3,3,4,4,5,5-Hexafluoro-1-[5-(3-fluoro­phen­yl)-2-methyl-3-thien­yl]-2-(2-methyl-5-phenyl-3-thien­yl)cyclo­pent-1-ene

In the crystal structure of the title compound, C₂₇H₁₇F₇S₂, there are two mol­ecules in the asymmetric unit. In the two mol­ecules, the distances between the two reactive C atoms, i.e. the ring C atoms to which the methyl groups are attached, are 3.553 (6) and 3.624 (6) Å. The dihedral angles between the thio­phene ring and the adjacent benzene rings are 13.7 (1) and 20.9 (2)° in one mol­ecule, and 28.2 (1) and 10.1 (1)° in the other.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](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

---

S1. Comment

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.

S2. Experimental

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.

S3. Refinement

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 U_iso(H) values of 1.2 or 1.5 (for methyl) times U_eq(C).

Computing details

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.

Figures

	Fig. 1. View of one independent molecule of the title compound, shown with 35% probability ellipsoids; H atoms are shown as spheres of arbitrary radii. Only one component of the disordered F atom is shown.
	Fig. 2. View of the second molecule of the title compound, shown with 35% probability ellipsoids; H atoms are shown as spheres of arbitrary radii. Only one component of the disordered F atom is shown.

3,3,4,4,5,5-Hexafluoro-1-[5-(3-fluorophenyl)-2-methyl-3-thienyl]- 2-(2-methyl-5-phenyl-3-thienyl)cyclopent-1-ene

Crystal data

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) Å^3	Prism, colorless
Z = 8	0.6 × 0.5 × 0.2 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.143	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.001P)^2 + 1P] where P = (Fo^2 + 2Fc^2)/3
8526 reflections	(Δ/σ)max = 0.002
661 parameters	Δρmax = 0.88 e Å^−3
4 restraints	Δρmin = −0.40 e Å^−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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