1-(2-Chloro-phen-yl)-2-(2-methyl-5-phenyl-3-thien-yl)-3,3,4,4,5,5-hexa-fluoro-cyclo-pent-1-ene: a new photochromic diaryl-ethene.

The title compound, C(22)H(13)ClF(6)S, is a hybrid diaryl-ethene derivative with one 3-thienyl substituent, and a Cl-substituted six-membered aryl unit bonded to the double bond of a hexa-fluoro-cyclo-pentene ring. In the crystal structure, the mol-ecule adopts a photo-active anti-parallel conformation that can undergo effective photocyclization reactions. The distance between the two reactive C atoms is 3.848 (3) Å. The dihedral angles between the least-squares cyclo-pentene plane and those of the adjacent thio-phene and chloro-phenyl rings are 49.39 (8) and 59.88 (8)°, respectively. The F atoms are disordered over two positions, with site occupancy factors of 0.6 and 0.4.

Related literature

For related literature, see: Dürr & Bouas-Laurent (1990 ▶); Irie (2000 ▶); Kobatake & Irie (2004 ▶); Ramamurthy & Venkatesan (1987 ▶); Tian & Yang (2004 ▶); Woodward & Hoffmann (1970 ▶); Zheng et al. (2007 ▶); Peters et al. (2003 ▶).

Experimental

Crystal data

C22H13ClF6S

M = 458.83

Triclinic,

a = 8.8064 (10) Å

b = 10.4185 (12) Å

c = 11.6563 (13) Å

α = 85.265 (1)°

β = 76.935 (1)°

γ = 76.324 (1)°

V = 1011.8 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.35 mm−1

T = 291 (2) K

0.46 × 0.37 × 0.27 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.835, T max = 0.910

7557 measured reflections

3741 independent reflections

3039 reflections with I > 2σ(I)

R int = 0.013

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.100

S = 1.03

3741 reflections

326 parameters

66 restraints

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.17 e Å−3

Data collection: SMART (Bruker,1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013330/dn2342sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808013330/dn2342Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C22H13ClF6S	Z = 2
Mr = 458.83	F000 = 464
Triclinic, P1	Dx = 1.506 Mg m−3
Hall symbol: -P 1	Melting point: 361 K
a = 8.8064 (10) Å	Mo Kα radiation λ = 0.71073 Å
b = 10.4185 (12) Å	Cell parameters from 3385 reflections
c = 11.6563 (13) Å	θ = 2.4–26.1º
α = 85.265 (1)º	µ = 0.35 mm−1
β = 76.935 (1)º	T = 291 (2) K
γ = 76.324 (1)º	Block, colorless
V = 1011.8 (2) Å3	0.46 × 0.37 × 0.27 mm

Bruker SMART CCD area-detector diffractometer	3741 independent reflections
Radiation source: fine-focus sealed tube	3039 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.013
T = 291(2) K	θmax = 25.5º
φ and ω scans	θmin = 2.4º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.835, Tmax = 0.910	k = −12→12
7557 measured reflections	l = −14→14

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036	H-atom parameters constrained
wR(F2) = 0.100	w = 1/[σ2(Fo2) + (0.0465P)2 + 0.2265P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.011
3741 reflections	Δρmax = 0.15 e Å−3
326 parameters	Δρmin = −0.17 e Å−3
66 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)
Cl1	1.14956 (8)	0.27691 (8)	0.88868 (6)	0.0850 (2)
S1	1.13849 (8)	0.12027 (6)	0.49405 (5)	0.06425 (19)
C1	1.0219 (3)	0.4151 (2)	0.84413 (19)	0.0613 (6)
C2	1.0746 (4)	0.5329 (3)	0.8166 (2)	0.0871 (9)
H2	1.1790	0.5350	0.8185	0.105*
C3	0.9723 (5)	0.6447 (3)	0.7868 (3)	0.0994 (11)
H3	1.0086	0.7222	0.7673	0.119*
C4	0.8182 (5)	0.6444 (3)	0.7854 (3)	0.0918 (9)
H4	0.7492	0.7217	0.7667	0.110*
C5	0.7651 (3)	0.5291 (2)	0.8119 (2)	0.0710 (6)
H5	0.6596	0.5295	0.8113	0.085*
C6	0.8666 (3)	0.4114 (2)	0.83974 (17)	0.0538 (5)
C7	0.8062 (2)	0.28882 (19)	0.86731 (17)	0.0508 (5)
C11	0.8598 (2)	0.17209 (19)	0.81392 (17)	0.0491 (5)
C12	0.9819 (3)	0.13402 (19)	0.70679 (17)	0.0497 (5)
C13	0.9865 (3)	0.2030 (2)	0.60054 (17)	0.0543 (5)
C14	1.1993 (3)	−0.0064 (2)	0.59067 (18)	0.0556 (5)
C15	1.1036 (3)	0.0151 (2)	0.69936 (18)	0.0535 (5)
H15	1.1161	−0.0426	0.7635	0.064*
C16	0.8792 (3)	0.3280 (2)	0.5679 (2)	0.0715 (7)
H16A	0.7735	0.3348	0.6155	0.107*
H16B	0.8756	0.3272	0.4863	0.107*
H16C	0.9196	0.4022	0.5810	0.107*
C17	1.3338 (3)	−0.1188 (2)	0.5501 (2)	0.0620 (6)
C18	1.4225 (4)	−0.1226 (3)	0.4357 (3)	0.0872 (8)
H18	1.4001	−0.0518	0.3835	0.105*
C19	1.5454 (4)	−0.2320 (4)	0.3981 (3)	0.1079 (11)
H19	1.6042	−0.2332	0.3209	0.130*
C20	1.5801 (4)	−0.3361 (4)	0.4721 (4)	0.1062 (11)
H20	1.6610	−0.4093	0.4457	0.127*
C21	1.4962 (4)	−0.3333 (3)	0.5850 (3)	0.1009 (10)
H21	1.5212	−0.4042	0.6366	0.121*
C22	1.3741 (3)	−0.2260 (3)	0.6245 (3)	0.0823 (8)
H22	1.3180	−0.2258	0.7023	0.099*
C8	0.6691 (4)	0.2848 (3)	0.9689 (2)	0.0766 (7)
F81	0.5227 (6)	0.3659 (5)	0.9349 (4)	0.0822 (12)	0.60
F82	0.6655 (6)	0.3429 (5)	1.0655 (3)	0.0934 (13)	0.60
F81A	0.5616 (11)	0.3714 (7)	0.9937 (8)	0.129 (4)	0.40
F82A	0.7574 (8)	0.2683 (6)	1.0735 (4)	0.104 (2)	0.40
C9	0.6459 (3)	0.1441 (2)	0.9782 (2)	0.0668 (6)
F91	0.6251 (6)	0.0807 (5)	1.0781 (4)	0.1038 (17)	0.60
F92	0.5129 (5)	0.1513 (4)	0.9324 (4)	0.1069 (12)	0.60
F91A	0.7063 (9)	0.1016 (7)	1.0795 (5)	0.101 (2)	0.40
F92A	0.4934 (7)	0.1351 (6)	1.0116 (6)	0.098 (2)	0.40
C10	0.7729 (3)	0.0714 (2)	0.8807 (2)	0.0700 (7)
F101	0.7425 (5)	−0.0114 (4)	0.8142 (4)	0.0895 (11)	0.60
F102	0.8871 (6)	−0.0155 (4)	0.9402 (5)	0.0906 (13)	0.60
F11A	0.6530 (8)	0.0595 (7)	0.8101 (5)	0.1013 (18)	0.40
F12A	0.8365 (11)	−0.0405 (6)	0.9036 (7)	0.105 (3)	0.40

	U11	U22	U33	U12	U13	U23
Cl1	0.0693 (4)	0.1060 (5)	0.0829 (5)	−0.0199 (4)	−0.0218 (3)	−0.0053 (4)
S1	0.0813 (4)	0.0650 (4)	0.0454 (3)	−0.0197 (3)	−0.0090 (3)	0.0011 (2)
C1	0.0701 (14)	0.0671 (14)	0.0502 (12)	−0.0294 (11)	−0.0016 (10)	−0.0122 (10)
C2	0.100 (2)	0.095 (2)	0.0793 (18)	−0.0620 (18)	0.0027 (15)	−0.0207 (15)
C3	0.147 (3)	0.0639 (18)	0.091 (2)	−0.058 (2)	0.009 (2)	−0.0118 (15)
C4	0.129 (3)	0.0499 (14)	0.088 (2)	−0.0247 (16)	−0.0012 (18)	−0.0013 (13)
C5	0.0841 (17)	0.0511 (13)	0.0742 (15)	−0.0175 (12)	−0.0073 (13)	−0.0013 (11)
C6	0.0685 (13)	0.0472 (11)	0.0465 (11)	−0.0224 (10)	−0.0023 (9)	−0.0061 (8)
C7	0.0599 (12)	0.0462 (11)	0.0484 (11)	−0.0188 (9)	−0.0088 (9)	−0.0016 (8)
C11	0.0628 (12)	0.0438 (10)	0.0450 (10)	−0.0169 (9)	−0.0160 (9)	0.0020 (8)
C12	0.0646 (12)	0.0444 (10)	0.0448 (10)	−0.0184 (9)	−0.0148 (9)	−0.0015 (8)
C13	0.0725 (14)	0.0486 (11)	0.0466 (11)	−0.0207 (10)	−0.0160 (10)	0.0007 (9)
C14	0.0656 (13)	0.0533 (12)	0.0525 (12)	−0.0199 (10)	−0.0143 (10)	−0.0051 (9)
C15	0.0675 (13)	0.0471 (11)	0.0485 (11)	−0.0152 (9)	−0.0161 (10)	0.0002 (8)
C16	0.0987 (19)	0.0595 (13)	0.0574 (13)	−0.0132 (13)	−0.0271 (13)	0.0076 (10)
C17	0.0607 (13)	0.0640 (14)	0.0649 (14)	−0.0175 (11)	−0.0122 (11)	−0.0163 (11)
C18	0.0876 (19)	0.0861 (19)	0.0776 (18)	−0.0161 (15)	0.0043 (15)	−0.0154 (14)
C19	0.086 (2)	0.120 (3)	0.103 (2)	−0.013 (2)	0.0134 (18)	−0.040 (2)
C20	0.081 (2)	0.097 (2)	0.135 (3)	0.0066 (18)	−0.025 (2)	−0.041 (2)
C21	0.099 (2)	0.088 (2)	0.108 (3)	0.0151 (17)	−0.038 (2)	−0.0191 (18)
C22	0.0875 (18)	0.0765 (17)	0.0766 (17)	0.0023 (14)	−0.0240 (14)	−0.0102 (14)
C8	0.0927 (19)	0.0690 (16)	0.0682 (16)	−0.0414 (15)	0.0130 (14)	−0.0194 (13)
F81	0.0592 (15)	0.061 (2)	0.114 (4)	−0.0057 (13)	−0.002 (2)	−0.001 (2)
F82	0.111 (3)	0.117 (3)	0.0605 (18)	−0.061 (3)	0.013 (2)	−0.035 (2)
F81A	0.133 (9)	0.061 (3)	0.146 (9)	−0.027 (5)	0.081 (6)	−0.034 (6)
F82A	0.156 (6)	0.113 (4)	0.055 (2)	−0.086 (4)	0.019 (3)	−0.024 (3)
C9	0.0682 (15)	0.0615 (14)	0.0710 (15)	−0.0266 (12)	−0.0060 (12)	0.0075 (11)
F91	0.141 (4)	0.087 (2)	0.074 (2)	−0.055 (3)	0.025 (3)	0.0028 (16)
F92	0.070 (2)	0.098 (2)	0.159 (4)	−0.0215 (17)	−0.029 (3)	−0.014 (3)
F91A	0.165 (7)	0.084 (4)	0.045 (2)	−0.011 (4)	−0.028 (4)	0.014 (2)
F92A	0.076 (3)	0.071 (3)	0.140 (5)	−0.039 (2)	0.017 (4)	−0.007 (4)
C10	0.106 (2)	0.0546 (14)	0.0540 (13)	−0.0381 (13)	−0.0062 (12)	−0.0007 (10)
F101	0.131 (3)	0.069 (2)	0.081 (2)	−0.0582 (19)	−0.003 (2)	−0.0177 (19)
F102	0.102 (3)	0.063 (3)	0.089 (3)	−0.009 (2)	−0.0082 (19)	0.033 (2)
F11A	0.138 (5)	0.130 (5)	0.067 (3)	−0.094 (4)	−0.015 (3)	−0.013 (3)
F12A	0.141 (7)	0.033 (2)	0.109 (7)	−0.022 (3)	0.041 (5)	−0.003 (3)

Cl1—C1	1.727 (3)	C16—H16C	0.9600
S1—C13	1.719 (2)	C17—C18	1.383 (4)
S1—C14	1.729 (2)	C17—C22	1.384 (4)
C1—C6	1.390 (3)	C18—C19	1.396 (4)
C1—C2	1.400 (3)	C18—H18	0.9300
C2—C3	1.366 (5)	C19—C20	1.350 (5)
C2—H2	0.9300	C19—H19	0.9300
C3—C4	1.361 (5)	C20—C21	1.356 (5)
C3—H3	0.9300	C20—H20	0.9300
C4—C5	1.378 (4)	C21—C22	1.382 (4)
C4—H4	0.9300	C21—H21	0.9300
C5—C6	1.398 (3)	C22—H22	0.9300
C5—H5	0.9300	C8—F81A	1.144 (8)
C6—C7	1.481 (3)	C8—F82	1.313 (4)
C7—C11	1.345 (3)	C8—F81	1.481 (6)
C7—C8	1.493 (3)	C8—C9	1.520 (3)
C11—C12	1.465 (3)	C8—F82A	1.566 (7)
C11—C10	1.506 (3)	C9—F91	1.288 (5)
C12—C13	1.377 (3)	C9—F92A	1.334 (6)
C12—C15	1.427 (3)	C9—F92	1.378 (4)
C13—C16	1.494 (3)	C9—F91A	1.400 (6)
C14—C15	1.357 (3)	C9—C10	1.511 (3)
C14—C17	1.477 (3)	C10—F12A	1.205 (7)
C15—H15	0.9300	C10—F101	1.315 (4)
C16—H16A	0.9600	C10—F102	1.446 (6)
C16—H16B	0.9600	C10—F11A	1.510 (6)
C13—S1—C14	93.38 (10)	C19—C20—H20	120.3
C6—C1—C2	120.2 (3)	C21—C20—H20	120.3
C6—C1—Cl1	120.61 (17)	C20—C21—C22	120.7 (3)
C2—C1—Cl1	119.2 (2)	C20—C21—H21	119.7
C3—C2—C1	119.8 (3)	C22—C21—H21	119.7
C3—C2—H2	120.1	C21—C22—C17	121.2 (3)
C1—C2—H2	120.1	C21—C22—H22	119.4
C4—C3—C2	121.1 (3)	C17—C22—H22	119.4
C4—C3—H3	119.5	F81A—C8—F82	65.8 (5)
C2—C3—H3	119.5	F81A—C8—F81	34.6 (5)
C3—C4—C5	119.6 (3)	F82—C8—F81	100.4 (4)
C3—C4—H4	120.2	F81A—C8—C7	124.0 (5)
C5—C4—H4	120.2	F82—C8—C7	117.8 (3)
C4—C5—C6	121.4 (3)	F81—C8—C7	107.7 (3)
C4—C5—H5	119.3	F81A—C8—C9	120.2 (5)
C6—C5—H5	119.3	F82—C8—C9	118.8 (3)
C1—C6—C5	117.9 (2)	F81—C8—C9	104.6 (3)
C1—C6—C7	122.0 (2)	C7—C8—C9	106.1 (2)
C5—C6—C7	120.1 (2)	F81A—C8—F82A	104.8 (6)
C11—C7—C6	129.06 (19)	F82—C8—F82A	39.3 (2)
C11—C7—C8	111.42 (18)	F81—C8—F82A	139.3 (4)
C6—C7—C8	119.51 (18)	C7—C8—F82A	100.1 (3)
C7—C11—C12	130.30 (18)	C9—C8—F82A	95.4 (3)
C7—C11—C10	110.21 (19)	F91—C9—F92A	70.4 (4)
C12—C11—C10	119.49 (17)	F91—C9—F92	107.3 (3)
C13—C12—C15	112.38 (19)	F92A—C9—F92	39.2 (3)
C13—C12—C11	124.34 (19)	F91—C9—F91A	34.3 (3)
C15—C12—C11	123.14 (17)	F92A—C9—F91A	103.0 (5)
C12—C13—C16	130.1 (2)	F92—C9—F91A	141.3 (4)
C12—C13—S1	110.26 (16)	F91—C9—C10	115.5 (3)
C16—C13—S1	119.55 (16)	F92A—C9—C10	127.6 (4)
C15—C14—C17	129.2 (2)	F92—C9—C10	99.4 (3)
C15—C14—S1	109.74 (17)	F91A—C9—C10	103.5 (4)
C17—C14—S1	121.03 (17)	F91—C9—C8	121.5 (3)
C14—C15—C12	114.24 (19)	F92A—C9—C8	114.0 (3)
C14—C15—H15	122.9	F92—C9—C8	104.8 (3)
C12—C15—H15	122.9	F91A—C9—C8	98.6 (3)
C13—C16—H16A	109.5	C10—C9—C8	105.60 (19)
C13—C16—H16B	109.5	F12A—C10—F101	69.7 (4)
H16A—C16—H16B	109.5	F12A—C10—F102	32.6 (4)
C13—C16—H16C	109.5	F101—C10—F102	101.7 (3)
H16A—C16—H16C	109.5	F12A—C10—C11	124.5 (5)
H16B—C16—H16C	109.5	F101—C10—C11	114.7 (2)
C18—C17—C22	117.3 (2)	F102—C10—C11	105.3 (3)
C18—C17—C14	121.4 (2)	F12A—C10—F11A	105.4 (5)
C22—C17—C14	121.3 (2)	F101—C10—F11A	38.6 (2)
C17—C18—C19	120.5 (3)	F102—C10—F11A	138.0 (3)
C17—C18—H18	119.8	C11—C10—F11A	105.3 (3)
C19—C18—H18	119.8	F12A—C10—C9	116.6 (4)
C20—C19—C18	120.9 (3)	F101—C10—C9	122.1 (3)
C20—C19—H19	119.6	F102—C10—C9	104.9 (3)
C18—C19—H19	119.6	C11—C10—C9	106.42 (18)
C19—C20—C21	119.5 (3)	F11A—C10—C9	93.3 (3)