1-(2-Chloro­phen­yl)-2-(2-methyl-5-phenyl-3-thien­yl)-3,3,4,4,5,5-hexa­fluoro­cyclo­pent-1-ene: a new photochromic diaryl­ethene

Gong, S.; Fan, C.; Liu, W.; Liu, G.

doi:10.1107/S1600536808013330

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1028

doi:10.1107/S1600536808013330

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1-(2-Chlorophenyl)-2-(2-methyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluorocyclopent-1-ene: a new photochromic diarylethene

Shanshan Gong,^a Congbin Fan,^a ^* Weijun Liu ^a and Gang Liu ^a

^aJiangxi Key Laboratory of Organic Chemistry, Jiangxi Science & Technology Normal University, Nanchang 330013, People's Republic of China
^*Correspondence e-mail: congbinfan@yahoo.com.cn

(Received 21 April 2008; accepted 6 May 2008; online 10 May 2008)

The title compound, C₂₂H₁₃ClF₆S, is a hybrid diarylethene derivative with one 3-thienyl substituent, and a Cl-substituted six-membered aryl unit bonded to the double bond of a hexafluorocyclopentene ring. In the crystal structure, the molecule adopts a photo-active antiparallel 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 cyclopentene plane and those of the adjacent thiophene and chlorophenyl 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_r = 458.83
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.036
wR(F²) = 0.100
S = 1.03
3741 reflections
326 parameters
66 restraints
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −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.

Supporting information

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

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

checkCIF report

Comment top

Organic photochromic materials have attracted much attention, because of their potential application to optical memory media and optical switches. (Dürr & Bouas-Laurent, 1990; Tian & Yang, 2004). Among all organic photochromic compounds, diarylethenes with heterocyclic aryl groups are the most promising candidates for those application, mainly due to the excellent thermal stability of the respective isomers, notable fatigue resistance, and high reactivity in the solid state (Irie, 2000). The backbone of all photochromic perfluorocyclopentene systems are composed of five-membered heterocyclic rings (Zheng et al., 2007) or the combination of a five-membered aryl ring and a vinyl group. we decided to investigate if replacing the five-membered heterocyclic ring in the diarylethene with a six-membered aryl ring would induce novel characteristics. This paper presents the synthesis and crystal structure of the title compound a six-membered aryl ring group bearing a Cl atom.

The thienyl and the 2-chlorophenyl rings are in cis-position with respect to the C7=C11 double bond (Fig. 1). They are located on each side of the fluorocyclopentene ring, as reflected by the torsion angles C1—C6—C7—C11 [-60.52 ( 0.31)°] and C7—C11—C12—C13 [45.95 (23)°]. The dihedral angles between the least-square cyclopentene plane and those of the adjacent thiophene and chloro-phenyl rings are 49.39 (8)° and 59.88 (8)° respectively.

Such conformation is crucial for the compound to exhibit photochromic and photoinduced properties (Woodward & Hoffmann, 1970). The intramolecular distance between the two reactive C atoms (C1—C13) is 3.848 (3) Å. This distance indicates that the crystal can be expected to undergo photochromism to form compound (Ib)( Fig. 2), because photochromic reactivity usually appears when distance between the reactive C atoms is less than 4.2 Å (Ramamurthy & Venkatesan, 1987; Kobatake et al., 2004). Crystal of (Ib) shows photochromism in accordance with the expected ring closure to form (Ib). Upon irradiation with 313 nm light, the colorless single-crystal of (Ia) turned red quickly. When the red crystal was dissolved in hexane, the solution also showed a red color, with an absorption maximum at 523 nm, consistent with the presence of the closed-ring isomer (Ib). Upon irradiation with visible light with wavelength greater than 510 nm, the red crystal can return to its initial colorless state, and the absorption spectrum of the hexane solution containing the colorless crystal is the same as that of solution of the open-ring form, (Ia), with the absorption maximum at 273 nm.

Related literature top

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 top

Compound (Ia) was prepared from (2-methyl-5-phenyl-3-thienyl)- 3,3,4,4,5,5-hexafluorocyclopent-1-ene (1.83 g, 5.00 mmol) (Peters et al., 2003) and 2-bromo-chlorobenzene (0.96 g, 5.00 mmol). To a stirred solution of compound 2-bromo-chlorobenzene (0.96 g, 5.00 mmol) in THF (80 ml) was added dropwise a 2.5 mol/L n-BuLi in hexane (2.0 ml) at 195 K under a nitrogen atmosphere (Fig. 3). Stirring was continued for 30 min, (2-methyl-5-phenyl-3-thienyl)- 3,3,4,4,5,5-hexafluorocyclopent-1-ene (1.83 g, 5.00 mmol) was slowly added to the reaction mixture, and the mixture was stirred for 2.0 h at 195 K. The reaction was stopped by the addition of water. Through a series of operations, [1-(2-methyl-5-phenyl-3-thienyl), 2-(2-chlorophenyl)]- 3,3,4,4,5,5-hexafluorocyclopent-1-ene (1.32 g, 2.88 mmol) was obtained in 57.5% yield by column chromatography on SiO₂ using hexane as the eluent. Finally the colorless crystals were obtained by slow vapour diffusion of chloroform and hexane(1:2). The title compound was characterized by melting point, elemental analysis and NMR(m.p.361.1–361.7 K). ¹HNMR (400 MHz, CDCl₃, TMS): δ 2.08 (s, 3H, –CH₃), 7.14 (s, 1H, thiophene-H), 7.27, 7.29 (d, 2H, J = 8.0 Hz, benzene-H), 7.33–7.38 (m, 4H, benzene-H), 7.40 (m, 1H, benzene-H), 7.46, 7.48 (d, 2H, J = 8.0 Hz, benzene-H); ¹³C NMR (100 MHz, CDCl₃): δ 14.55, 123.10, 125.11, 125.59, 126.98, 127.75, 128.91, 130.43, 130.55, 131.25, 133.45, 133.70, 140.70, 141.73; IR (KBr, cm^-1): 754, 853, 987, 1053, 1132, 1192, 1272, 1330, 1441, 1473, 1502, 1598, 1674, 2925, 3064; Anal. Calcd. for C₂₄H₁₉ClF₆S(%): C, 57.59, H, 2.86, Found: C, 57.28, H, 2.59.

Computing details top

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: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular view of title compound with the atom-labelling scheme. Ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Only the major component of the disordered F atoms are shown for clarity.
	Fig. 2. Photochromic interconvertion of the title compound.
	Fig. 3. Synthesis of the title compound.

1-(2-Chlorophenyl)-2-(2-methyl-5-phenyl-3-thienyl)-3,3,4,4,5,5- hexafluorocyclopent-1-ene top

Crystal data top

C₂₂H₁₃ClF₆S	Z = 2
M_r = 458.83	F(000) = 464
Triclinic, P1	D_x = 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 = 2.4–26.1°
α = 85.265 (1)°	µ = 0.35 mm⁻¹
β = 76.935 (1)°	T = 291 K
γ = 76.324 (1)°	Block, colorless
V = 1011.8 (2) Å³	0.46 × 0.37 × 0.27 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3741 independent reflections
Radiation source: fine-focus sealed tube	3039 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.835, T_max = 0.910	k = −12→12
7557 measured reflections	l = −14→14

Refinement top

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0465P)² + 0.2265P] where P = (F_o² + 2F_c²)/3
3741 reflections	(Δ/σ)_max = 0.011
326 parameters	Δρ_max = 0.15 e Å⁻³
66 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₂₂H₁₃ClF₆S	γ = 76.324 (1)°
M_r = 458.83	V = 1011.8 (2) Å³
Triclinic, P1	Z = 2
a = 8.8064 (10) Å	Mo Kα radiation
b = 10.4185 (12) Å	µ = 0.35 mm⁻¹
c = 11.6563 (13) Å	T = 291 K
α = 85.265 (1)°	0.46 × 0.37 × 0.27 mm
β = 76.935 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3741 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3039 reflections with I > 2σ(I)
T_min = 0.835, T_max = 0.910	R_int = 0.013
7557 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	66 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.03	Δρ_max = 0.15 e Å⁻³
3741 reflections	Δρ_min = −0.17 e Å⁻³
326 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Experimental details

Crystal data
Chemical formula	C₂₂H₁₃ClF₆S
M_r	458.83
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	8.8064 (10), 10.4185 (12), 11.6563 (13)
α, β, γ (°)	85.265 (1), 76.935 (1), 76.324 (1)
V (Å³)	1011.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.46 × 0.37 × 0.27

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.835, 0.910
No. of measured, independent and observed [I > 2σ(I)] reflections	7557, 3741, 3039
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.100, 1.03
No. of reflections	3741
No. of parameters	326
No. of restraints	66
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.17

Computer programs: SMART (Bruker,1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997).

Acknowledgements

This work was supported by the Natural Science Foundation of Jiangxi, China (0620012) and the Science Fund of the Education Office of Jiangxi, China ([2007]279).

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