3,3,4,4,5,5-Hexafluoro-1,2-bis­[2-methyl-5-(3-methyl­phen­yl)-3-thien­yl]cyclo­pent-1-ene, a new photochromic diaryl­ethene compound

Pu, S.-Z.; Yang, T.-S.; Chen, B.; Xu, J.

doi:10.1107/S1600536805041966

3,3,4,4,5,5-Hexafluoro-1,2-bis[2-methyl-5-(3-methylphenyl)-3-thienyl]cyclopent-1-ene, a new photochromic diarylethene compound

The new title symmetric photochromic diarylethene compound, C₂₉H₂₂F₆S₂, which contains a 3-methylphenyl substituent, adopts an antiparallel conformation in the crystal structure. The distance between the two reactive C atoms, i.e. the ring C atoms to which the methyl groups are attached, is 3.559 (8) Å. The dihedral angles between the central cyclopentene ring and the adjacent thiophene rings are 40.8 (7) and 45.1 (5)°, and those between the thiophene rings and the adjacent benzene rings are 3.3 (6) and 25.7 (9)°.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805041966/lh6564sup1.cif Contains datablocks global, Ia
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805041966/lh6564Iasup2.hkl Contains datablock Ia

CCDC reference: 296612

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.003 Å
Disorder in main residue
R factor = 0.041
wR factor = 0.112
Data-to-parameter ratio = 12.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT213_ALERT_2_B Atom C17'    has ADP max/min Ratio .............       4.20 oblate
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       4.04 Ratio
PLAT432_ALERT_2_B Short Inter X...Y Contact  C29    ..  F6'     ..       2.86 Ang.

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.728     0.970
            Tmin(prime) and Tmax expected:      0.936     0.973
            RR(prime) =      0.781
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.78
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C14
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C15
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for       C16'
PLAT301_ALERT_3_C Main Residue  Disorder .........................      23.00 Perc.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C10    -   C11    ...       1.37 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C18    -   C19    ...       1.37 Ang.

   0 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

A photochromic compound is defined as one that can be transformed reversibly between two isomers having different absorption spectra (Brown, 1971; Dürr & Bouas-Laurent, 1990). Although various types of photochromic compounds have been reported, compounds that undergo thermally stable photochromic reactions are limited to diarylethenes, fulgides and phenoxynaphthacenequinones (Kobatake & Irie, 2003). Of all the photochromic compounds, diarylethenes are the most promising candidates because of their good thermal stability, high sensitivity, fast response and high fatigue resistance (Irie, 2000; Tian & Yang, 2004). A large numbers of diarylethene crystal structures and their properties have already been reported (Matsuda & Irie, 2004; Morimoto et al., 2004; Morimoto & Irie, 2005; Kobatake & Irie, 2004), including some structures we have determined (Pu et al., 2003, 2004; Pu, Fan et al., 2005; Pu, Li et al., 2005; Pu, Liu et al., 2005; Pu, Xu et al., 2005; Pu, Xiao et al., 2005; Pu, Yang, Wang et al., 2005; Pu, Yang, Yan et al., 2005). For further background information see Pu, Liu et al. (2005). A new diarylethene compound, (Ia), with methyl groups at the meta-positions of both terminal phenyl groups was synthesized, and its crystal structure is reported here.

The molecular structure of (Ia) is shown in Fig. 1 and selected geometric parameters are given in Table 1. The molecule contains two thiophene rings substituted by two meta-methylbenzene rings in a photoactive antiparallel conformation, i.e. the molecule has molecular C₂ symmetry. The central hexafluorocyclopentene ring is disordered over two sites (see Fig. 2 and Experimental section). In the cyclopent-1-ene ring, the C13═C17 bond is clearly a double bond, and the other bonds in the ring are clearly single bonds (see Table 1).

The two thiophene moieties are linked by the C13=C17 double bond. The two methyl groups located on different sides of the double bond and are thus trans with respect to the double bond. Such a conformation is crucial for the compound to exhibit photochromic and photoinduced properties (Woodward & Hoffmann, 1970). The dihedral angles between the least-squares plane of the atoms of the central cyclopent-1-ene ring and the adjacent thiophene rings are 40.8 (7)° for S1/C8–C11 and 45.1 (5)° for S2/C18–C22, and those between thiophene rings and the adjacent benzene rings are 3.3 (6)° for C1–C4/C6/C7 and 25.7 (9)° for C23–C27/C29, respectively. The distance between the two reactive C atoms (C13···C17) is 3.559 (8) Å. This distance indicates that the crystal can undergo photochromism in the crystalline phase because the photochromic reactivity of crystals depends on the distance between the reactive C atoms being less than 4.2 Å (Ramamurthy & Venkatesan, 1987; Shibata et al., 2002; Kobatake et al., 2004).

Upon irradiation with 313 nm light, colorless single crystals of (Ia) 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 absorption maximum of this solution was observed at a wavelength of 580 nm, consistent with the presence of the closed-ring isomer, (Ib). This result suggests that the title compound undergoes a photochromic reaction to produce the closed-ring molecule of (Ib) in single-crystal phase. We have not, so far, been able to determine the crystal structure of (Ib). Furthermore, upon irradiation with wavelengths longer than 450 nm, the blue crystal changes back to colourless, 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 279 nm.

Experimental top

The title compound was originally derived from 2-methylthiophene (I). 3-Bromo-2-methyl-5-(3-methylphenyl)thiophene, (2) (3.57 g, 13.4 mmol), in 83.7% yield was synthesized by reacting (I) (3.53 g, 16.0 mmol) (Pu, Liu et al., 2005) with 3-bromo-1-methylbenzene (2.74 g, 16.0 mmol) in the presence of Pd(PPh₃)₄ (0.5 g) and Na₂CO₃ (2 mol l⁻¹, 30 mmol) in tetrahydrofuran (THF, 80 ml) for 16 h at 343 K. To a stirred THF solution (60 ml) of (2) (3.57 g, 13.4 mmol) 5.4 ml of n-BuLi/hexane solution (2.5 mol l⁻¹, 13.5 mmol) was slowly added at 195 K under a nitrogen atmosphere. 30 min later, octafluorocyclopentene (0.91 ml, 6.7 mmol) was added and the mixture was stirred for 2 h. The reaction mixture was extracted with ether and evaporated in vacuo, then purifed by column chromatography (oil ether) to give the title compound (1.25 g, 2.3 mmol) in 34.3% yield. The compound crystallized from hexane at room temperature and produced single crystals suitable for X-ray analysis. The structure of (Ia) was confirmed by melting point, element analysis and NMR (m.p. 417 K). Analysis calculated for C₂₉H₂₂F₆S₂: C 63.49, H 4.04%; found: C 63.53, H 4.09%; ¹H NMR (400 MHz, CDCl₃): δ 1.948 (s, 6H, –CH₃), 2.373 (s, 6H, –CH₃), 6.720 (s, 2H, thiophene-H), 7.049–7.127 (m, 4H, ben-H), 7.288 (s, 2H, ben-H), 7.338–7.380 (t, 2H, J = 8.4 Hz, ben-H); ¹⁹F NMR (400 MHz, CDCl₃): δ 109.96 (4 F), 131.79 (2 F).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids. The disorder is not shown.
	Fig. 2. A view of a portion of (Ia), showing the disorder. Displacement ellipsoids are drawn at the 30% probability level, and primed (') atom labels and open bonds indicate the minor component of disorder.

3,3,4,4,5,5-Hexafluoro-1,2-bis[2-methyl-5-(3-methylphenyl)-3- thienyl]cyclopent-1-ene top

Crystal data top

C₂₉H₂₂F₆S₂	F(000) = 1128
M_r = 548.59	D_x = 1.432 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 417 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 11.9825 (16) Å	Cell parameters from 3825 reflections
b = 9.2708 (12) Å	θ = 2.4–25.3°
c = 22.935 (3) Å	µ = 0.27 mm⁻¹
β = 92.934 (2)°	T = 294 K
V = 2544.4 (6) Å³	Prism, colorless
Z = 4	0.24 × 0.22 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	5176 independent reflections
Radiation source: fine-focus sealed tube	3308 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 26.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.728, T_max = 0.970	k = −11→11
13927 measured reflections	l = −13→28

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0506P)² + 0.4455P] where P = (F_o² + 2F_c²)/3
5176 reflections	(Δ/σ)_max = 0.003
426 parameters	Δρ_max = 0.22 e Å⁻³
158 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₉H₂₂F₆S₂	V = 2544.4 (6) Å³
M_r = 548.59	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.9825 (16) Å	µ = 0.27 mm⁻¹
b = 9.2708 (12) Å	T = 294 K
c = 22.935 (3) Å	0.24 × 0.22 × 0.10 mm
β = 92.934 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5176 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3308 reflections with I > 2σ(I)
T_min = 0.728, T_max = 0.970	R_int = 0.033
13927 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	158 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.02	Δρ_max = 0.22 e Å⁻³
5176 reflections	Δρ_min = −0.18 e Å⁻³
426 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.15810 (5)	0.37494 (7)	0.21653 (3)	0.05074 (19)
S2	0.47119 (5)	0.60684 (6)	0.39871 (3)	0.04938 (18)
C1	−0.0699 (2)	0.4819 (3)	0.16456 (12)	0.0666 (8)
H1	−0.0040	0.4827	0.1448	0.080*
C2	−0.1673 (3)	0.5350 (4)	0.13787 (14)	0.0807 (9)
H2	−0.1666	0.5711	0.1001	0.097*
C3	−0.2643 (2)	0.5352 (3)	0.16624 (14)	0.0715 (8)
H3	−0.3286	0.5736	0.1478	0.086*
C4	−0.2690 (2)	0.4798 (3)	0.22158 (12)	0.0611 (7)
C5	−0.3776 (2)	0.4736 (5)	0.25194 (14)	0.1013 (13)
H5A	−0.3850	0.5586	0.2753	0.152*
H5B	−0.3781	0.3897	0.2765	0.152*
H5C	−0.4388	0.4685	0.2233	0.152*
C6	−0.17088 (19)	0.4252 (3)	0.24850 (11)	0.0554 (7)
H6	−0.1728	0.3863	0.2858	0.066*
C7	−0.07027 (18)	0.4275 (2)	0.22081 (10)	0.0457 (6)
C8	0.03302 (17)	0.3727 (2)	0.25089 (10)	0.0426 (5)
C9	0.05030 (17)	0.3199 (2)	0.30580 (10)	0.0436 (6)
H9	−0.0069	0.3096	0.3314	0.052*
C10	0.16291 (17)	0.2816 (2)	0.32097 (9)	0.0395 (5)
C11	0.23243 (17)	0.3060 (2)	0.27637 (10)	0.0430 (5)
C12	0.35557 (18)	0.2826 (3)	0.27291 (11)	0.0570 (7)
H12A	0.3947	0.3696	0.2839	0.085*
H12B	0.3718	0.2570	0.2337	0.085*
H12C	0.3791	0.2061	0.2990	0.085*
F1	0.0237 (4)	0.1225 (6)	0.4050 (2)	0.0666 (11)	0.758 (5)
F2	0.1244 (6)	−0.0134 (8)	0.3647 (3)	0.091 (2)	0.758 (5)
F3	0.1916 (3)	−0.0709 (4)	0.4771 (2)	0.1022 (17)	0.758 (5)
F4	0.1286 (2)	0.1363 (4)	0.50310 (10)	0.0931 (12)	0.758 (5)
F5	0.3797 (3)	0.0368 (3)	0.44727 (16)	0.0689 (9)	0.758 (5)
F6	0.3384 (3)	0.1923 (4)	0.51272 (15)	0.0675 (9)	0.758 (5)
C13	0.201 (3)	0.221 (3)	0.3780 (10)	0.0396 (7)	0.758 (5)
C14	0.1346 (6)	0.0991 (9)	0.4017 (3)	0.0469 (7)	0.758 (5)
C15	0.1861 (5)	0.0684 (5)	0.4627 (3)	0.0566 (14)	0.758 (5)
C16	0.3017 (5)	0.1347 (8)	0.4612 (3)	0.051 (2)	0.758 (5)
C17	0.2947 (5)	0.2433 (8)	0.4127 (4)	0.035 (2)	0.758 (5)
F1'	0.0409 (13)	0.1545 (18)	0.4253 (6)	0.068 (4)	0.242 (5)
F2'	0.1508 (16)	−0.032 (2)	0.3748 (9)	0.055 (4)	0.242 (5)
F3'	0.2558 (8)	−0.0886 (7)	0.4328 (4)	0.087 (3)	0.242 (5)
F4'	0.1544 (9)	0.0021 (14)	0.4978 (4)	0.080 (3)	0.242 (5)
F5'	0.3979 (10)	0.0817 (14)	0.4742 (6)	0.090 (4)	0.242 (5)
F6'	0.2793 (12)	0.2141 (14)	0.5145 (5)	0.091 (4)	0.242 (5)
C13'	0.196 (8)	0.214 (10)	0.378 (3)	0.0396 (7)	0.242 (5)
C14'	0.1332 (17)	0.092 (3)	0.4045 (10)	0.0469 (7)	0.242 (5)
C15'	0.2157 (15)	0.0385 (13)	0.4524 (7)	0.053 (5)	0.242 (5)
C16'	0.3027 (12)	0.1574 (19)	0.4618 (7)	0.038 (7)	0.242 (5)
C17'	0.2772 (15)	0.267 (2)	0.4143 (12)	0.025 (5)	0.242 (5)
C18	0.37348 (17)	0.3654 (2)	0.41034 (9)	0.0387 (5)
C19	0.35007 (17)	0.5062 (2)	0.39683 (9)	0.0401 (5)
C20	0.23997 (18)	0.5777 (3)	0.38399 (12)	0.0537 (6)
H20A	0.2196	0.5690	0.3431	0.081*
H20B	0.2454	0.6779	0.3943	0.081*
H20C	0.1841	0.5323	0.4063	0.081*
C21	0.49003 (17)	0.3411 (2)	0.42248 (9)	0.0431 (5)
H21	0.5192	0.2513	0.4330	0.052*
C22	0.55435 (17)	0.4601 (2)	0.41735 (10)	0.0422 (5)
C23	0.67728 (17)	0.4702 (3)	0.42400 (10)	0.0435 (6)
C24	0.73606 (19)	0.3696 (3)	0.45813 (11)	0.0519 (6)
H24	0.6976	0.2991	0.4779	0.062*
C25	0.8514 (2)	0.3735 (3)	0.46294 (12)	0.0600 (7)
H25	0.8903	0.3055	0.4858	0.072*
C26	0.9084 (2)	0.4764 (3)	0.43429 (11)	0.0563 (7)
H26	0.9861	0.4772	0.4378	0.068*
C27	0.85363 (19)	0.5793 (3)	0.40029 (11)	0.0529 (6)
C28	0.9171 (2)	0.6920 (3)	0.36827 (14)	0.0829 (10)
H28A	0.9406	0.7672	0.3949	0.124*
H28B	0.8697	0.7318	0.3373	0.124*
H28C	0.9814	0.6486	0.3522	0.124*
C29	0.73755 (19)	0.5752 (3)	0.39552 (11)	0.0499 (6)
H29	0.6992	0.6440	0.3728	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0417 (3)	0.0672 (4)	0.0435 (4)	0.0016 (3)	0.0038 (3)	0.0029 (3)
S2	0.0374 (3)	0.0424 (3)	0.0679 (4)	−0.0033 (3)	−0.0019 (3)	0.0027 (3)
C1	0.0477 (16)	0.090 (2)	0.0613 (18)	−0.0126 (14)	−0.0067 (13)	0.0223 (16)
C2	0.067 (2)	0.097 (2)	0.075 (2)	−0.0121 (17)	−0.0217 (17)	0.0352 (18)
C3	0.0517 (17)	0.077 (2)	0.083 (2)	0.0031 (14)	−0.0226 (16)	0.0151 (17)
C4	0.0433 (15)	0.0761 (19)	0.0625 (18)	0.0047 (13)	−0.0109 (13)	−0.0099 (15)
C5	0.0479 (18)	0.179 (4)	0.076 (2)	0.026 (2)	−0.0019 (15)	−0.014 (2)
C6	0.0433 (14)	0.0768 (18)	0.0456 (15)	0.0064 (13)	−0.0029 (11)	−0.0023 (13)
C7	0.0398 (13)	0.0488 (14)	0.0477 (14)	−0.0037 (11)	−0.0056 (11)	−0.0002 (11)
C8	0.0357 (12)	0.0484 (14)	0.0435 (13)	−0.0029 (10)	−0.0008 (10)	−0.0006 (11)
C9	0.0323 (12)	0.0532 (14)	0.0453 (14)	−0.0048 (10)	0.0022 (10)	0.0026 (11)
C10	0.0332 (12)	0.0417 (13)	0.0432 (13)	−0.0048 (10)	−0.0018 (10)	−0.0003 (10)
C11	0.0353 (12)	0.0462 (13)	0.0476 (14)	−0.0020 (10)	0.0022 (10)	−0.0044 (11)
C12	0.0362 (13)	0.0751 (18)	0.0600 (16)	0.0035 (12)	0.0067 (11)	0.0006 (14)
F1	0.0361 (14)	0.087 (3)	0.077 (3)	−0.0091 (14)	0.0054 (16)	0.021 (2)
F2	0.126 (5)	0.063 (3)	0.083 (3)	−0.041 (3)	0.000 (3)	−0.005 (2)
F3	0.093 (3)	0.070 (2)	0.140 (4)	−0.0243 (18)	−0.031 (3)	0.055 (2)
F4	0.0708 (16)	0.150 (3)	0.0604 (15)	−0.0147 (17)	0.0198 (12)	−0.0004 (16)
F5	0.0603 (17)	0.0553 (17)	0.091 (2)	0.0197 (13)	0.0009 (15)	0.0148 (15)
F6	0.0712 (19)	0.081 (2)	0.0486 (15)	−0.0176 (17)	−0.0140 (15)	0.0105 (13)
C13	0.033 (3)	0.040 (3)	0.0458 (14)	−0.0022 (12)	0.0020 (13)	0.0003 (17)
C14	0.0375 (13)	0.0483 (17)	0.0548 (17)	−0.0064 (12)	0.0018 (11)	0.0003 (14)
C15	0.044 (3)	0.056 (3)	0.071 (3)	−0.006 (2)	0.007 (2)	0.019 (3)
C16	0.051 (4)	0.047 (3)	0.053 (4)	−0.003 (3)	−0.008 (3)	0.010 (2)
C17	0.026 (2)	0.034 (3)	0.046 (3)	0.007 (3)	0.001 (2)	−0.001 (3)
F1'	0.050 (6)	0.080 (7)	0.077 (8)	0.005 (5)	0.020 (5)	0.014 (5)
F2'	0.057 (5)	0.042 (5)	0.069 (7)	0.000 (4)	0.011 (5)	−0.015 (5)
F3'	0.112 (6)	0.044 (4)	0.102 (6)	0.010 (4)	−0.024 (5)	−0.007 (4)
F4'	0.085 (6)	0.095 (8)	0.059 (5)	−0.025 (6)	0.009 (4)	0.029 (5)
F5'	0.077 (6)	0.086 (7)	0.106 (8)	0.002 (5)	−0.016 (5)	0.046 (6)
F6'	0.132 (8)	0.080 (5)	0.062 (5)	−0.019 (7)	0.016 (6)	−0.012 (4)
C13'	0.033 (3)	0.040 (3)	0.0458 (14)	−0.0022 (12)	0.0020 (13)	0.0003 (17)
C14'	0.0375 (13)	0.0483 (17)	0.0548 (17)	−0.0064 (12)	0.0018 (11)	0.0003 (14)
C15'	0.046 (8)	0.059 (9)	0.054 (8)	0.006 (6)	0.003 (6)	0.014 (6)
C16'	0.025 (9)	0.031 (8)	0.056 (11)	−0.004 (5)	−0.002 (7)	−0.015 (7)
C17'	0.030 (8)	0.016 (6)	0.028 (7)	0.019 (5)	0.003 (5)	0.005 (5)
C18	0.0321 (11)	0.0425 (14)	0.0410 (12)	−0.0014 (9)	−0.0039 (9)	−0.0009 (10)
C19	0.0323 (11)	0.0437 (13)	0.0439 (13)	0.0003 (10)	−0.0002 (10)	0.0008 (10)
C20	0.0382 (13)	0.0473 (14)	0.0751 (18)	0.0045 (11)	−0.0034 (12)	0.0033 (13)
C21	0.0375 (12)	0.0411 (13)	0.0499 (14)	0.0008 (10)	−0.0062 (10)	0.0028 (11)
C22	0.0327 (12)	0.0482 (14)	0.0452 (14)	−0.0007 (10)	−0.0010 (10)	−0.0016 (11)
C23	0.0339 (12)	0.0494 (14)	0.0468 (14)	−0.0040 (10)	−0.0017 (10)	−0.0060 (11)
C24	0.0377 (13)	0.0592 (16)	0.0580 (15)	−0.0071 (11)	−0.0038 (11)	0.0061 (13)
C25	0.0417 (14)	0.0698 (18)	0.0674 (17)	0.0020 (13)	−0.0077 (12)	0.0110 (15)
C26	0.0339 (13)	0.0700 (18)	0.0645 (17)	−0.0026 (12)	−0.0023 (12)	−0.0041 (14)
C27	0.0395 (14)	0.0550 (15)	0.0647 (17)	−0.0043 (12)	0.0082 (12)	−0.0031 (13)
C28	0.0558 (18)	0.077 (2)	0.117 (3)	−0.0102 (15)	0.0147 (18)	0.0226 (19)
C29	0.0414 (14)	0.0513 (15)	0.0568 (15)	−0.0006 (11)	−0.0008 (11)	0.0009 (12)

Geometric parameters (Å, º) top

S1—C11	1.720 (2)	C15—C16	1.518 (6)
S1—C8	1.729 (2)	C16—C17	1.500 (6)
S2—C19	1.724 (2)	C17—C18	1.477 (5)
S2—C22	1.727 (2)	F1'—C14'	1.358 (10)
C1—C2	1.381 (4)	F2'—C14'	1.355 (10)
C1—C7	1.386 (3)	F3'—C15'	1.357 (10)
C1—H1	0.9300	F4'—C15'	1.348 (10)
C2—C3	1.361 (4)	F5'—C16'	1.357 (10)
C2—H2	0.9300	F6'—C16'	1.359 (10)
C3—C4	1.373 (4)	C13'—C17'	1.34 (2)
C3—H3	0.9300	C13'—C14'	1.514 (10)
C4—C6	1.395 (3)	C14'—C15'	1.522 (10)
C4—C5	1.508 (4)	C15'—C16'	1.525 (10)
C5—H5A	0.9600	C16'—C17'	1.511 (10)
C5—H5B	0.9600	C17'—C18	1.476 (10)
C5—H5C	0.9600	C18—C19	1.367 (3)
C6—C7	1.391 (3)	C18—C21	1.428 (3)
C6—H6	0.9300	C19—C20	1.492 (3)
C7—C8	1.476 (3)	C20—H20A	0.9600
C8—C9	1.357 (3)	C20—H20B	0.9600
C9—C10	1.421 (3)	C20—H20C	0.9600
C9—H9	0.9300	C21—C22	1.355 (3)
C10—C11	1.370 (3)	C21—H21	0.9300
C10—C13	1.475 (5)	C22—C23	1.476 (3)
C10—C13'	1.478 (10)	C23—C24	1.387 (3)
C11—C12	1.498 (3)	C23—C29	1.394 (3)
C12—H12A	0.9600	C24—C25	1.381 (3)
C12—H12B	0.9600	C24—H24	0.9300
C12—H12C	0.9600	C25—C26	1.362 (4)
F1—C14	1.353 (5)	C25—H25	0.9300
F2—C14	1.346 (5)	C26—C27	1.377 (3)
F3—C15	1.334 (5)	C26—H26	0.9300
F4—C15	1.341 (6)	C27—C29	1.390 (3)
F5—C16	1.353 (6)	C27—C28	1.505 (3)
F6—C16	1.349 (5)	C28—H28A	0.9600
C13—C17	1.354 (11)	C28—H28B	0.9600
C13—C14	1.504 (5)	C28—H28C	0.9600
C14—C15	1.526 (6)	C29—H29	0.9300

C11—S1—C8	93.29 (11)	C18—C17—C16	122.0 (6)
C19—S2—C22	93.11 (11)	C17'—C13'—C10	123 (2)
C2—C1—C7	120.0 (3)	C17'—C13'—C14'	112.3 (17)
C2—C1—H1	120.0	C10—C13'—C14'	124 (2)
C7—C1—H1	120.0	F2'—C14'—F1'	134 (2)
C3—C2—C1	120.8 (3)	F2'—C14'—C13'	110 (5)
C3—C2—H2	119.6	F1'—C14'—C13'	105 (6)
C1—C2—H2	119.6	F2'—C14'—C15'	88.7 (15)
C2—C3—C4	121.2 (3)	F1'—C14'—C15'	113.3 (17)
C2—C3—H3	119.4	C13'—C14'—C15'	102.5 (17)
C4—C3—H3	119.4	F4'—C15'—F3'	104.8 (11)
C3—C4—C6	118.1 (2)	F4'—C15'—C14'	106.2 (17)
C3—C4—C5	121.2 (3)	F3'—C15'—C14'	105.6 (13)
C6—C4—C5	120.6 (3)	F4'—C15'—C16'	117.8 (15)
C4—C5—H5A	109.5	F3'—C15'—C16'	115.1 (12)
C4—C5—H5B	109.5	C14'—C15'—C16'	106.4 (13)
H5A—C5—H5B	109.5	F5'—C16'—F6'	102.9 (12)
C4—C5—H5C	109.5	F5'—C16'—C17'	129.5 (16)
H5A—C5—H5C	109.5	F6'—C16'—C17'	109.7 (18)
H5B—C5—H5C	109.5	F5'—C16'—C15'	102.5 (14)
C7—C6—C4	121.5 (2)	F6'—C16'—C15'	103.6 (14)
C7—C6—H6	119.2	C17'—C16'—C15'	105.9 (10)
C4—C6—H6	119.2	C13'—C17'—C18	137 (3)
C1—C7—C6	118.3 (2)	C13'—C17'—C16'	108.5 (18)
C1—C7—C8	121.2 (2)	C18—C17'—C16'	109.3 (14)
C6—C7—C8	120.5 (2)	C19—C18—C21	112.48 (19)
C9—C8—C7	130.0 (2)	C19—C18—C17'	116.8 (9)
C9—C8—S1	109.43 (16)	C21—C18—C17'	130.5 (9)
C7—C8—S1	120.57 (17)	C19—C18—C17	128.0 (4)
C8—C9—C10	114.5 (2)	C21—C18—C17	119.5 (3)
C8—C9—H9	122.7	C18—C19—C20	129.6 (2)
C10—C9—H9	122.7	C18—C19—S2	110.38 (15)
C11—C10—C9	112.46 (19)	C20—C19—S2	119.95 (17)
C11—C10—C13	123.4 (15)	C19—C20—H20A	109.5
C9—C10—C13	124.1 (15)	C19—C20—H20B	109.5
C11—C10—C13'	125 (5)	H20A—C20—H20B	109.5
C9—C10—C13'	122 (5)	C19—C20—H20C	109.5
C10—C11—C12	130.8 (2)	H20A—C20—H20C	109.5
C10—C11—S1	110.30 (16)	H20B—C20—H20C	109.5
C12—C11—S1	118.87 (17)	C22—C21—C18	114.2 (2)
C11—C12—H12A	109.5	C22—C21—H21	122.9
C11—C12—H12B	109.5	C18—C21—H21	122.9
H12A—C12—H12B	109.5	C21—C22—C23	127.7 (2)
C11—C12—H12C	109.5	C21—C22—S2	109.85 (16)
H12A—C12—H12C	109.5	C23—C22—S2	122.38 (17)
H12B—C12—H12C	109.5	C24—C23—C29	118.3 (2)
C17—C13—C10	132.4 (11)	C24—C23—C22	119.4 (2)
C17—C13—C14	109.9 (5)	C29—C23—C22	122.3 (2)
C10—C13—C14	117.3 (7)	C25—C24—C23	120.3 (2)
F2—C14—F1	95.8 (6)	C25—C24—H24	119.8
F2—C14—C13	112.9 (15)	C23—C24—H24	119.8
F1—C14—C13	116.2 (18)	C26—C25—C24	120.3 (2)
F2—C14—C15	116.9 (7)	C26—C25—H25	119.9
F1—C14—C15	109.3 (6)	C24—C25—H25	119.9
C13—C14—C15	105.9 (5)	C25—C26—C27	121.5 (2)
F3—C15—F4	107.6 (5)	C25—C26—H26	119.3
F3—C15—C16	111.4 (5)	C27—C26—H26	119.3
F4—C15—C16	109.0 (5)	C26—C27—C29	118.1 (2)
F3—C15—C14	114.9 (6)	C26—C27—C28	121.3 (2)
F4—C15—C14	110.4 (5)	C29—C27—C28	120.6 (2)
C16—C15—C14	103.4 (5)	C27—C28—H28A	109.5
F6—C16—F5	106.0 (4)	C27—C28—H28B	109.5
F6—C16—C17	112.8 (7)	H28A—C28—H28B	109.5
F5—C16—C17	106.7 (6)	C27—C28—H28C	109.5
F6—C16—C15	113.5 (5)	H28A—C28—H28C	109.5
F5—C16—C15	112.0 (5)	H28B—C28—H28C	109.5
C17—C16—C15	105.7 (4)	C27—C29—C23	121.5 (2)
C13—C17—C18	127.2 (7)	C27—C29—H29	119.2
C13—C17—C16	110.4 (4)	C23—C29—H29	119.2

C7—C1—C2—C3	0.2 (5)	C17'—C13'—C14'—F2'	−115 (9)
C1—C2—C3—C4	−1.5 (5)	C10—C13'—C14'—F2'	73 (12)
C2—C3—C4—C6	1.0 (4)	C17'—C13'—C14'—F1'	96 (9)
C2—C3—C4—C5	−177.1 (3)	C10—C13'—C14'—F1'	−75 (11)
C3—C4—C6—C7	0.7 (4)	C17'—C13'—C14'—C15'	−22 (11)
C5—C4—C6—C7	178.8 (3)	C10—C13'—C14'—C15'	166 (10)
C2—C1—C7—C6	1.4 (4)	F2'—C14'—C15'—F4'	−107.5 (16)
C2—C1—C7—C8	−178.8 (3)	F1'—C14'—C15'—F4'	30 (2)
C4—C6—C7—C1	−1.9 (4)	C13'—C14'—C15'—F4'	143 (6)
C4—C6—C7—C8	178.3 (2)	F2'—C14'—C15'—F3'	3.4 (19)
C1—C7—C8—C9	177.8 (3)	F1'—C14'—C15'—F3'	141.4 (17)
C6—C7—C8—C9	−2.4 (4)	C13'—C14'—C15'—F3'	−106 (6)
C1—C7—C8—S1	0.0 (3)	F2'—C14'—C15'—C16'	126.2 (16)
C6—C7—C8—S1	179.81 (19)	F1'—C14'—C15'—C16'	−96 (2)
C11—S1—C8—C9	−0.36 (19)	C13'—C14'—C15'—C16'	16 (6)
C11—S1—C8—C7	177.88 (19)	F4'—C15'—C16'—F5'	96.1 (14)
C7—C8—C9—C10	−177.7 (2)	F3'—C15'—C16'—F5'	−28.3 (19)
S1—C8—C9—C10	0.3 (3)	C14'—C15'—C16'—F5'	−144.8 (13)
C8—C9—C10—C11	−0.1 (3)	F4'—C15'—C16'—F6'	−10.6 (19)
C8—C9—C10—C13	−179.6 (15)	F3'—C15'—C16'—F6'	−135.0 (13)
C8—C9—C10—C13'	−176 (5)	C14'—C15'—C16'—F6'	108.4 (13)
C9—C10—C11—C12	179.8 (2)	F4'—C15'—C16'—C17'	−126.1 (18)
C13—C10—C11—C12	−0.7 (15)	F3'—C15'—C16'—C17'	109.5 (19)
C13'—C10—C11—C12	−4 (4)	C14'—C15'—C16'—C17'	−7.1 (18)
C9—C10—C11—S1	−0.2 (2)	C10—C13'—C17'—C18	−20 (18)
C13—C10—C11—S1	179.3 (14)	C14'—C13'—C17'—C18	168 (4)
C13'—C10—C11—S1	176 (4)	C10—C13'—C17'—C16'	−170 (9)
C8—S1—C11—C10	0.32 (18)	C14'—C13'—C17'—C16'	18 (11)
C8—S1—C11—C12	−179.65 (19)	F5'—C16'—C17'—C13'	115 (7)
C11—C10—C13—C17	40 (5)	F6'—C16'—C17'—C13'	−118 (7)
C9—C10—C13—C17	−141 (4)	C15'—C16'—C17'—C13'	−7 (7)
C13'—C10—C13—C17	162 (100)	F5'—C16'—C17'—C18	−43 (3)
C11—C10—C13—C14	−132 (2)	F6'—C16'—C17'—C18	84 (2)
C9—C10—C13—C14	48 (4)	C15'—C16'—C17'—C18	−165.2 (17)
C13'—C10—C13—C14	−9 (100)	C13'—C17'—C18—C19	66 (9)
C17—C13—C14—F2	−118 (2)	C16'—C17'—C18—C19	−144.9 (14)
C10—C13—C14—F2	56 (4)	C13'—C17'—C18—C21	−120 (9)
C17—C13—C14—F1	133 (2)	C16'—C17'—C18—C21	30 (3)
C10—C13—C14—F1	−53 (4)	C13'—C17'—C18—C17	−95 (12)
C17—C13—C14—C15	12 (3)	C16'—C17'—C18—C17	54 (5)
C10—C13—C14—C15	−175 (3)	C13—C17—C18—C19	35 (3)
F2—C14—C15—F3	−14.8 (9)	C16—C17—C18—C19	−136.6 (6)
F1—C14—C15—F3	92.6 (7)	C13—C17—C18—C21	−144 (3)
C13—C14—C15—F3	−142 (2)	C16—C17—C18—C21	44.2 (10)
F2—C14—C15—F4	−136.7 (6)	C13—C17—C18—C17'	57 (7)
F1—C14—C15—F4	−29.4 (8)	C16—C17—C18—C17'	−115 (7)
C13—C14—C15—F4	96.5 (19)	C21—C18—C19—C20	−177.1 (2)
F2—C14—C15—C16	106.8 (7)	C17'—C18—C19—C20	−1.3 (14)
F1—C14—C15—C16	−145.9 (6)	C17—C18—C19—C20	3.7 (7)
C13—C14—C15—C16	−20 (2)	C21—C18—C19—S2	0.4 (2)
F3—C15—C16—F6	−90.7 (7)	C17'—C18—C19—S2	176.2 (14)
F4—C15—C16—F6	28.0 (7)	C17—C18—C19—S2	−178.8 (6)
C14—C15—C16—F6	145.4 (6)	C22—S2—C19—C18	0.26 (18)
F3—C15—C16—F5	29.3 (8)	C22—S2—C19—C20	178.04 (19)
F4—C15—C16—F5	147.9 (4)	C19—C18—C21—C22	−1.1 (3)
C14—C15—C16—F5	−94.7 (5)	C17'—C18—C21—C22	−176.1 (17)
F3—C15—C16—C17	145.2 (7)	C17—C18—C21—C22	178.2 (5)
F4—C15—C16—C17	−96.2 (6)	C18—C21—C22—C23	−176.8 (2)
C14—C15—C16—C17	21.2 (7)	C18—C21—C22—S2	1.2 (2)
C10—C13—C17—C18	18 (6)	C19—S2—C22—C21	−0.85 (18)
C14—C13—C17—C18	−170.0 (15)	C19—S2—C22—C23	177.27 (19)
C10—C13—C17—C16	−170 (4)	C21—C22—C23—C24	−25.3 (4)
C14—C13—C17—C16	2 (3)	S2—C22—C23—C24	156.91 (19)
F6—C16—C17—C13	−140 (2)	C21—C22—C23—C29	152.5 (2)
F5—C16—C17—C13	104 (2)	S2—C22—C23—C29	−25.2 (3)
C15—C16—C17—C13	−15 (2)	C29—C23—C24—C25	−0.7 (4)
F6—C16—C17—C18	32.8 (10)	C22—C23—C24—C25	177.3 (2)
F5—C16—C17—C18	−83.1 (9)	C23—C24—C25—C26	0.1 (4)
C15—C16—C17—C18	157.4 (7)	C24—C25—C26—C27	0.4 (4)
C11—C10—C13'—C17'	59 (14)	C25—C26—C27—C29	−0.4 (4)
C9—C10—C13'—C17'	−126 (9)	C25—C26—C27—C28	−179.4 (3)
C13—C10—C13'—C17'	−1 (100)	C26—C27—C29—C23	−0.1 (4)
C11—C10—C13'—C14'	−131 (9)	C28—C27—C29—C23	178.9 (2)
C9—C10—C13'—C14'	45 (13)	C24—C23—C29—C27	0.7 (4)
C13—C10—C13'—C14'	170 (100)	C22—C23—C29—C27	−177.2 (2)

Experimental details

Crystal data
Chemical formula	C₂₉H₂₂F₆S₂
M_r	548.59
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	11.9825 (16), 9.2708 (12), 22.935 (3)
β (°)	92.934 (2)
V (Å³)	2544.4 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.24 × 0.22 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.728, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	13927, 5176, 3308
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.112, 1.02
No. of reflections	5176
No. of parameters	426
No. of restraints	158
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.18

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

Selected geometric parameters (Å, º) top

S1—C11	1.720 (2)	C16—C17	1.500 (6)
S1—C8	1.729 (2)	C13'—C17'	1.34 (2)
S2—C19	1.724 (2)	C13'—C14'	1.514 (10)
S2—C22	1.727 (2)	C14'—C15'	1.522 (10)
C13—C17	1.354 (11)	C15'—C16'	1.525 (10)
C13—C14	1.504 (5)	C16'—C17'	1.511 (10)
C14—C15	1.526 (6)	C17'—C18	1.476 (10)
C15—C16	1.518 (6)

C6—C7—C8—S1	179.81 (19)	C10—C13'—C17'—C18	−20 (18)
C11—C10—C13—C17	40 (5)	C13'—C17'—C18—C19	66 (9)
C10—C13—C17—C18	18 (6)	C13—C17—C18—C19	35 (3)
C11—C10—C13'—C17'	59 (14)	S2—C22—C23—C24	156.91 (19)

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

3,3,4,4,5,5-Hexafluoro-1,2-bis­[2-methyl-5-(3-methyl­phen­yl)-3-thien­yl]cyclo­pent-1-ene, a new photochromic diaryl­ethene compound

Supporting information

Key indicators

checkCIF/PLATON results

3,3,4,4,5,5-Hexafluoro-1,2-bis[2-methyl-5-(3-methylphenyl)-3-thienyl]cyclopent-1-ene, a new photochromic diarylethene compound