3-(4-{3,3,4,4,5,5-Hexafluoro-2-[5-(3-methoxy­phen­yl)-2-methyl-3-thien­yl]cyclo­pent-1-en­yl}-5-methyl-2-thien­yl)benzonitrile

Chen, A.; Le, Z.-G.; Liu, G.; Pu, S.-Z.; Fan, C.-B.

doi:10.1107/S1600536809034771

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2352

doi:10.1107/S1600536809034771

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3-(4-{3,3,4,4,5,5-Hexafluoro-2-[5-(3-methoxyphenyl)-2-methyl-3-thienyl]cyclopent-1-enyl}-5-methyl-2-thienyl)benzonitrile

An-yin Chen,^a,^b Zhang-Gao Le,^a Gang Liu,^b Shou-Zhi Pu ^b ^* and Cong-Bin Fan ^b

^aCollege of Biology, Chemistry and Material Science, East China Institute of Technology, Fuzhou 344000, People's Republic of China, and ^bJiangxi 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 17 July 2009; accepted 30 August 2009; online 5 September 2009)

The title compound, C₂₉H₁₉F₆NOS₂, is a new unsymmetrical photochromic diarylethene derivative with different meta-phenyl substituents. The distance between the two reactive (i.e. can be irradiated to form a new chemical bond) C atoms is 3.501 (4) Å; the dihedral angles between the mean plane of the main central cyclopentene ring and the thiophene rings are 47.7 (5) and 45.1 (2)°, and those between the thiophene rings and the adjacent benzene rings are 29.4 (2) and 28.4 (3)°. The three C atoms and the F atoms of hexafuorocyclopentene ring are disordered over two positions, with site-occupancy factors of 0.751 (4) and 0.249 (4).

Related literature

For related compounds, see: Irie (2000 ); Irie et al. (2001 ); Pu et al. (2007 , 2008 ). For the synthesis of the precursors, see: Pu et al. (2006 ); Yang et al. (2007 ). For ring-closure reactions, see: Ramamurthy & Venkatesan (1987 ).

Experimental

Crystal data

C₂₉H₁₉F₆NOS₂
M_r = 575.57
Triclinic, $[P \overline 1]$
a = 8.6134 (11) Å
b = 11.5938 (15) Å
c = 14.5281 (19) Å
α = 68.346 (2)°
β = 88.783 (2)°
γ = 82.158 (2)°
V = 1335.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 296 K
0.15 × 0.13 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.961, T_max = 0.974
10275 measured reflections
4948 independent reflections
3155 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.127
S = 1.03
4948 reflections
383 parameters
16 restraints
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.23 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809034771/is2442sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034771/is2442Isup2.hkl

checkCIF report

Comment top

Photochromic diarylethene is one of the most promising candidates for photoelectronic applications, such as optical storage (Irie, 2000; Pu et al., 2008), photoswitches (Irie et al., 2001; Pu et al., 2007) and waveguides. In the hexafluorocyclophentene ring of the title compound, C1=C5 [1.342 (4) Å] is clearly a double bond, being significantly shorter than the other single bonds, such as C1-C2 [1.502 (6) Å], C2-C3 [1.530 (6) Å], C3-C4 [1.583 (1) Å], C1-C7 [1.467 (4) Å], C5-C19 [1.471 (4) Å]. The title compound shows a photoactive antiparallel conformation (Fig. 1). The two independent planar thiophene ring systems have essentially identical geometries, and the dihedral angles between the main central cyclopent-1-ene ring and those of the two thiophene rings, S1/C6-C9 and S2/C18-C21, are 47.7 (5) and 45.1 (2)°, respectively. The dihedral angle between the thiophene and adjacent benzene ring is 29.4 (2)° for the C11-C16 benzene ring and 28.4 (3)° for the C23-C28 benzene ring. The two thiophene groups are linked by the C1=C5 double bond, with both of them attached to the ethylene group via the 2-position. The distance between the two reactive C atoms (C6···C18) is 3.501 (4) Å, which is short enough, theoretically, for the ring-closure reaction to take place in the crystalline phase (Ramamurthy & Venkatesan, 1987). Crystals of the title compound (1a) show photochromism in accordance with the expected ring closure, to form (1b) (Fig. 2); upon irradiation with 313 nm light, the colorless crystals turn blue rapidly. The blue compound when dissolved in hexane displays an absorption maximum at 583 nm. Upon irradiation with visible light with a wavelength greater than 450 nm, the blue crystals again turn initial colorless; a hexane solution has an absorption maximum at 294 nm.

Related literature top

For related compounds, see: Irie (2000); Irie et al. (2001); Pu et al. (2007, 2008). For the synthesis of the precursors, see: Pu et al. (2006); Yang et al. (2007). For ring-closure reactions, see: Ramamurthy & Venkatesan (1987).

Experimental top

The title compound was originally derived from 3-bromo-5-(3-methoxyphenyl)-2-methylthiophene (1) (Yang et al., 2007) (5.0 g, 17.6 mmol) with an n-BuLi/hexane solution (7.1 mL, 2.5 M, 17.6 mmol) at 195 K under a nitrogen atmosphere, after 30 min, perfluorocyclopentene (2.2 mL, 17.6 mmol) was added quickly to the reaction solution. The mixture was stirred for 3 h at this temperature. The reaction mixture was filtered and evaporated in vacuo. The residue was purified by column chromatography on silica gel (hexane) to give (2-methyl-5- (3-methoxylphenyl)thiophene)perfluorocyclopent-1-ene, (2) (4.53 g, 11.3 mmol). Finally, to a stirred THF solution (50 ml) of 3-bromo-5-(3-cyanophenyl)-2-methylthiophene, (3) (Pu et al., 2006) (2.6 g, 9.6 mmol), an n-BuLi/hexane solution (3.8 ml, 2.5 M, 9.6 mmol) was slowly added in at 195 K under a nitrogen atmosphere. After 30 min, compound (2) (3.8 g, 9.6 mmol) was added and the mixture was stirred for 2 h at this temperature. The reaction mixture was extracted with diethyl ether and evaporated in vacuo, then purified by column chromatography (petroleum ether) to give the title compound, (Ia) (2.41 g, 4.2 mmol), in 43.7% yield. ¹H NMR (400 MHz, CDCl₃, TMS): δ 1.88 (s, 3H, -CH₃),1.90 (s, 3H, -CH₃), 3.76 (s, 3H, -OCH₃), 6.76-6.78 (dd, 1H, Hz, thiophene-H), 6.97 (s, 1H, thiophene-H), 7.04, 7.06 (d, 1H, J=8.0 Hz, phenyl -H), 7.17-7.24 (m, 2H, phenyl -H), 7.27 (s, 1H, phenyl-H), 7.41 (t, 1H, J=8.0 Hz, phenyl -H), 7.48, 7.50 (d, 1H, J=8.0 Hz, phenyl -H), 7.66, 7.68 (d, 1H, J=8.0 Hz, phenyl -H), 7.72 (s, 1H, phenyl-H); Elemental analysis: calc. for C₂₉H₁₉F₆NOS₂: C 60.20, H 3.83%. Found: C 58.84, H 3.77%; m.p.: 369.4–370.8 K.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound; thermal displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radius. Only the major component of the disordered groups are shown.
	Fig. 2. Photochromic interconvertion of the title compound.

3-(4-{3,3,4,4,5,5-Hexafluoro-2-[5-(3-methoxyphenyl)-2-methyl-3- thienyl]cyclopent-1-enyl}-5-methyl-2-thienyl)benzonitrile top

Crystal data top

C₂₉H₁₉F₆NOS₂	Z = 2
M_r = 575.57	F(000) = 588
Triclinic, P1	D_x = 1.432 Mg m⁻³
a = 8.6134 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.5938 (15) Å	Cell parameters from 1963 reflections
c = 14.5281 (19) Å	θ = 2.4–21.8°
α = 68.346 (2)°	µ = 0.27 mm⁻¹
β = 88.783 (2)°	T = 296 K
γ = 82.158 (2)°	Block, colourless
V = 1335.1 (3) Å³	0.15 × 0.13 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	4948 independent reflections
Radiation source: fine-focus sealed tube	3155 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.961, T_max = 0.974	k = −14→14
10275 measured reflections	l = −17→17

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0556P)² + 0.1414P] where P = (F_o² + 2F_c²)/3
4948 reflections	(Δ/σ)_max < 0.001
383 parameters	Δρ_max = 0.30 e Å⁻³
16 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂₉H₁₉F₆NOS₂	γ = 82.158 (2)°
M_r = 575.57	V = 1335.1 (3) Å³
Triclinic, P1	Z = 2
a = 8.6134 (11) Å	Mo Kα radiation
b = 11.5938 (15) Å	µ = 0.27 mm⁻¹
c = 14.5281 (19) Å	T = 296 K
α = 68.346 (2)°	0.15 × 0.13 × 0.10 mm
β = 88.783 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4948 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3155 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.974	R_int = 0.029
10275 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	16 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.03	Δρ_max = 0.30 e Å⁻³
4948 reflections	Δρ_min = −0.23 e Å⁻³
383 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)
C2	0.8607 (7)	0.8219 (8)	0.1970 (5)	0.0616 (8)	0.751 (4)
C3	0.9550 (6)	0.8673 (5)	0.2620 (5)	0.0653 (13)	0.751 (4)
C4	0.8293 (11)	0.9522 (4)	0.2991 (4)	0.0510 (14)	0.751 (4)
F1	0.9173 (6)	0.7019 (6)	0.2107 (4)	0.0911 (14)	0.751 (4)
F2	0.8822 (6)	0.8920 (4)	0.1004 (4)	0.0963 (15)	0.751 (4)
F3	1.0171 (4)	0.7695 (3)	0.3431 (2)	0.1018 (11)	0.751 (4)
F4	1.0726 (3)	0.9286 (4)	0.2184 (3)	0.0965 (11)	0.751 (4)
F5	0.8628 (3)	0.9419 (3)	0.3914 (2)	0.0814 (9)	0.751 (4)
F6	0.8338 (4)	1.0749 (3)	0.2401 (2)	0.0802 (11)	0.751 (4)
C2'	0.8610 (15)	0.822 (2)	0.1990 (15)	0.0616 (8)	0.249 (4)
C3'	0.9453 (17)	0.9039 (17)	0.2351 (15)	0.0653 (13)	0.249 (4)
C4'	0.848 (4)	0.9271 (15)	0.2995 (13)	0.0510 (14)	0.249 (4)
F1'	0.904 (2)	0.700 (2)	0.2492 (14)	0.0911 (14)	0.249 (4)
F2'	0.877 (2)	0.8315 (16)	0.1047 (14)	0.0963 (15)	0.249 (4)
F3'	1.0853 (14)	0.8369 (11)	0.2718 (9)	0.1018 (11)	0.249 (4)
F4'	0.9731 (9)	0.9989 (10)	0.1527 (8)	0.0965 (11)	0.249 (4)
F5'	0.8899 (11)	0.8652 (10)	0.3949 (8)	0.0814 (9)	0.249 (4)
F6'	0.8456 (16)	1.0469 (13)	0.2921 (9)	0.0802 (11)	0.249 (4)
C1	0.6932 (3)	0.8443 (2)	0.2242 (2)	0.0474 (7)
C5	0.6795 (3)	0.9091 (2)	0.28436 (19)	0.0460 (7)
C6	0.4380 (3)	0.8805 (2)	0.13185 (19)	0.0451 (6)
C7	0.5704 (3)	0.8033 (2)	0.1798 (2)	0.0461 (7)
C8	0.5748 (3)	0.6789 (3)	0.1826 (2)	0.0516 (7)
H8	0.6580	0.6159	0.2111	0.062*
C9	0.4467 (3)	0.6608 (2)	0.1399 (2)	0.0482 (7)
C10	0.3912 (3)	1.0166 (2)	0.1107 (2)	0.0545 (7)
H10A	0.3333	1.0270	0.1650	0.082*
H10B	0.3269	1.0533	0.0511	0.082*
H10C	0.4834	1.0571	0.1024	0.082*
C11	0.4066 (4)	0.5459 (3)	0.1315 (2)	0.0520 (7)
C12	0.2517 (4)	0.5282 (3)	0.1271 (2)	0.0593 (8)
H12	0.1722	0.5894	0.1304	0.071*
C13	0.2130 (4)	0.4207 (3)	0.1178 (2)	0.0673 (9)
C14	0.3297 (5)	0.3315 (3)	0.1111 (2)	0.0739 (10)
H14	0.3046	0.2602	0.1029	0.089*
C15	0.4834 (5)	0.3476 (3)	0.1163 (2)	0.0688 (9)
H15	0.5620	0.2861	0.1126	0.083*
C16	0.5244 (4)	0.4538 (3)	0.1270 (2)	0.0620 (8)
H16	0.6293	0.4631	0.1310	0.074*
C17	0.0082 (6)	0.3090 (4)	0.1022 (4)	0.1315 (19)
H17A	0.0523	0.3022	0.0429	0.197*
H17B	−0.1042	0.3193	0.0965	0.197*
H17C	0.0442	0.2343	0.1580	0.197*
C18	0.4268 (3)	0.8736 (3)	0.37482 (19)	0.0480 (7)
C19	0.5397 (3)	0.9477 (2)	0.33159 (19)	0.0452 (7)
C20	0.5058 (3)	1.0699 (3)	0.33379 (19)	0.0480 (7)
H20	0.5720	1.1306	0.3087	0.058*
C21	0.3672 (3)	1.0900 (3)	0.3761 (2)	0.0503 (7)
C22	0.4206 (4)	0.7390 (3)	0.3910 (2)	0.0602 (8)
H22A	0.3639	0.7343	0.3366	0.090*
H22B	0.3687	0.7003	0.4515	0.090*
H22C	0.5253	0.6962	0.3951	0.090*
C23	0.2932 (3)	1.2076 (3)	0.38317 (19)	0.0511 (7)
C24	0.1306 (4)	1.2368 (3)	0.3827 (2)	0.0610 (8)
H24	0.0666	1.1797	0.3799	0.073*
C25	0.0641 (4)	1.3508 (3)	0.3865 (2)	0.0698 (9)
C26	0.1566 (5)	1.4367 (3)	0.3904 (2)	0.0796 (10)
H26	0.1110	1.5126	0.3935	0.095*
C27	0.3175 (5)	1.4096 (3)	0.3896 (3)	0.0760 (10)
H27	0.3805	1.4679	0.3912	0.091*
C28	0.3851 (4)	1.2964 (3)	0.3863 (2)	0.0619 (8)
H28	0.4937	1.2789	0.3863	0.074*
C29	−0.1043 (5)	1.3799 (4)	0.3840 (3)	0.0919 (13)
N1	−0.2356 (4)	1.4047 (4)	0.3815 (3)	0.1329 (16)
O1	0.0558 (3)	0.4145 (2)	0.1161 (2)	0.0975 (9)
S1	0.32016 (9)	0.79945 (7)	0.09174 (5)	0.0523 (2)
S2	0.28003 (9)	0.95549 (7)	0.41707 (6)	0.0570 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0492 (19)	0.066 (2)	0.075 (2)	0.0006 (16)	0.0011 (16)	−0.0354 (18)
C3	0.036 (2)	0.067 (4)	0.096 (5)	0.000 (2)	−0.005 (2)	−0.035 (3)
C4	0.048 (3)	0.050 (3)	0.063 (2)	−0.008 (3)	0.0055 (16)	−0.0309 (19)
F1	0.0546 (17)	0.0930 (16)	0.155 (5)	0.0099 (12)	0.006 (3)	−0.087 (3)
F2	0.0647 (14)	0.153 (5)	0.0747 (16)	−0.029 (3)	0.0199 (11)	−0.042 (3)
F3	0.092 (2)	0.095 (2)	0.114 (3)	0.0270 (18)	−0.0439 (19)	−0.045 (2)
F4	0.0457 (17)	0.140 (3)	0.145 (3)	−0.0392 (19)	0.0381 (17)	−0.093 (2)
F5	0.0607 (16)	0.130 (3)	0.0804 (16)	−0.0208 (19)	−0.0012 (12)	−0.067 (2)
F6	0.0650 (15)	0.057 (2)	0.115 (3)	−0.0247 (14)	0.024 (2)	−0.023 (2)
C2'	0.0492 (19)	0.066 (2)	0.075 (2)	0.0006 (16)	0.0011 (16)	−0.0354 (18)
C3'	0.036 (2)	0.067 (4)	0.096 (5)	0.000 (2)	−0.005 (2)	−0.035 (3)
C4'	0.048 (3)	0.050 (3)	0.063 (2)	−0.008 (3)	0.0055 (16)	−0.0309 (19)
F1'	0.0546 (17)	0.0930 (16)	0.155 (5)	0.0099 (12)	0.006 (3)	−0.087 (3)
F2'	0.0647 (14)	0.153 (5)	0.0747 (16)	−0.029 (3)	0.0199 (11)	−0.042 (3)
F3'	0.092 (2)	0.095 (2)	0.114 (3)	0.0270 (18)	−0.0439 (19)	−0.045 (2)
F4'	0.0457 (17)	0.140 (3)	0.145 (3)	−0.0392 (19)	0.0381 (17)	−0.093 (2)
F5'	0.0607 (16)	0.130 (3)	0.0804 (16)	−0.0208 (19)	−0.0012 (12)	−0.067 (2)
F6'	0.0650 (15)	0.057 (2)	0.115 (3)	−0.0247 (14)	0.024 (2)	−0.023 (2)
C1	0.0408 (16)	0.0449 (16)	0.0557 (17)	−0.0031 (13)	0.0014 (13)	−0.0187 (14)
C5	0.0428 (16)	0.0451 (15)	0.0501 (16)	−0.0076 (12)	0.0010 (13)	−0.0170 (13)
C6	0.0476 (16)	0.0459 (16)	0.0465 (16)	−0.0076 (13)	0.0049 (13)	−0.0224 (13)
C7	0.0415 (16)	0.0491 (16)	0.0538 (17)	−0.0065 (13)	0.0037 (13)	−0.0261 (14)
C8	0.0479 (17)	0.0475 (17)	0.0603 (18)	0.0008 (13)	−0.0026 (14)	−0.0231 (14)
C9	0.0516 (17)	0.0431 (15)	0.0531 (17)	−0.0030 (13)	0.0019 (13)	−0.0226 (13)
C10	0.0567 (18)	0.0443 (16)	0.0621 (19)	−0.0028 (14)	−0.0032 (14)	−0.0205 (14)
C11	0.066 (2)	0.0456 (16)	0.0459 (16)	−0.0046 (15)	−0.0030 (14)	−0.0198 (13)
C12	0.068 (2)	0.0485 (17)	0.0628 (19)	−0.0063 (15)	−0.0068 (16)	−0.0218 (15)
C13	0.087 (3)	0.0470 (18)	0.068 (2)	−0.0173 (18)	−0.0074 (18)	−0.0186 (16)
C14	0.115 (3)	0.0417 (18)	0.069 (2)	−0.018 (2)	−0.003 (2)	−0.0227 (16)
C15	0.094 (3)	0.0420 (18)	0.068 (2)	0.0048 (18)	0.0031 (19)	−0.0227 (16)
C16	0.075 (2)	0.0513 (18)	0.0618 (19)	−0.0045 (16)	0.0054 (16)	−0.0252 (15)
C17	0.135 (4)	0.084 (3)	0.179 (5)	−0.048 (3)	−0.038 (3)	−0.038 (3)
C18	0.0487 (17)	0.0518 (16)	0.0472 (16)	−0.0107 (13)	0.0008 (13)	−0.0212 (14)
C19	0.0427 (16)	0.0483 (16)	0.0472 (16)	−0.0083 (13)	0.0006 (13)	−0.0200 (13)
C20	0.0450 (17)	0.0511 (17)	0.0520 (16)	−0.0127 (13)	0.0014 (13)	−0.0218 (14)
C21	0.0439 (17)	0.0579 (18)	0.0505 (16)	−0.0038 (14)	−0.0013 (13)	−0.0228 (14)
C22	0.068 (2)	0.0564 (18)	0.0583 (18)	−0.0188 (16)	0.0079 (15)	−0.0204 (15)
C23	0.0500 (17)	0.0582 (18)	0.0454 (16)	0.0004 (14)	−0.0003 (13)	−0.0221 (14)
C24	0.056 (2)	0.067 (2)	0.0564 (18)	−0.0040 (16)	0.0048 (15)	−0.0202 (16)
C25	0.061 (2)	0.070 (2)	0.062 (2)	0.0079 (18)	0.0113 (16)	−0.0133 (18)
C26	0.090 (3)	0.062 (2)	0.078 (2)	0.018 (2)	0.005 (2)	−0.0260 (19)
C27	0.087 (3)	0.059 (2)	0.086 (2)	−0.0044 (19)	−0.002 (2)	−0.0330 (19)
C28	0.059 (2)	0.063 (2)	0.067 (2)	−0.0024 (16)	−0.0043 (16)	−0.0303 (17)
C29	0.067 (3)	0.087 (3)	0.091 (3)	0.017 (2)	0.022 (2)	−0.008 (2)
N1	0.078 (3)	0.123 (3)	0.143 (3)	0.021 (2)	0.034 (2)	0.001 (2)
O1	0.096 (2)	0.0707 (16)	0.129 (2)	−0.0306 (15)	−0.0231 (17)	−0.0324 (16)
S1	0.0505 (4)	0.0490 (4)	0.0619 (5)	−0.0042 (3)	−0.0044 (3)	−0.0264 (4)
S2	0.0502 (5)	0.0664 (5)	0.0616 (5)	−0.0165 (4)	0.0121 (4)	−0.0295 (4)

Geometric parameters (Å, º) top

C2—F1	1.352 (5)	C12—C13	1.386 (4)
C2—F2	1.361 (6)	C12—H12	0.9300
C2—C1	1.502 (6)	C13—O1	1.367 (4)
C2—C3	1.530 (6)	C13—C14	1.370 (5)
C3—F4	1.331 (5)	C14—C15	1.370 (5)
C3—F3	1.354 (5)	C14—H14	0.9300
C3—C4	1.583 (11)	C15—C16	1.388 (4)
C4—F5	1.337 (5)	C15—H15	0.9300
C4—F6	1.369 (5)	C16—H16	0.9300
C4—C5	1.492 (8)	C17—O1	1.424 (4)
C2'—F2'	1.340 (10)	C17—H17A	0.9600
C2'—F1'	1.339 (10)	C17—H17B	0.9600
C2'—C1	1.494 (10)	C17—H17C	0.9600
C2'—C3'	1.505 (10)	C18—C19	1.372 (4)
C3'—F4'	1.338 (10)	C18—C22	1.499 (4)
C3'—F3'	1.345 (10)	C18—S2	1.716 (3)
C3'—C4'	1.32 (4)	C19—C20	1.420 (4)
C4'—F5'	1.334 (10)	C20—C21	1.362 (4)
C4'—F6'	1.350 (10)	C20—H20	0.9300
C4'—C5	1.53 (3)	C21—C23	1.462 (4)
C1—C5	1.342 (4)	C21—S2	1.722 (3)
C1—C7	1.467 (4)	C22—H22A	0.9600
C5—C19	1.471 (4)	C22—H22B	0.9600
C6—C7	1.371 (4)	C22—H22C	0.9600
C6—C10	1.490 (3)	C23—C28	1.395 (4)
C6—S1	1.715 (3)	C23—C24	1.395 (4)
C7—C8	1.423 (3)	C24—C25	1.387 (4)
C8—C9	1.355 (4)	C24—H24	0.9300
C8—H8	0.9300	C25—C26	1.375 (5)
C9—C11	1.468 (4)	C25—C29	1.441 (5)
C9—S1	1.727 (3)	C26—C27	1.379 (5)
C10—H10A	0.9600	C26—H26	0.9300
C10—H10B	0.9600	C27—C28	1.379 (4)
C10—H10C	0.9600	C27—H27	0.9300
C11—C12	1.384 (4)	C28—H28	0.9300
C11—C16	1.389 (4)	C29—N1	1.126 (4)

F1—C2—F2	106.8 (5)	C12—C11—C16	119.0 (3)
F1—C2—C1	115.7 (5)	C12—C11—C9	120.8 (3)
F2—C2—C1	111.1 (5)	C16—C11—C9	120.2 (3)
F1—C2—C3	109.8 (6)	C13—C12—C11	121.1 (3)
F2—C2—C3	108.3 (6)	C13—C12—H12	119.5
C1—C2—C3	105.0 (4)	C11—C12—H12	119.5
F4—C3—F3	106.9 (4)	O1—C13—C14	125.5 (3)
F4—C3—C4	111.4 (5)	O1—C13—C12	114.9 (3)
F3—C3—C4	107.3 (5)	C14—C13—C12	119.6 (3)
F4—C3—C2	115.7 (6)	C13—C14—C15	119.8 (3)
F3—C3—C2	110.6 (5)	C13—C14—H14	120.1
C4—C3—C2	104.7 (5)	C15—C14—H14	120.1
F5—C4—F6	106.4 (4)	C14—C15—C16	121.4 (3)
F5—C4—C5	116.0 (6)	C14—C15—H15	119.3
F6—C4—C5	111.9 (5)	C16—C15—H15	119.3
F5—C4—C3	111.8 (5)	C15—C16—C11	119.1 (3)
F6—C4—C3	108.4 (6)	C15—C16—H16	120.5
C5—C4—C3	102.3 (4)	C11—C16—H16	120.5
F2'—C2'—F1'	102.3 (18)	O1—C17—H17A	109.5
F2'—C2'—C1	112.5 (15)	O1—C17—H17B	109.5
F1'—C2'—C1	103.8 (14)	H17A—C17—H17B	109.5
F2'—C2'—C3'	118.5 (18)	O1—C17—H17C	109.5
F1'—C2'—C3'	113.2 (17)	H17A—C17—H17C	109.5
C1—C2'—C3'	105.8 (11)	H17B—C17—H17C	109.5
F4'—C3'—F3'	106.7 (13)	C19—C18—C22	129.6 (3)
F4'—C3'—C4'	118.9 (17)	C19—C18—S2	110.3 (2)
F3'—C3'—C4'	116.3 (19)	C22—C18—S2	120.0 (2)
F4'—C3'—C2'	104.6 (18)	C18—C19—C20	112.7 (2)
F3'—C3'—C2'	106.0 (16)	C18—C19—C5	125.0 (2)
C4'—C3'—C2'	102.8 (16)	C20—C19—C5	122.3 (2)
F5'—C4'—F6'	101.1 (13)	C21—C20—C19	113.8 (2)
F5'—C4'—C5	108 (2)	C21—C20—H20	123.1
F6'—C4'—C5	107 (2)	C19—C20—H20	123.1
F5'—C4'—C3'	116 (2)	C20—C21—C23	127.3 (3)
F6'—C4'—C3'	110 (2)	C20—C21—S2	110.0 (2)
C5—C4'—C3'	113.5 (15)	C23—C21—S2	122.7 (2)
C5—C1—C7	129.3 (2)	C18—C22—H22A	109.5
C5—C1—C2'	110.0 (9)	C18—C22—H22B	109.5
C7—C1—C2'	120.6 (9)	H22A—C22—H22B	109.5
C5—C1—C2	111.0 (4)	C18—C22—H22C	109.5
C7—C1—C2	119.5 (4)	H22A—C22—H22C	109.5
C1—C5—C19	129.6 (2)	H22B—C22—H22C	109.5
C1—C5—C4'	103.5 (10)	C28—C23—C24	118.2 (3)
C19—C5—C4'	126.8 (9)	C28—C23—C21	120.1 (3)
C1—C5—C4	112.9 (3)	C24—C23—C21	121.6 (3)
C19—C5—C4	117.5 (4)	C25—C24—C23	120.2 (3)
C7—C6—C10	129.4 (2)	C25—C24—H24	119.9
C7—C6—S1	110.49 (19)	C23—C24—H24	119.9
C10—C6—S1	120.1 (2)	C26—C25—C24	120.8 (3)
C6—C7—C8	112.6 (2)	C26—C25—C29	120.0 (3)
C6—C7—C1	123.7 (2)	C24—C25—C29	119.2 (4)
C8—C7—C1	123.7 (2)	C25—C26—C27	119.6 (3)
C9—C8—C7	113.7 (2)	C25—C26—H26	120.2
C9—C8—H8	123.1	C27—C26—H26	120.2
C7—C8—H8	123.1	C28—C27—C26	120.1 (3)
C8—C9—C11	129.6 (3)	C28—C27—H27	119.9
C8—C9—S1	110.2 (2)	C26—C27—H27	119.9
C11—C9—S1	120.3 (2)	C27—C28—C23	121.1 (3)
C6—C10—H10A	109.5	C27—C28—H28	119.5
C6—C10—H10B	109.5	C23—C28—H28	119.5
H10A—C10—H10B	109.5	N1—C29—C25	178.8 (5)
C6—C10—H10C	109.5	C13—O1—C17	117.6 (3)
H10A—C10—H10C	109.5	C6—S1—C9	92.97 (13)
H10B—C10—H10C	109.5	C18—S2—C21	93.21 (13)

F1—C2—C3—F4	94.8 (6)	C3—C4—C5—C1	−16.5 (4)
F2—C2—C3—F4	−21.6 (6)	F5—C4—C5—C19	44.6 (5)
C1—C2—C3—F4	−140.3 (5)	F6—C4—C5—C19	−77.6 (5)
F1—C2—C3—F3	−26.9 (6)	C3—C4—C5—C19	166.6 (3)
F2—C2—C3—F3	−143.2 (5)	F5—C4—C5—C4'	−100 (4)
C1—C2—C3—F3	98.0 (5)	F6—C4—C5—C4'	138 (5)
F1—C2—C3—C4	−142.2 (4)	C3—C4—C5—C4'	22 (4)
F2—C2—C3—C4	101.5 (5)	C10—C6—C7—C8	−178.1 (3)
C1—C2—C3—C4	−17.3 (6)	S1—C6—C7—C8	0.5 (3)
F4—C3—C4—F5	−89.5 (6)	C10—C6—C7—C1	2.5 (4)
F3—C3—C4—F5	27.2 (7)	S1—C6—C7—C1	−178.9 (2)
C2—C3—C4—F5	144.8 (6)	C5—C1—C7—C6	48.2 (4)
F4—C3—C4—F6	27.5 (7)	C2'—C1—C7—C6	−127.5 (10)
F3—C3—C4—F6	144.1 (5)	C2—C1—C7—C6	−127.0 (4)
C2—C3—C4—F6	−98.3 (6)	C5—C1—C7—C8	−131.2 (3)
F4—C3—C4—C5	145.8 (5)	C2'—C1—C7—C8	53.2 (11)
F3—C3—C4—C5	−97.5 (5)	C2—C1—C7—C8	53.6 (5)
C2—C3—C4—C5	20.0 (5)	C6—C7—C8—C9	−1.5 (3)
F2'—C2'—C3'—F4'	21.7 (19)	C1—C7—C8—C9	177.9 (3)
F1'—C2'—C3'—F4'	141.4 (14)	C7—C8—C9—C11	−177.7 (3)
C1—C2'—C3'—F4'	−105.6 (16)	C7—C8—C9—S1	1.9 (3)
F2'—C2'—C3'—F3'	−91 (2)	C8—C9—C11—C12	150.9 (3)
F1'—C2'—C3'—F3'	28.8 (18)	S1—C9—C11—C12	−28.6 (4)
C1—C2'—C3'—F3'	141.8 (14)	C8—C9—C11—C16	−29.7 (4)
F2'—C2'—C3'—C4'	146.6 (15)	S1—C9—C11—C16	150.8 (2)
F1'—C2'—C3'—C4'	−93.7 (14)	C16—C11—C12—C13	−0.3 (4)
C1—C2'—C3'—C4'	19.3 (17)	C9—C11—C12—C13	179.1 (3)
F4'—C3'—C4'—F5'	−140.1 (16)	C11—C12—C13—O1	178.9 (3)
F3'—C3'—C4'—F5'	−10 (3)	C11—C12—C13—C14	−1.2 (5)
C2'—C3'—C4'—F5'	105 (2)	O1—C13—C14—C15	−178.3 (3)
F4'—C3'—C4'—F6'	−26 (3)	C12—C13—C14—C15	1.8 (5)
F3'—C3'—C4'—F6'	104 (2)	C13—C14—C15—C16	−0.9 (5)
C2'—C3'—C4'—F6'	−141.1 (17)	C14—C15—C16—C11	−0.6 (5)
F4'—C3'—C4'—C5	94 (2)	C12—C11—C16—C15	1.1 (4)
F3'—C3'—C4'—C5	−136.5 (16)	C9—C11—C16—C15	−178.2 (3)
C2'—C3'—C4'—C5	−21.2 (16)	C22—C18—C19—C20	−177.6 (3)
F2'—C2'—C1—C5	−141.7 (14)	S2—C18—C19—C20	0.3 (3)
F1'—C2'—C1—C5	108.5 (15)	C22—C18—C19—C5	4.4 (5)
C3'—C2'—C1—C5	−10.9 (15)	S2—C18—C19—C5	−177.7 (2)
F2'—C2'—C1—C7	35 (2)	C1—C5—C19—C18	42.1 (4)
F1'—C2'—C1—C7	−75.1 (15)	C4'—C5—C19—C18	−133.1 (7)
C3'—C2'—C1—C7	165.6 (8)	C4—C5—C19—C18	−141.5 (3)
F2'—C2'—C1—C2	15 (61)	C1—C5—C19—C20	−135.7 (3)
F1'—C2'—C1—C2	−95 (63)	C4'—C5—C19—C20	49.1 (8)
C3'—C2'—C1—C2	146 (63)	C4—C5—C19—C20	40.6 (4)
F1—C2—C1—C5	129.1 (6)	C18—C19—C20—C21	−1.4 (3)
F2—C2—C1—C5	−108.9 (5)	C5—C19—C20—C21	176.7 (2)
C3—C2—C1—C5	7.9 (6)	C19—C20—C21—C23	−175.1 (2)
F1—C2—C1—C7	−54.9 (7)	C19—C20—C21—S2	1.8 (3)
F2—C2—C1—C7	67.1 (7)	C20—C21—C23—C28	−28.5 (4)
C3—C2—C1—C7	−176.0 (3)	S2—C21—C23—C28	155.0 (2)
F1—C2—C1—C2'	105 (62)	C20—C21—C23—C24	148.8 (3)
F2—C2—C1—C2'	−133 (62)	S2—C21—C23—C24	−27.7 (4)
C3—C2—C1—C2'	−16 (62)	C28—C23—C24—C25	−0.7 (4)
C7—C1—C5—C19	6.8 (5)	C21—C23—C24—C25	−178.0 (3)
C2'—C1—C5—C19	−177.1 (9)	C23—C24—C25—C26	0.2 (5)
C2—C1—C5—C19	−177.6 (4)	C23—C24—C25—C29	178.8 (3)
C7—C1—C5—C4'	−177.1 (6)	C24—C25—C26—C27	0.6 (5)
C2'—C1—C5—C4'	−1.1 (11)	C29—C25—C26—C27	−178.0 (3)
C2—C1—C5—C4'	−1.6 (7)	C25—C26—C27—C28	−0.9 (5)
C7—C1—C5—C4	−169.6 (3)	C26—C27—C28—C23	0.4 (5)
C2'—C1—C5—C4	6.4 (10)	C24—C23—C28—C27	0.4 (4)
C2—C1—C5—C4	5.9 (5)	C21—C23—C28—C27	177.8 (3)
F5'—C4'—C5—C1	−115.1 (14)	C14—C13—O1—C17	−2.6 (5)
F6'—C4'—C5—C1	136.6 (12)	C12—C13—O1—C17	177.3 (3)
C3'—C4'—C5—C1	15.1 (13)	C7—C6—S1—C9	0.5 (2)
F5'—C4'—C5—C19	61.1 (15)	C10—C6—S1—C9	179.3 (2)
F6'—C4'—C5—C19	−47.2 (15)	C8—C9—S1—C6	−1.4 (2)
C3'—C4'—C5—C19	−168.7 (9)	C11—C9—S1—C6	178.2 (2)
F5'—C4'—C5—C4	101 (5)	C19—C18—S2—C21	0.6 (2)
F6'—C4'—C5—C4	−7 (3)	C22—C18—S2—C21	178.7 (2)
C3'—C4'—C5—C4	−129 (5)	C20—C21—S2—C18	−1.4 (2)
F5—C4—C5—C1	−138.4 (4)	C23—C21—S2—C18	175.7 (2)
F6—C4—C5—C1	99.4 (5)

Experimental details

Crystal data
Chemical formula	C₂₉H₁₉F₆NOS₂
M_r	575.57
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.6134 (11), 11.5938 (15), 14.5281 (19)
α, β, γ (°)	68.346 (2), 88.783 (2), 82.158 (2)
V (Å³)	1335.1 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.15 × 0.13 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.961, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	10275, 4948, 3155
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.127, 1.03
No. of reflections	4948
No. of parameters	383
No. of restraints	16
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.23

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the fund of the Key Laboratory of Nuclear Resources and Environment, East China Institute of Technology, Ministry of Education, China (No. 060607), the Key Scientific Project of the Education Ministry of China (208069), and the Graduate Innovation Fund of East China Institute of Technology (DYCA09002).

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