yield in the presence of compound (2) (16.3 g, 63.7 mmol), n-BuLi/hexane solution (2.5 mol l−1, 65 mmol) and tri-n-butylborate (18.8 ml, 68.9 mmol) at 195 K under nitrogen atmosphere. 3-Bromo-2-methyl-5-(3-fluorinephenyl)thiophene, (4) (6.8 g, 25.1 mmol), was prepared in 82.5% yield by reacting compound (3) (6.7 g, 30.4 mmol) with 3-bromo-1-fluorinebenzene (5.3 g, 30.4 mmol) in the presence of Pd(PPh3)4 (1.0 g) and Na2CO3 (2 mol l−1, 114 mmol) in tetrahydrofuran (THF, 120 ml) for 15 h at 343 K. Finally, to a stirred THF solution (100 ml) of compound (4) (1.9 g, 7.0 mmol), n-BuLi/hexane solution (2.8 ml, 2.5 mol l−1, 7.0 mmol) was added slowly at 195 K under a nitrogen atmosphere. 30 min later, (2-methyl-5-phenyl-3- thienyl)perfluorocyclopent- 1-ene, (5) (Peters et al., 2003) (2.6 g, 7.1 mmol), was added and the mixture was stirred for 2 h at this temperature. The reaction mixture was extracted with ether and evaporated in vacuo, then purifed by column chromatography (oil ether) to give the title compound (Ia) (1.5 g, 2.8 mmol) in 40% yield. The compound crystallized from hexane at room temperature and produced crystals suitable for X-ray analysis. The structure of (Ia) was confirmed by melting point, element analysis, NMR and IR: m.p. 393.8–394.3 K. Analysis calculated for C27H17F7S2: C 60.22, H 3.18%; found: C 60.31, H 3.23%. 1H NMR (400 MHz, CDCl3): δ 1.965 (s, 3H), 1.969 (s, 3H), 6.977–7.015 (t, 1H, J = 7.6 Hz, ben-H), 7.223 (s, 1H, thiophene-H), 7.278 (s, 1H, thiophene-H), 7.293–7.305 (d, 2H, J = 4.8 Hz, ben-H), 7.324 (s, 1H, ben-H), 7.337–7.357 (t, 1H, J = 7.6 Hz, ben-H), 7.370–7.408 (t, 2H, J = 7.6 Hz, ben-H), 7.535–7.553 (d, 2H, J = 7.2 Hz, ben-H); 19F NMR (400 MHz, CDCl3): 110.01 (4 F), 112.33 (1 F), 131.79 (2 F); IR (KBr): ν (cm−1) 759, 783, 821, 986, 1055, 1112, 1138, 1186, 1274, 1340, 1442, 1470, 1502, 1586, 1612.
In each independent molecule, the m-substituted F atom of the benzene ring is disordered over the two meta positions of both rings but only one meta position in each ring is occupied by partial F atoms, the H atoms in these positions being equally disordered. The site occupancies of the disordered atoms F7/F8 and F15/F16 are 0.497 (5)/0.503 (5) and 0.481 (5)/0.519 (5), repectively. H atoms were positioned geometrically [0.93 (CH) and 0.96 Å (CH3)] and constrained to ride on their parent atoms with Uiso(H) values of 1.2 or 1.5 (for methyl) times Ueq(C).
Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS; data reduction: XSCANS; 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.
C27H17F7S2 | F(000) = 2192 |
Mr = 538.53 | Dx = 1.473 Mg m−3 |
Monoclinic, P21/c | Melting point = 393.8–394.3 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 18.945 (2) Å | Cell parameters from 50 reflections |
b = 11.7925 (19) Å | θ = 5.0–12.5° |
c = 21.876 (4) Å | µ = 0.29 mm−1 |
β = 96.587 (12)° | T = 295 K |
V = 4855.1 (13) Å3 | Prism, colorless |
Z = 8 | 0.6 × 0.5 × 0.2 mm |
Bruker P4 diffractometer | Rint = 0.036 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.9° |
Graphite monochromator | h = −22→1 |
ω scans | k = −1→14 |
10367 measured reflections | l = −25→26 |
8526 independent reflections | 3 standard reflections every 97 reflections |
5532 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.001P)2 + 1P] where P = (Fo2 + 2Fc2)/3 |
8526 reflections | (Δ/σ)max = 0.002 |
661 parameters | Δρmax = 0.88 e Å−3 |
4 restraints | Δρmin = −0.40 e Å−3 |
C27H17F7S2 | V = 4855.1 (13) Å3 |
Mr = 538.53 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 18.945 (2) Å | µ = 0.29 mm−1 |
b = 11.7925 (19) Å | T = 295 K |
c = 21.876 (4) Å | 0.6 × 0.5 × 0.2 mm |
β = 96.587 (12)° |
Bruker P4 diffractometer | Rint = 0.036 |
10367 measured reflections | 3 standard reflections every 97 reflections |
8526 independent reflections | intensity decay: none |
5532 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.068 | 4 restraints |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.88 e Å−3 |
8526 reflections | Δρmin = −0.40 e Å−3 |
661 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 | Occ. (<1) | |
S1 | 0.23307 (5) | 0.46803 (11) | 0.15973 (6) | 0.0667 (3) | |
S2 | 0.37133 (7) | 0.18437 (10) | −0.00328 (5) | 0.0739 (3) | |
S3 | 0.85988 (8) | 0.44442 (11) | −0.00360 (6) | 0.0830 (4) | |
S4 | 0.73581 (6) | 0.14790 (12) | 0.17379 (6) | 0.0754 (4) | |
F1 | 0.57386 (15) | 0.2234 (3) | 0.17741 (17) | 0.1088 (11) | |
F2 | 0.59085 (15) | 0.3746 (3) | 0.12497 (15) | 0.1109 (11) | |
F3 | 0.55298 (16) | 0.3345 (3) | 0.27345 (14) | 0.1033 (10) | |
F4 | 0.62185 (13) | 0.4547 (3) | 0.23388 (15) | 0.1019 (10) | |
F5 | 0.51620 (14) | 0.5819 (2) | 0.19336 (15) | 0.0943 (9) | |
F6 | 0.47258 (14) | 0.5068 (3) | 0.27013 (13) | 0.0931 (9) | |
F7 | 0.2706 (4) | 0.9990 (6) | 0.1261 (4) | 0.141 (2) | 0.497 (5) |
F8 | 0.4892 (4) | −0.3002 (6) | 0.0814 (4) | 0.141 (2) | 0.503 (5) |
F9 | 0.98182 (16) | 0.1270 (3) | 0.26818 (15) | 0.1154 (12) | |
F10 | 1.01856 (15) | 0.0528 (2) | 0.18873 (18) | 0.1099 (11) | |
F11 | 1.0568 (2) | 0.2969 (4) | 0.27108 (17) | 0.1365 (14) | |
F12 | 1.12375 (15) | 0.1900 (3) | 0.2238 (2) | 0.1370 (15) | |
F13 | 1.08485 (16) | 0.2873 (4) | 0.11982 (17) | 0.1498 (17) | |
F14 | 1.06255 (16) | 0.4206 (3) | 0.18046 (18) | 0.1205 (12) | |
F15 | 0.9886 (4) | 0.9270 (7) | 0.0628 (5) | 0.157 (2) | 0.481 (5) |
F16 | 0.7754 (4) | −0.3778 (6) | 0.1311 (4) | 0.157 (2) | 0.519 (5) |
C1 | 0.44197 (19) | 0.4218 (3) | 0.17232 (18) | 0.0526 (9) | |
C2 | 0.4725 (2) | 0.3374 (3) | 0.14334 (19) | 0.0580 (10) | |
C3 | 0.5506 (2) | 0.3298 (4) | 0.1666 (2) | 0.0726 (13) | |
C4 | 0.5594 (2) | 0.4015 (4) | 0.2237 (2) | 0.0722 (13) | |
C5 | 0.4959 (2) | 0.4826 (4) | 0.2158 (2) | 0.0633 (11) | |
C6 | 0.3100 (2) | 0.3890 (4) | 0.16551 (18) | 0.0569 (10) | |
C7 | 0.36754 (19) | 0.4599 (3) | 0.16609 (18) | 0.0520 (9) | |
C8 | 0.3486 (2) | 0.5763 (3) | 0.16261 (18) | 0.0556 (10) | |
H8A | 0.3818 | 0.6345 | 0.1633 | 0.067* | |
C9 | 0.2772 (2) | 0.5951 (4) | 0.15823 (18) | 0.0561 (10) | |
C10 | 0.2390 (2) | 0.7035 (4) | 0.15288 (19) | 0.0616 (11) | |
C11 | 0.2731 (2) | 0.8022 (4) | 0.1389 (2) | 0.0767 (13) | |
H11A | 0.3206 | 0.8004 | 0.1319 | 0.092* | |
C12 | 0.2364 (3) | 0.9033 (5) | 0.1353 (3) | 0.0914 (16) | |
H12A | 0.2601 | 0.9691 | 0.1261 | 0.110* | 0.503 (5) |
C13 | 0.1668 (3) | 0.9114 (5) | 0.1451 (2) | 0.0920 (17) | |
H13A | 0.1437 | 0.9811 | 0.1430 | 0.110* | |
C14 | 0.1322 (3) | 0.8152 (5) | 0.1580 (2) | 0.0879 (16) | |
H14A | 0.0845 | 0.8189 | 0.1641 | 0.106* | |
C15 | 0.1673 (2) | 0.7103 (5) | 0.1622 (2) | 0.0766 (13) | |
H15A | 0.1429 | 0.6451 | 0.1713 | 0.092* | |
C16 | 0.3052 (2) | 0.2629 (4) | 0.1708 (2) | 0.0736 (13) | |
H16A | 0.3475 | 0.2345 | 0.1941 | 0.110* | |
H16B | 0.3002 | 0.2298 | 0.1305 | 0.110* | |
H16C | 0.2647 | 0.2434 | 0.1913 | 0.110* | |
C17 | 0.4015 (3) | 0.2979 (4) | 0.0413 (2) | 0.0673 (12) | |
C18 | 0.4409 (2) | 0.2618 (3) | 0.09434 (19) | 0.0595 (10) | |
C19 | 0.4471 (2) | 0.1413 (4) | 0.0968 (2) | 0.0625 (11) | |
H19A | 0.4733 | 0.1034 | 0.1291 | 0.075* | |
C20 | 0.4118 (2) | 0.0868 (4) | 0.0483 (2) | 0.0630 (11) | |
C21 | 0.4063 (3) | −0.0351 (4) | 0.0363 (2) | 0.0658 (11) | |
C22 | 0.4550 (3) | −0.1096 (4) | 0.0653 (2) | 0.0766 (13) | |
H22A | 0.4926 | −0.0831 | 0.0927 | 0.092* | |
C23 | 0.4478 (3) | −0.2216 (4) | 0.0535 (3) | 0.0895 (16) | |
H23A | 0.4814 | −0.2696 | 0.0742 | 0.107* | 0.497 (5) |
C24 | 0.3965 (4) | −0.2669 (5) | 0.0147 (3) | 0.110 (2) | |
H24A | 0.3941 | −0.3447 | 0.0079 | 0.132* | |
C25 | 0.3475 (4) | −0.1955 (5) | −0.0149 (3) | 0.120 (2) | |
H25A | 0.3105 | −0.2245 | −0.0421 | 0.144* | |
C26 | 0.3525 (3) | −0.0798 (4) | −0.0044 (2) | 0.0890 (16) | |
H26A | 0.3190 | −0.0316 | −0.0252 | 0.107* | |
C27 | 0.3860 (3) | 0.4177 (4) | 0.0197 (2) | 0.0903 (16) | |
H27A | 0.4236 | 0.4667 | 0.0368 | 0.136* | |
H27B | 0.3419 | 0.4423 | 0.0330 | 0.136* | |
H27C | 0.3825 | 0.4203 | −0.0244 | 0.136* | |
C28 | 0.9667 (2) | 0.2990 (3) | 0.14261 (19) | 0.0568 (10) | |
C29 | 0.9414 (2) | 0.2101 (3) | 0.17125 (18) | 0.0551 (10) | |
C30 | 0.9996 (2) | 0.1515 (4) | 0.2121 (2) | 0.0687 (12) | |
C31 | 1.0612 (3) | 0.2339 (5) | 0.2161 (3) | 0.0923 (17) | |
C32 | 1.0451 (2) | 0.3156 (4) | 0.1635 (2) | 0.0694 (12) | |
C33 | 0.8908 (3) | 0.3336 (4) | 0.0429 (2) | 0.0674 (12) | |
C34 | 0.9312 (2) | 0.3734 (3) | 0.09439 (19) | 0.0594 (10) | |
C35 | 0.9369 (2) | 0.4936 (4) | 0.0944 (2) | 0.0641 (11) | |
H35A | 0.9633 | 0.5334 | 0.1259 | 0.077* | |
C36 | 0.9014 (3) | 0.5453 (4) | 0.0456 (2) | 0.0666 (12) | |
C37 | 0.8948 (3) | 0.6655 (4) | 0.0319 (2) | 0.0678 (12) | |
C38 | 0.9483 (3) | 0.7394 (4) | 0.0538 (3) | 0.0855 (15) | |
H38A | 0.9891 | 0.7128 | 0.0770 | 0.103* | |
C39 | 0.9400 (4) | 0.8531 (5) | 0.0408 (3) | 0.1005 (18) | |
H39A | 0.9765 | 0.9017 | 0.0562 | 0.121* | 0.519 (5) |
C40 | 0.8837 (4) | 0.8979 (5) | 0.0068 (3) | 0.1004 (18) | |
H40A | 0.8810 | 0.9754 | −0.0010 | 0.120* | |
C41 | 0.8300 (4) | 0.8267 (5) | −0.0162 (3) | 0.0992 (18) | |
H41A | 0.7904 | 0.8549 | −0.0405 | 0.119* | |
C42 | 0.8357 (3) | 0.7109 (4) | −0.0028 (2) | 0.0842 (15) | |
H42A | 0.7987 | 0.6628 | −0.0176 | 0.101* | |
C43 | 0.8750 (3) | 0.2128 (4) | 0.0226 (2) | 0.0867 (15) | |
H43A | 0.9150 | 0.1655 | 0.0361 | 0.130* | |
H43B | 0.8660 | 0.2100 | −0.0215 | 0.130* | |
H43C | 0.8340 | 0.1860 | 0.0402 | 0.130* | |
C44 | 0.8097 (2) | 0.2319 (4) | 0.17476 (19) | 0.0624 (11) | |
C45 | 0.8684 (2) | 0.1657 (4) | 0.16939 (18) | 0.0552 (10) | |
C46 | 0.8522 (2) | 0.0476 (4) | 0.16482 (19) | 0.0596 (10) | |
H46A | 0.8864 | −0.0078 | 0.1613 | 0.072* | |
C47 | 0.7819 (2) | 0.0233 (4) | 0.16612 (19) | 0.0626 (11) | |
C48 | 0.7452 (2) | −0.0881 (4) | 0.16126 (18) | 0.0609 (11) | |
C49 | 0.7804 (3) | −0.1827 (4) | 0.1461 (2) | 0.0777 (14) | |
H49A | 0.8272 | −0.1794 | 0.1373 | 0.093* | |
C50 | 0.7440 (3) | −0.2827 (5) | 0.1442 (3) | 0.0928 (16) | |
H50A | 0.7680 | −0.3477 | 0.1341 | 0.111* | 0.481 (5) |
C51 | 0.6757 (3) | −0.2959 (6) | 0.1557 (2) | 0.0961 (19) | |
H51A | 0.6536 | −0.3664 | 0.1536 | 0.115* | |
C52 | 0.6412 (3) | −0.2000 (6) | 0.1706 (2) | 0.0924 (17) | |
H52A | 0.5943 | −0.2049 | 0.1791 | 0.111* | |
C53 | 0.6749 (2) | −0.0949 (5) | 0.1734 (2) | 0.0817 (14) | |
H53A | 0.6507 | −0.0300 | 0.1833 | 0.098* | |
C54 | 0.8032 (3) | 0.3574 (4) | 0.1817 (2) | 0.0858 (15) | |
H54A | 0.8475 | 0.3876 | 0.2007 | 0.129* | |
H54B | 0.7663 | 0.3740 | 0.2069 | 0.129* | |
H54C | 0.7918 | 0.3913 | 0.1419 | 0.129* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0463 (6) | 0.0730 (7) | 0.0802 (8) | −0.0050 (5) | 0.0045 (5) | −0.0012 (6) |
S2 | 0.0983 (9) | 0.0588 (7) | 0.0623 (7) | 0.0121 (6) | −0.0005 (6) | 0.0014 (6) |
S3 | 0.1215 (11) | 0.0586 (7) | 0.0642 (7) | −0.0088 (7) | −0.0098 (7) | 0.0015 (6) |
S4 | 0.0472 (6) | 0.0924 (9) | 0.0875 (8) | 0.0084 (6) | 0.0113 (5) | 0.0029 (7) |
F1 | 0.0716 (18) | 0.077 (2) | 0.171 (3) | 0.0274 (16) | −0.0177 (19) | −0.013 (2) |
F2 | 0.0694 (18) | 0.149 (3) | 0.120 (2) | −0.0067 (19) | 0.0385 (17) | −0.011 (2) |
F3 | 0.098 (2) | 0.113 (2) | 0.095 (2) | 0.0121 (19) | −0.0057 (17) | 0.026 (2) |
F4 | 0.0518 (15) | 0.109 (2) | 0.141 (3) | −0.0065 (16) | −0.0073 (16) | −0.012 (2) |
F5 | 0.0672 (16) | 0.0593 (16) | 0.152 (3) | −0.0125 (14) | −0.0083 (17) | 0.0077 (17) |
F6 | 0.0672 (16) | 0.125 (3) | 0.0853 (19) | −0.0013 (16) | −0.0013 (14) | −0.0398 (18) |
F7 | 0.144 (5) | 0.094 (4) | 0.186 (6) | 0.027 (3) | 0.025 (4) | 0.029 (4) |
F8 | 0.144 (5) | 0.094 (4) | 0.186 (6) | 0.027 (3) | 0.025 (4) | 0.029 (4) |
F9 | 0.083 (2) | 0.163 (3) | 0.096 (2) | 0.013 (2) | −0.0072 (17) | 0.048 (2) |
F10 | 0.0698 (18) | 0.0670 (19) | 0.187 (3) | 0.0200 (15) | −0.0118 (19) | −0.017 (2) |
F11 | 0.139 (3) | 0.153 (4) | 0.110 (3) | −0.026 (3) | −0.016 (2) | −0.021 (3) |
F12 | 0.0502 (17) | 0.140 (3) | 0.215 (4) | 0.0065 (19) | −0.007 (2) | 0.041 (3) |
F13 | 0.0703 (19) | 0.269 (5) | 0.118 (3) | −0.024 (3) | 0.0420 (19) | −0.034 (3) |
F14 | 0.091 (2) | 0.075 (2) | 0.184 (3) | −0.0152 (17) | −0.037 (2) | −0.014 (2) |
F15 | 0.142 (5) | 0.113 (4) | 0.214 (7) | −0.019 (4) | 0.008 (5) | 0.013 (5) |
F16 | 0.142 (5) | 0.113 (4) | 0.214 (7) | −0.019 (4) | 0.008 (5) | 0.013 (5) |
C1 | 0.049 (2) | 0.048 (2) | 0.061 (2) | −0.0012 (18) | 0.0072 (18) | 0.0059 (19) |
C2 | 0.056 (2) | 0.053 (2) | 0.066 (3) | 0.005 (2) | 0.009 (2) | 0.004 (2) |
C3 | 0.056 (3) | 0.067 (3) | 0.094 (4) | 0.011 (2) | 0.010 (2) | 0.000 (3) |
C4 | 0.048 (2) | 0.077 (3) | 0.089 (3) | −0.002 (2) | −0.004 (2) | 0.010 (3) |
C5 | 0.052 (2) | 0.059 (3) | 0.079 (3) | −0.005 (2) | 0.006 (2) | −0.005 (2) |
C6 | 0.054 (2) | 0.057 (3) | 0.060 (2) | −0.0033 (19) | 0.0041 (19) | −0.003 (2) |
C7 | 0.049 (2) | 0.050 (2) | 0.057 (2) | −0.0006 (18) | 0.0060 (17) | −0.0042 (19) |
C8 | 0.048 (2) | 0.054 (2) | 0.066 (3) | −0.0009 (18) | 0.0077 (18) | −0.006 (2) |
C9 | 0.048 (2) | 0.061 (3) | 0.059 (2) | 0.0017 (19) | 0.0060 (18) | −0.002 (2) |
C10 | 0.054 (2) | 0.072 (3) | 0.058 (3) | 0.011 (2) | 0.0042 (19) | −0.004 (2) |
C11 | 0.062 (3) | 0.071 (3) | 0.097 (4) | 0.015 (2) | 0.011 (3) | 0.000 (3) |
C12 | 0.096 (4) | 0.066 (3) | 0.112 (4) | 0.017 (3) | 0.010 (3) | 0.007 (3) |
C13 | 0.090 (4) | 0.094 (4) | 0.092 (4) | 0.040 (3) | 0.011 (3) | −0.005 (3) |
C14 | 0.070 (3) | 0.107 (5) | 0.087 (4) | 0.030 (3) | 0.009 (3) | −0.008 (3) |
C15 | 0.058 (3) | 0.090 (4) | 0.083 (3) | 0.012 (3) | 0.011 (2) | −0.002 (3) |
C16 | 0.071 (3) | 0.064 (3) | 0.085 (3) | −0.011 (2) | 0.006 (2) | 0.002 (3) |
C17 | 0.085 (3) | 0.052 (3) | 0.064 (3) | 0.010 (2) | 0.009 (2) | 0.005 (2) |
C18 | 0.065 (3) | 0.050 (2) | 0.064 (3) | 0.009 (2) | 0.011 (2) | 0.001 (2) |
C19 | 0.069 (3) | 0.054 (3) | 0.064 (3) | 0.012 (2) | 0.008 (2) | 0.006 (2) |
C20 | 0.075 (3) | 0.055 (3) | 0.060 (3) | 0.010 (2) | 0.012 (2) | 0.002 (2) |
C21 | 0.088 (3) | 0.055 (3) | 0.057 (3) | 0.007 (2) | 0.018 (2) | 0.000 (2) |
C22 | 0.094 (4) | 0.053 (3) | 0.083 (3) | 0.009 (3) | 0.011 (3) | 0.001 (2) |
C23 | 0.126 (5) | 0.058 (3) | 0.089 (4) | 0.020 (3) | 0.030 (3) | 0.014 (3) |
C24 | 0.181 (7) | 0.056 (3) | 0.094 (4) | −0.002 (4) | 0.023 (4) | −0.008 (3) |
C25 | 0.172 (7) | 0.076 (4) | 0.105 (5) | −0.006 (4) | −0.017 (5) | −0.013 (4) |
C26 | 0.132 (5) | 0.056 (3) | 0.074 (3) | 0.006 (3) | −0.011 (3) | −0.007 (3) |
C27 | 0.128 (5) | 0.060 (3) | 0.080 (3) | 0.018 (3) | −0.004 (3) | 0.013 (3) |
C28 | 0.055 (2) | 0.049 (2) | 0.067 (3) | −0.0016 (19) | 0.0107 (19) | −0.007 (2) |
C29 | 0.050 (2) | 0.054 (2) | 0.062 (2) | 0.0034 (19) | 0.0079 (18) | 0.001 (2) |
C30 | 0.054 (2) | 0.069 (3) | 0.083 (3) | 0.006 (2) | 0.004 (2) | 0.012 (3) |
C31 | 0.060 (3) | 0.084 (4) | 0.128 (5) | 0.004 (3) | −0.012 (3) | 0.001 (4) |
C32 | 0.062 (3) | 0.066 (3) | 0.081 (3) | −0.010 (2) | 0.012 (2) | −0.012 (3) |
C33 | 0.087 (3) | 0.058 (3) | 0.056 (3) | −0.008 (2) | 0.005 (2) | −0.005 (2) |
C34 | 0.069 (3) | 0.052 (2) | 0.058 (2) | −0.005 (2) | 0.011 (2) | −0.002 (2) |
C35 | 0.079 (3) | 0.049 (2) | 0.064 (3) | −0.009 (2) | 0.008 (2) | −0.006 (2) |
C36 | 0.087 (3) | 0.055 (3) | 0.058 (3) | −0.006 (2) | 0.009 (2) | 0.000 (2) |
C37 | 0.089 (3) | 0.051 (3) | 0.064 (3) | −0.002 (2) | 0.015 (2) | 0.000 (2) |
C38 | 0.093 (4) | 0.062 (3) | 0.101 (4) | −0.006 (3) | 0.008 (3) | 0.005 (3) |
C39 | 0.119 (5) | 0.060 (3) | 0.123 (5) | −0.020 (3) | 0.016 (4) | −0.008 (3) |
C40 | 0.144 (6) | 0.058 (3) | 0.100 (4) | 0.012 (4) | 0.017 (4) | 0.007 (3) |
C41 | 0.124 (5) | 0.065 (3) | 0.110 (5) | 0.006 (3) | 0.018 (4) | −0.003 (3) |
C42 | 0.104 (4) | 0.067 (3) | 0.080 (3) | −0.001 (3) | 0.003 (3) | 0.004 (3) |
C43 | 0.121 (4) | 0.058 (3) | 0.079 (3) | −0.013 (3) | 0.000 (3) | −0.003 (3) |
C44 | 0.056 (2) | 0.066 (3) | 0.065 (3) | 0.010 (2) | 0.009 (2) | 0.005 (2) |
C45 | 0.048 (2) | 0.062 (3) | 0.056 (2) | 0.0044 (19) | 0.0062 (18) | 0.006 (2) |
C46 | 0.049 (2) | 0.062 (3) | 0.069 (3) | 0.001 (2) | 0.0082 (19) | 0.010 (2) |
C47 | 0.048 (2) | 0.078 (3) | 0.061 (3) | 0.001 (2) | 0.0047 (19) | 0.012 (2) |
C48 | 0.058 (2) | 0.076 (3) | 0.049 (2) | −0.010 (2) | 0.0058 (19) | 0.009 (2) |
C49 | 0.064 (3) | 0.079 (3) | 0.089 (4) | −0.014 (3) | 0.007 (2) | 0.013 (3) |
C50 | 0.100 (4) | 0.084 (4) | 0.093 (4) | −0.008 (3) | 0.006 (3) | 0.014 (3) |
C51 | 0.097 (4) | 0.110 (5) | 0.079 (4) | −0.051 (4) | 0.001 (3) | 0.015 (3) |
C52 | 0.081 (4) | 0.119 (5) | 0.078 (4) | −0.033 (4) | 0.013 (3) | 0.002 (3) |
C53 | 0.061 (3) | 0.105 (4) | 0.079 (3) | −0.022 (3) | 0.011 (2) | 0.001 (3) |
C54 | 0.076 (3) | 0.079 (3) | 0.105 (4) | 0.018 (3) | 0.018 (3) | −0.007 (3) |
S1—C9 | 1.718 (4) | C22—C23 | 1.350 (7) |
S1—C6 | 1.721 (4) | C22—H22A | 0.9300 |
S2—C17 | 1.715 (5) | C23—C24 | 1.327 (8) |
S2—C20 | 1.728 (4) | C23—H23A | 0.9300 |
S3—C33 | 1.718 (5) | C24—C25 | 1.360 (8) |
S3—C36 | 1.731 (4) | C24—H24A | 0.9300 |
S4—C44 | 1.713 (4) | C25—C26 | 1.385 (7) |
S4—C47 | 1.727 (5) | C25—H25A | 0.9300 |
F1—C3 | 1.342 (5) | C26—H26A | 0.9300 |
F2—C3 | 1.361 (5) | C27—H27A | 0.9600 |
F3—C4 | 1.361 (5) | C27—H27B | 0.9600 |
F4—C4 | 1.336 (5) | C27—H27C | 0.9600 |
F5—C5 | 1.344 (5) | C28—C29 | 1.338 (5) |
F6—C5 | 1.345 (5) | C28—C34 | 1.474 (6) |
F7—C12 | 1.328 (5) | C28—C32 | 1.516 (6) |
F8—C23 | 1.319 (4) | C29—C45 | 1.475 (5) |
F9—C30 | 1.340 (5) | C29—C30 | 1.505 (6) |
F10—C30 | 1.337 (5) | C30—C31 | 1.514 (7) |
F11—C31 | 1.425 (7) | C31—C32 | 1.505 (7) |
F12—C31 | 1.286 (5) | C33—C34 | 1.371 (6) |
F13—C32 | 1.324 (5) | C33—C43 | 1.512 (6) |
F14—C32 | 1.323 (5) | C34—C35 | 1.421 (6) |
F15—C39 | 1.317 (5) | C35—C36 | 1.342 (6) |
F16—C50 | 1.316 (5) | C35—H35A | 0.9300 |
C1—C2 | 1.346 (5) | C36—C37 | 1.451 (6) |
C1—C7 | 1.471 (5) | C37—C38 | 1.380 (6) |
C1—C5 | 1.496 (6) | C37—C42 | 1.386 (7) |
C2—C18 | 1.468 (6) | C38—C39 | 1.377 (7) |
C2—C3 | 1.511 (6) | C38—H38A | 0.9300 |
C3—C4 | 1.501 (7) | C39—C40 | 1.338 (8) |
C4—C5 | 1.531 (6) | C39—H39A | 0.9301 |
C6—C7 | 1.373 (5) | C40—C41 | 1.369 (8) |
C6—C16 | 1.496 (6) | C40—H40A | 0.9300 |
C7—C8 | 1.419 (5) | C41—C42 | 1.399 (7) |
C8—C9 | 1.363 (5) | C41—H41A | 0.9300 |
C8—H8A | 0.9300 | C42—H42A | 0.9300 |
C9—C10 | 1.467 (6) | C43—H43A | 0.9600 |
C10—C11 | 1.383 (6) | C43—H43B | 0.9600 |
C10—C15 | 1.400 (6) | C43—H43C | 0.9600 |
C11—C12 | 1.378 (6) | C44—C45 | 1.375 (5) |
C11—H11A | 0.9300 | C44—C54 | 1.495 (6) |
C12—C13 | 1.362 (7) | C45—C46 | 1.427 (6) |
C12—H12A | 0.9300 | C46—C47 | 1.367 (5) |
C13—C14 | 1.356 (7) | C46—H46A | 0.9300 |
C13—H13A | 0.9300 | C47—C48 | 1.484 (6) |
C14—C15 | 1.403 (7) | C48—C49 | 1.360 (6) |
C14—H14A | 0.9300 | C48—C53 | 1.390 (6) |
C15—H15A | 0.9300 | C49—C50 | 1.364 (7) |
C16—H16A | 0.9600 | C49—H49A | 0.9300 |
C16—H16B | 0.9600 | C50—C51 | 1.355 (7) |
C16—H16C | 0.9600 | C50—H50A | 0.9301 |
C17—C18 | 1.373 (6) | C51—C52 | 1.364 (8) |
C17—C27 | 1.508 (6) | C51—H51A | 0.9300 |
C18—C19 | 1.427 (6) | C52—C53 | 1.393 (7) |
C19—C20 | 1.351 (6) | C52—H52A | 0.9300 |
C19—H19A | 0.9300 | C53—H53A | 0.9300 |
C20—C21 | 1.463 (6) | C54—H54A | 0.9600 |
C21—C22 | 1.376 (6) | C54—H54B | 0.9600 |
C21—C26 | 1.379 (6) | C54—H54C | 0.9600 |
C9—S1—C6 | 93.65 (19) | H27A—C27—H27C | 109.5 |
C17—S2—C20 | 93.1 (2) | H27B—C27—H27C | 109.5 |
C33—S3—C36 | 93.1 (2) | C29—C28—C34 | 130.1 (4) |
C44—S4—C47 | 94.1 (2) | C29—C28—C32 | 110.6 (4) |
C2—C1—C7 | 129.9 (4) | C34—C28—C32 | 119.3 (4) |
C2—C1—C5 | 110.8 (4) | C28—C29—C45 | 130.5 (4) |
C7—C1—C5 | 119.3 (4) | C28—C29—C30 | 111.1 (4) |
C1—C2—C18 | 129.2 (4) | C45—C29—C30 | 118.3 (4) |
C1—C2—C3 | 110.0 (4) | F10—C30—F9 | 105.6 (4) |
C18—C2—C3 | 120.7 (4) | F10—C30—C29 | 112.5 (4) |
F1—C3—F2 | 106.4 (4) | F9—C30—C29 | 113.5 (4) |
F1—C3—C4 | 112.2 (4) | F10—C30—C31 | 109.9 (4) |
F2—C3—C4 | 108.7 (4) | F9—C30—C31 | 111.1 (5) |
F1—C3—C2 | 113.9 (4) | C29—C30—C31 | 104.3 (4) |
F2—C3—C2 | 110.7 (4) | F12—C31—F11 | 104.0 (5) |
C4—C3—C2 | 105.0 (4) | F12—C31—C32 | 117.4 (5) |
F4—C4—F3 | 107.4 (4) | F11—C31—C32 | 106.6 (4) |
F4—C4—C3 | 114.5 (4) | F12—C31—C30 | 116.2 (5) |
F3—C4—C3 | 109.1 (4) | F11—C31—C30 | 105.2 (5) |
F4—C4—C5 | 113.2 (4) | C32—C31—C30 | 106.3 (4) |
F3—C4—C5 | 108.2 (4) | F13—C32—F14 | 107.1 (4) |
C3—C4—C5 | 104.3 (4) | F13—C32—C31 | 108.0 (5) |
F5—C5—F6 | 105.9 (4) | F14—C32—C31 | 111.2 (4) |
F5—C5—C1 | 112.8 (4) | F13—C32—C28 | 111.6 (4) |
F6—C5—C1 | 113.2 (3) | F14—C32—C28 | 114.2 (4) |
F5—C5—C4 | 109.4 (4) | C31—C32—C28 | 104.6 (4) |
F6—C5—C4 | 111.5 (4) | C34—C33—C43 | 129.6 (4) |
C1—C5—C4 | 104.1 (4) | C34—C33—S3 | 110.2 (3) |
C7—C6—C16 | 131.3 (4) | C43—C33—S3 | 120.0 (3) |
C7—C6—S1 | 109.6 (3) | C33—C34—C35 | 112.2 (4) |
C16—C6—S1 | 119.1 (3) | C33—C34—C28 | 123.3 (4) |
C6—C7—C8 | 113.1 (3) | C35—C34—C28 | 124.4 (4) |
C6—C7—C1 | 124.6 (4) | C36—C35—C34 | 114.9 (4) |
C8—C7—C1 | 122.3 (3) | C36—C35—H35A | 122.6 |
C9—C8—C7 | 113.8 (4) | C34—C35—H35A | 122.6 |
C9—C8—H8A | 123.1 | C35—C36—C37 | 129.1 (4) |
C7—C8—H8A | 123.1 | C35—C36—S3 | 109.5 (3) |
C8—C9—C10 | 128.6 (4) | C37—C36—S3 | 121.3 (4) |
C8—C9—S1 | 109.8 (3) | C38—C37—C42 | 117.4 (5) |
C10—C9—S1 | 121.7 (3) | C38—C37—C36 | 120.2 (5) |
C11—C10—C15 | 118.1 (4) | C42—C37—C36 | 122.4 (5) |
C11—C10—C9 | 120.9 (4) | C39—C38—C37 | 118.9 (5) |
C15—C10—C9 | 121.1 (4) | C39—C38—H38A | 120.6 |
C12—C11—C10 | 119.7 (5) | C37—C38—H38A | 120.6 |
C12—C11—H11A | 120.2 | F15—C39—C40 | 114.9 (7) |
C10—C11—H11A | 120.2 | F15—C39—C38 | 120.7 (7) |
F7—C12—C13 | 117.5 (6) | C40—C39—C38 | 124.3 (6) |
F7—C12—C11 | 119.4 (6) | C40—C39—H39A | 118.1 |
C13—C12—C11 | 122.9 (5) | C38—C39—H39A | 117.6 |
C13—C12—H12A | 118.4 | C39—C40—C41 | 118.3 (6) |
C11—C12—H12A | 118.7 | C39—C40—H40A | 120.9 |
C14—C13—C12 | 118.3 (5) | C41—C40—H40A | 120.9 |
C14—C13—H13A | 120.9 | C40—C41—C42 | 119.1 (6) |
C12—C13—H13A | 120.9 | C40—C41—H41A | 120.5 |
C13—C14—C15 | 121.0 (5) | C42—C41—H41A | 120.5 |
C13—C14—H14A | 119.5 | C37—C42—C41 | 122.0 (5) |
C15—C14—H14A | 119.5 | C37—C42—H42A | 119.0 |
C10—C15—C14 | 120.1 (5) | C41—C42—H42A | 119.0 |
C10—C15—H15A | 120.0 | C33—C43—H43A | 109.5 |
C14—C15—H15A | 120.0 | C33—C43—H43B | 109.5 |
C6—C16—H16A | 109.5 | H43A—C43—H43B | 109.5 |
C6—C16—H16B | 109.5 | C33—C43—H43C | 109.5 |
H16A—C16—H16B | 109.5 | H43A—C43—H43C | 109.5 |
C6—C16—H16C | 109.5 | H43B—C43—H43C | 109.5 |
H16A—C16—H16C | 109.5 | C45—C44—C54 | 130.3 (4) |
H16B—C16—H16C | 109.5 | C45—C44—S4 | 109.8 (3) |
C18—C17—C27 | 128.5 (4) | C54—C44—S4 | 119.8 (3) |
C18—C17—S2 | 110.6 (3) | C44—C45—C46 | 112.9 (4) |
C27—C17—S2 | 120.8 (3) | C44—C45—C29 | 124.2 (4) |
C17—C18—C19 | 112.0 (4) | C46—C45—C29 | 122.8 (4) |
C17—C18—C2 | 124.4 (4) | C47—C46—C45 | 113.9 (4) |
C19—C18—C2 | 123.6 (4) | C47—C46—H46A | 123.0 |
C20—C19—C18 | 114.4 (4) | C45—C46—H46A | 123.0 |
C20—C19—H19A | 122.8 | C46—C47—C48 | 129.3 (4) |
C18—C19—H19A | 122.8 | C46—C47—S4 | 109.2 (3) |
C19—C20—C21 | 128.8 (4) | C48—C47—S4 | 121.5 (3) |
C19—C20—S2 | 109.8 (3) | C49—C48—C53 | 120.4 (5) |
C21—C20—S2 | 121.4 (3) | C49—C48—C47 | 120.4 (4) |
C22—C21—C26 | 117.5 (4) | C53—C48—C47 | 119.2 (5) |
C22—C21—C20 | 120.9 (4) | C48—C49—C50 | 117.2 (5) |
C26—C21—C20 | 121.6 (4) | C48—C49—H49A | 121.4 |
C23—C22—C21 | 119.2 (5) | C50—C49—H49A | 121.4 |
C23—C22—H22A | 120.4 | F16—C50—C51 | 114.1 (7) |
C21—C22—H22A | 120.4 | F16—C50—C49 | 120.2 (6) |
F8—C23—C24 | 111.5 (6) | C51—C50—C49 | 125.7 (6) |
F8—C23—C22 | 123.9 (7) | C51—C50—H50A | 116.9 |
C24—C23—C22 | 124.6 (5) | C49—C50—H50A | 117.5 |
C24—C23—H23A | 118.5 | C50—C51—C52 | 116.3 (6) |
C22—C23—H23A | 116.9 | C50—C51—H51A | 121.8 |
C23—C24—C25 | 117.7 (6) | C52—C51—H51A | 121.8 |
C23—C24—H24A | 121.1 | C51—C52—C53 | 121.2 (5) |
C25—C24—H24A | 121.1 | C51—C52—H52A | 119.4 |
C24—C25—C26 | 120.1 (6) | C53—C52—H52A | 119.4 |
C24—C25—H25A | 120.0 | C48—C53—C52 | 119.2 (5) |
C26—C25—H25A | 120.0 | C48—C53—H53A | 120.4 |
C21—C26—C25 | 121.0 (5) | C52—C53—H53A | 120.4 |
C21—C26—H26A | 119.5 | C44—C54—H54A | 109.5 |
C25—C26—H26A | 119.5 | C44—C54—H54B | 109.5 |
C17—C27—H27A | 109.5 | H54A—C54—H54B | 109.5 |
C17—C27—H27B | 109.5 | C44—C54—H54C | 109.5 |
H27A—C27—H27B | 109.5 | H54A—C54—H54C | 109.5 |
C17—C27—H27C | 109.5 | H54B—C54—H54C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | C27H17F7S2 |
Mr | 538.53 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 18.945 (2), 11.7925 (19), 21.876 (4) |
β (°) | 96.587 (12) |
V (Å3) | 4855.1 (13) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.6 × 0.5 × 0.2 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10367, 8526, 5532 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.143, 1.01 |
No. of reflections | 8526 |
No. of parameters | 661 |
No. of restraints | 4 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.88, −0.40 |
Computer programs: XSCANS (Bruker, 1997), XSCANS, SHELXTL (Bruker, 1997), SHELXTL.
S1—C9 | 1.718 (4) | C1—C7 | 1.471 (5) |
S1—C6 | 1.721 (4) | C1—C5 | 1.496 (6) |
S2—C17 | 1.715 (5) | C2—C18 | 1.468 (6) |
S2—C20 | 1.728 (4) | C2—C3 | 1.511 (6) |
S3—C33 | 1.718 (5) | C3—C4 | 1.501 (7) |
S3—C36 | 1.731 (4) | C4—C5 | 1.531 (6) |
S4—C44 | 1.713 (4) | C28—C29 | 1.338 (5) |
S4—C47 | 1.727 (5) | C28—C34 | 1.474 (6) |
F7—C12 | 1.328 (5) | C28—C32 | 1.516 (6) |
F8—C23 | 1.319 (4) | C29—C45 | 1.475 (5) |
F15—C39 | 1.317 (5) | C29—C30 | 1.505 (6) |
F16—C50 | 1.316 (5) | C30—C31 | 1.514 (7) |
C1—C2 | 1.346 (5) | C31—C32 | 1.505 (7) |
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Of all the photochromic compounds, diarylethenes are the most promising candidates because of their good thermally stabilty, high sensitivity, fast response and high fatigue resistance (Irie, 2000; Tian & Yang, 2004). For further background information see Pu, Liu, Chen & Wang (2005) and Pu, Fan et al. (2005). A large number of diarylethene crystal structures and their properties have been reported (Kobatake & Irie, 2004), including some structures we have determined (Pu et al., 2003, 2004; Pu, Fan et al., 2005; Pu, Xu et al., 2005; Pu, Xiao et al., 2005; Pu, Yang, Wang & Xu, 2005; Pu, Liu & Yan, 2005 ??; Pu, Yang & Yan, 2005). Many diarylethenes incorporating thienyl groups and a para-substituted benzene ring are known (Irie, 2000; Tian & Yang, 2004; Matsuda & Irie, 2004; Morimoto & Irie, 2005) but diarylethenes with a meta-substituted benzene ring are rare (Yamamoto et al., 2003; Pu, Liu & Yan, 2005 ??). In order to investigate the photochemical properties of a diarylethene with a meta-substituted benzene ring, we have synthesized the title compound, (Ia), and its structure is reported here.
The two independent molecules of (Ia) are shown in Figs. 1 and 2, and selected geometric parameters are given in Table 1. Both molecules show a photoactive antiparallel conformation i.e. the molecules have molecular C2 symmetry. In the hexafluorocyclopentene rings of the two molecules, the C1═C2 and C28═C29 bonds are clearly double bonds, while the other bonds in the ring are single. The thiophene rings are linked by the C1═C2 and C28═C29 double bonds; the two methyl groups are located on different sides of the double bond and thus are trans with respect to the double bond. Such a conformation is crucial for the compund to exhibit photochromic and photoinduced properties (Woodward & Hoffmann, 1970).
In one independent molecule of (Ia), the dihedral angles between the least-squares plane of atoms of the central cyclopent-1-ene ring and those of the thiophene rings are 49.6 (2)° for S1/C6–C9 and 47.7 (2)° for S2/C17–C20, and those between the thiophene rings and the adjacent benzene rings are 13.7 (1)° for C10–C15 and 20.9 (2)° for C21–C26. The distance between the two reactive C atoms (C6···C17) is 3.553 (6) Å and this distance indicates that the crystal can undergo photochromism in the crystalline phase (Ramamurthy & Venkatesan, 1987; Shibata et al., 2002; Kobatake et al., 2004). Similarly for the other independent molecule, the dihedral angles between the central cyclopent-1-ene ring and the thiophene rings are 45.1 (2)° for S3/C33–C36 and 49.7 (2)° for S4/C44–C47, and those between thiophene rings and the adjacent benzene rings are 28.2 (1)° for C37–C42 and 10.1 (1)° for C48–C53. This conformation leads to a C33···C44 separation of 3.624 (6) Å, which again is less than 4.2 Å, allowing photchromism.
When the title compound was irradiated with 313 nm light, the colorless single crystals turned to blue rapidly, and the blue color remained stable in the dark. When the blue crystals were dissolved in hexane, the solution also remained blue. The maximum absorption of this solution was observed at a wavelength of 577 nm, consistent with the presence of the closed-ring isomer, (Ib). This results suggest that the title compound undergoes a photochromic reaction to produce the closed-ring molecule of (Ib) in the single-crystal phase. We have not, so far, been able to determine the crystal structure of (Ib). Furthermore, upon irradiation with wavelengths greater than 450 nm, the blue crystal changes back to colorless, and the absorption spectrum of a hexane solution of the colorless crystals was the same as that of a solution of the open-ring form, (Ia), with the maximum absorption at 276 nm.