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The title compound, C23H22F6O4S2, a photochromic dithienyl­ethene, is a promising material for optical storage and other optoelectrical devices. The mol­ecule adopts a photoactive antiparallel conformation in the crystalline state. The distance between the two reactive C atoms which are involved in potential ring closure is 3.829 (4) Å. The dihedral angles between the central cyclo­pentene ring and the adjacent thio­phene rings are 55.38 (7) and 54.81 (9)°. The colourless crystals turn magenta when exposed to UV radiation and the process is reversible.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105025758/fg1872sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105025758/fg1872Isup2.hkl
Contains datablock I

CCDC reference: 285804

Comment top

Photochromic compounds have been extensively investigated for their possible application in optoelectronics, such as optical memories, photoswitches and waveguides (Crano & Guglielmetti, 1999). Among all photochromic systems, diarylethene derivatives are the most promising candidates for optical memories and other optoelectronic devices because of the good thermal stability of the two isomers and their high sensitivity, fast response and high fatigue resistance (Irie, 2000; Tian & Yang, 2004). Generally, diarylethenes with thiophene heterocyclic rings have two interconverting conformations in almost equal amounts in solution, i.e. anti-parallel and parallel conformations (Irie & Mohri, 1988; Uchida et al., 1990); only anti-parallel conformations can undergo effective photocyclization reactions by a conrotatory mechanism, while the parallel conformations are photochemically inactive (Yamada et al., 2000). However, there is no interconversion between the two conformers in the crystalline phase of diarylethenes and the molecules are regularly oriented in a fixed conformation (Pu et al., 2003, 2004, 2005), except for one example (Kobatake et al., 2005) where there are two independent molecules with different conformations in the asymmetric unit. In addition, photochromic diarylethene crystals with an anti-parallel conformation can reversibly turn various colours (yellow, red, blue or green) from colourless, depending on their molecular structure, upon irradiation with UV and appropriate wavelength visible light (Kobatake & Irie, 2004). These crystals also exhibit good thermal stability of the two isomers and remarkable fatigue resistance. Crystals of diarylethenes in the anti-parallel conformation are thus very promising for practical applications.

In the present work, the title photochromic diarylethene, (Ia), was synthesized. We have previously reported (Pu et al., 2002) the structure of the 2-methyl analogue, (II), of this compound. In order to investigate systematically the substituent effect at the 2-position of the thiophene of diarylethenes on their photochemical properties, we have now determined the structure of the title compound, (Ia). The 2-methyl and 2-ethyl compounds differ from each other, not only in their crystal structures but also in various photochemical properties, such as their absorption maxima, ease of cyclization, cycloreversion quantum yield and oxidation–reduction potentials.

The molecular structure of (Ia) is shown in Fig. 1, a packing diagram is shown in Fig. 2 and selected geometric parameters are given in Table 1. As shown in Fig. 1(a), the molecule has approximate twofold symmetry, with the two thiophene rings in a photoactive anti-parallel conformation in the crystal. The hexafluorocyclopentene ring adopts a C4-envelope conformation with the flap atom (C4) equally disordered over two sites (C4 and C4'), with concomitant disorder of the attached F atoms (see Fig. 1b, with details in the Experimental section). In the cyclopent-1-ene ring, the C1—C2 bond is clearly a double bond, and the other bonds from C1 and C2 (Table 1) are clearly single bonds.

The two independent planar thiophene ring systems have essentially identical geometries and the dihedral angles between the central cyclopent-1-ene ring and the adjacent thiophene rings are 55.38 (7) and 54.81 (9)°. The corresponding values in the methyl analogue, (II), are both 49°. This conformation leads to a C12···C22 separation of 3.829 (4) Å [compared with 3.67 Å in (II)], which is short enough, theoretically, for a ring-closure reaction to take place in the crystalline phase (Ramamurthy & Venkatesan, 1987) to generate compound (Ib). The orientations of the ethyl groups at C12 and C22 are defined by the torsion angles C13—C12—C16—C17 [−139.8 (4)°] and C23—C22—C26—C27 [120.8 (4)°].

The two terminal 1,3-dioxolane rings both have envelope conformations; the O31/C32/O33/C34/C35 ring has a C32-envelope conformation, while the O41/C42/O43/C44/C45 ring adopts an O41-envelope form. Their orientations relative to the thiophene rings are presumably largely determined by crystal-packing considerations and lead to torsion angles H32—C32—C15—S11 166° and H42—C42—C25—S21 − 176°.

In the crystal, molecules related by a 21 screw axis are linked by weak C—H···F intermolecular interactions from one of the dioxolane C—H groups to generate chains extending along the b direction, as shown in Fig. 2; details are given in Table 2.

Crystals of (Ia) showed photochromic reaction in accordance with the expected ring closure, to form (Ib). Upon irradiation with light of wavelength 254 nm, the colourless crystals of (Ia) quickly became magenta-coloured, as shown in Fig. 3. When observed under polarized light, the intensity of the magenta colour changed on rotation of the crystalline sample. This phenomenon suggests that the closed-ring molecules of (Ib) are packed regularly in the crystal, but we have not been able to establish the crystal structure of (Ib). When the magenta crystal was dissolved in hexane, the solution was magenta-coloured and the absorption maximum was observed at 542 nm, consistent with the presence of the closed-ring isomer, (Ib). The magenta colour disappeared upon irradiation with light of wavelength 510 nm or daylight, and the absorption spectrum of the solution containing the colourless material was the same as that of solutions of the open-ring isomer, (Ia).

Experimental top

The title diarylethene (Ia) was originally derived from 5-ethylthiophene-2-carbaldehyde, (1). First, 4-bromo-5-ethylthiophene-2-carbaldehyde, (2), was afforded in 73.3% yield by brominating compound (1) in acetic acid at room temperature. The dioxolane acetal, (3), was then prepared in 84.0% yield by refluxing under Dean–Stark conditions in the presence of compound (2), glycol and p-toluenesulfonic acid (TsOH) in benzene. Finally, to a stirred solution of compound (3) (2.296 g, 8.73 mmol) in tetrahydrofuran (50 ml) was added dropwise a 2.5 M n-BuLi Solution? In what solvent? (3.5 ml, 8.75 mmol) at 195 K under a nitrogen atmosphere. Stirring was continued for 30 min and then octafluorocyclopentene (0.59 ml, 4.36 mmol) was added slowly to the reaction mixture. The mixture was then stirred for 2.5 h at 195 K. The reaction was quenched by the addition of water. After a series of routine operations, the title compound, (Ia) (1.2 g, 2.2 mmol), was obtained in 50.9% yield by column chromatography on SiO2 using CHCl3 as the eluent. The compound was crystallized from chloroform–hexane (1:2, v/v at room temperature and produced crystals suitable for X-ray analysis. The crystals of (Ia) had the following elementary analysis and NMR data: m.p.: 400.4–400.6 K; analysis calculated for C23H22F6O4S2: C 51.11, H 4.10%; found: C 51.23, H 4.20%; 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 0.924–0.961 (t, 6H, J = 7.8 Hz, –CH3), 2.192–2.248 (q, 4H, J = 7.5 Hz, –CH2), 4.002–4.036 (t, 4H, J = 6.8 Hz, –CH2), 4.101–4.136 (t, 4H, J = 7.0 Hz, –CH2), 6.021 (s, 2H, –CH), 7.094 (s, 2H, thiophene-H).

Refinement top

It was obvious from electron-density maps that the CF2 group at C4 was disordered, corresponding with two orientations of the cyclopent-1-ene ring in a C4-envelope conformation. This disorder was readily modelled with atom C4 disordered over two sites (C4 and C4'), with F atoms F41 and F42, and F41' and F42', respectively. DFIX restraints were used to keep the C4—F, C4'—F and F···F separations to be in agreement with the observed C—F geometry at the C3 and C5 sites. Initially, the two disordered orientations were refined with tied occupancy parameters, but as these refined occupancy values were not significantly different from 1/2, the occupancies were then fixed at 0.5 for the final refinement cycles. All H atoms were clearly defined in difference maps and were allowed for as riding atoms, with C—H distances in the range 0.96–0.98 Å and with Uiso(H) = 1.2 and 1.5Ueq(C).

Computing details top

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 top
[Figure 1] Fig. 1. (a) The structure of the title compound, with 20% probability displacement ellipsoids. For clarity, only one orientation of the disordered cyclopent-1-ene ring is shown. (b) A ball-and-stick diagram, showing the disorder at C4 in the cyclopent-1-ene ring.
[Figure 2] Fig. 2. A view along the b direction, showing the C—H···F interactions in (Ia) (dashed lines). [Symmetry codes: (i) ?; (ii) ?.] Please provide missing symmetry codes.
[Figure 3] Fig. 3. A view of crystals of the colourless compound, (Ia), and the same crystals after exposure to UV radiation, (Ib).
1,2-Bis[5-(1,3-dioxolan-2-yl)-2-ethyl-3-thienyl]-3,3,4,4,5,5- hexafluorocyclopent-1-ene top
Crystal data top
C23H22F6O4S2F(000) = 1112
Mr = 540.53Dx = 1.489 Mg m3
Monoclinic, P21/nMelting point: 400 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 13.353 (2) ÅCell parameters from 24 reflections
b = 13.370 (2) Åθ = 4.9–12.9°
c = 13.600 (3) ŵ = 0.30 mm1
β = 96.796 (11)°T = 295 K
V = 2411.0 (7) Å3Grain, colourless
Z = 40.5 × 0.5 × 0.4 mm
Data collection top
Bruker P4
diffractometer
Rint = 0.026
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.0°
Graphite monochromatorh = 115
ω scansk = 115
5323 measured reflectionsl = 1616
4231 independent reflections3 standard reflections every 97 reflections
3377 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.144 w = 1/[σ2(Fo2) + (0.0639P)2 + 1.2878P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
4231 reflectionsΔρmax = 0.39 e Å3
340 parametersΔρmin = 0.29 e Å3
6 restraintsExtinction correction: SHELXTL (Bruker, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0021 (7)
Crystal data top
C23H22F6O4S2V = 2411.0 (7) Å3
Mr = 540.53Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.353 (2) ŵ = 0.30 mm1
b = 13.370 (2) ÅT = 295 K
c = 13.600 (3) Å0.5 × 0.5 × 0.4 mm
β = 96.796 (11)°
Data collection top
Bruker P4
diffractometer
Rint = 0.026
5323 measured reflections3 standard reflections every 97 reflections
4231 independent reflections intensity decay: none
3377 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0496 restraints
wR(F2) = 0.144H-atom parameters constrained
S = 1.05Δρmax = 0.39 e Å3
4231 reflectionsΔρmin = 0.29 e Å3
340 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
xyzUiso*/UeqOcc. (<1)
S110.61709 (5)0.50947 (6)0.43250 (7)0.0716 (3)
S210.59373 (6)0.17217 (6)0.73738 (6)0.0710 (3)
F310.9032 (2)0.0754 (2)0.59655 (16)0.1218 (9)
F320.81264 (16)0.03258 (15)0.46600 (19)0.1017 (7)
F411.0160 (3)0.1798 (4)0.5409 (4)0.1188 (18)0.50
F420.9775 (6)0.1094 (5)0.4036 (5)0.138 (4)0.50
F41'1.0146 (3)0.1375 (5)0.4464 (6)0.100 (2)0.50
F42'0.8857 (4)0.1186 (3)0.3437 (3)0.0966 (13)0.50
F510.96866 (15)0.32777 (17)0.4679 (2)0.1165 (9)
F520.87636 (19)0.2853 (3)0.33976 (16)0.1400 (12)
O310.77267 (19)0.69553 (15)0.39772 (17)0.0820 (7)
O330.68496 (19)0.70907 (15)0.52895 (17)0.0808 (6)
O410.41057 (15)0.02067 (16)0.66613 (16)0.0730 (6)
O430.53379 (16)0.0541 (2)0.7667 (2)0.0979 (9)
C10.80209 (18)0.27763 (18)0.48668 (18)0.0483 (5)
C20.78153 (18)0.19196 (18)0.53188 (18)0.0489 (6)
C30.8555 (2)0.11210 (19)0.5132 (2)0.0582 (6)
C40.9400 (4)0.1674 (9)0.4695 (6)0.0657 (15)0.50
C4'0.9157 (4)0.1531 (9)0.4339 (5)0.0657 (15)0.50
C50.8948 (2)0.2655 (2)0.4347 (2)0.0576 (6)
C120.6496 (2)0.3850 (2)0.4398 (2)0.0591 (7)
C130.74850 (18)0.37359 (18)0.47795 (18)0.0492 (6)
C140.79658 (19)0.46707 (18)0.50225 (19)0.0520 (6)
H140.86360.47280.52950.062*
C150.7354 (2)0.5462 (2)0.4819 (2)0.0569 (6)
C160.5725 (2)0.3066 (2)0.4062 (3)0.0797 (9)
H16A0.60750.24470.39540.096*
H16B0.53120.29480.45920.096*
C170.5054 (4)0.3308 (3)0.3153 (4)0.1203 (17)
H17A0.45690.27820.30140.180*
H17B0.54460.33740.26090.180*
H17C0.47100.39250.32440.180*
C220.6855 (2)0.2270 (2)0.6762 (2)0.0572 (6)
C230.70304 (18)0.17008 (18)0.59622 (18)0.0496 (6)
C240.6430 (2)0.08147 (19)0.5865 (2)0.0556 (6)
H240.64660.03450.53650.067*
C250.5804 (2)0.0727 (2)0.6570 (2)0.0593 (7)
C260.7361 (2)0.3200 (2)0.7176 (2)0.0709 (8)
H26A0.78930.33750.67790.085*
H26B0.76740.30630.78420.085*
C270.6668 (3)0.4083 (3)0.7207 (3)0.0992 (12)
H27A0.70570.46670.74090.149*
H27B0.61950.39540.76720.149*
H27C0.63090.41900.65620.149*
C320.7620 (2)0.6544 (2)0.4910 (2)0.0631 (7)
H320.82520.66230.53480.076*
C340.6800 (4)0.8022 (3)0.4808 (3)0.1126 (15)
H34A0.71090.85360.52480.135*
H34B0.61030.82050.46070.135*
C350.7335 (4)0.7920 (3)0.3956 (3)0.1049 (13)
H35A0.68810.80250.33530.126*
H35B0.78740.84090.39800.126*
C420.5107 (2)0.0115 (2)0.6726 (2)0.0672 (8)
H420.51660.06280.62220.081*
C440.4463 (2)0.0716 (3)0.8079 (3)0.0822 (9)
H44A0.44670.03520.86960.099*
H44B0.43900.14240.82100.099*
C450.3633 (2)0.0366 (3)0.7348 (2)0.0751 (8)
H45A0.32730.09280.70220.090*
H45B0.31620.00390.76640.090*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S110.0526 (4)0.0525 (4)0.1063 (6)0.0090 (3)0.0049 (4)0.0039 (4)
S210.0753 (5)0.0754 (5)0.0676 (5)0.0160 (4)0.0308 (4)0.0079 (4)
F310.1335 (19)0.143 (2)0.0867 (13)0.0869 (17)0.0042 (13)0.0186 (13)
F320.0857 (13)0.0736 (12)0.151 (2)0.0037 (10)0.0377 (13)0.0458 (12)
F410.056 (2)0.120 (4)0.175 (5)0.003 (2)0.007 (3)0.054 (4)
F420.167 (8)0.075 (4)0.197 (10)0.023 (5)0.132 (8)0.005 (5)
F41'0.056 (3)0.080 (5)0.169 (7)0.024 (3)0.040 (3)0.007 (4)
F42'0.132 (4)0.090 (3)0.075 (3)0.015 (3)0.042 (2)0.029 (2)
F510.0604 (11)0.0989 (15)0.199 (3)0.0187 (11)0.0508 (13)0.0499 (16)
F520.1163 (18)0.239 (3)0.0733 (13)0.071 (2)0.0452 (12)0.0389 (16)
O310.1070 (17)0.0510 (11)0.0954 (16)0.0094 (11)0.0425 (13)0.0095 (10)
O330.1079 (17)0.0520 (11)0.0884 (15)0.0146 (11)0.0371 (13)0.0010 (10)
O410.0530 (11)0.0783 (13)0.0878 (14)0.0024 (10)0.0091 (10)0.0252 (11)
O430.0567 (12)0.1094 (19)0.128 (2)0.0024 (12)0.0135 (12)0.0673 (16)
C10.0455 (12)0.0471 (13)0.0533 (13)0.0047 (10)0.0100 (10)0.0023 (10)
C20.0478 (13)0.0462 (13)0.0536 (13)0.0036 (10)0.0093 (10)0.0031 (11)
C30.0595 (15)0.0474 (14)0.0682 (16)0.0083 (12)0.0099 (13)0.0034 (12)
C40.045 (3)0.058 (3)0.096 (6)0.002 (3)0.018 (3)0.017 (4)
C4'0.045 (3)0.058 (3)0.096 (6)0.002 (3)0.018 (3)0.017 (4)
C50.0522 (14)0.0603 (16)0.0627 (15)0.0017 (12)0.0173 (12)0.0054 (13)
C120.0519 (14)0.0515 (15)0.0728 (17)0.0025 (12)0.0026 (12)0.0028 (13)
C130.0474 (13)0.0448 (13)0.0564 (13)0.0029 (10)0.0105 (10)0.0055 (11)
C140.0459 (13)0.0486 (13)0.0614 (15)0.0026 (11)0.0067 (11)0.0061 (11)
C150.0533 (14)0.0508 (14)0.0664 (16)0.0036 (11)0.0062 (12)0.0011 (12)
C160.0618 (17)0.0591 (17)0.114 (3)0.0041 (14)0.0057 (17)0.0008 (17)
C170.111 (3)0.094 (3)0.141 (4)0.017 (2)0.048 (3)0.002 (3)
C220.0549 (14)0.0580 (15)0.0604 (15)0.0047 (12)0.0136 (12)0.0007 (12)
C230.0495 (13)0.0486 (13)0.0525 (13)0.0029 (10)0.0128 (10)0.0046 (11)
C240.0602 (15)0.0453 (13)0.0637 (15)0.0021 (11)0.0177 (12)0.0029 (11)
C250.0579 (15)0.0547 (15)0.0674 (16)0.0026 (12)0.0159 (13)0.0044 (12)
C260.078 (2)0.075 (2)0.0614 (16)0.0200 (16)0.0156 (14)0.0108 (14)
C270.106 (3)0.077 (2)0.121 (3)0.011 (2)0.037 (2)0.033 (2)
C320.0621 (16)0.0486 (14)0.0775 (18)0.0070 (12)0.0034 (14)0.0009 (13)
C340.163 (4)0.064 (2)0.120 (3)0.039 (2)0.057 (3)0.018 (2)
C350.152 (4)0.068 (2)0.100 (3)0.033 (2)0.036 (3)0.0158 (19)
C420.0640 (17)0.0569 (16)0.084 (2)0.0032 (13)0.0240 (15)0.0066 (14)
C440.073 (2)0.096 (2)0.080 (2)0.0002 (18)0.0198 (17)0.0152 (18)
C450.0589 (17)0.084 (2)0.084 (2)0.0083 (15)0.0157 (15)0.0130 (17)
Geometric parameters (Å, º) top
S11—C151.713 (3)C14—H140.93
S11—C121.719 (3)C15—C321.491 (4)
S21—C251.717 (3)C16—C171.475 (5)
S21—C221.724 (3)C16—H16A0.97
F31—C31.327 (3)C16—H16B0.97
F32—C31.335 (3)C17—H17A0.96
F41—C41.328 (2)C17—H17B0.96
F42—C41.327 (2)C17—H17C0.96
F41'—C4'1.327 (2)C22—C231.370 (4)
F42'—C4'1.327 (2)C22—C261.494 (4)
F51—C51.329 (3)C23—C241.428 (4)
F52—C51.312 (3)C24—C251.349 (4)
O31—C351.392 (4)C24—H240.93
O31—C321.405 (4)C25—C421.492 (4)
O33—C341.404 (4)C26—C271.503 (5)
O33—C321.409 (4)C26—H26A0.97
O41—C421.397 (4)C26—H26B0.97
O41—C451.413 (4)C27—H27A0.96
O43—C441.373 (4)C27—H27B0.96
O43—C421.402 (4)C27—H27C0.96
C1—C21.344 (3)C32—H320.98
C1—C131.467 (3)C34—C351.438 (5)
C1—C51.505 (3)C34—H34A0.97
C2—C231.472 (3)C34—H34B0.97
C2—C31.496 (3)C35—H35A0.97
C3—C4'1.523 (11)C35—H35B0.97
C3—C41.528 (12)C42—H420.98
C4—C51.498 (11)C44—C451.475 (5)
C4'—C51.529 (12)C44—H44A0.97
C12—C131.369 (4)C44—H44B0.97
C12—C161.503 (4)C45—H45A0.97
C13—C141.426 (3)C45—H45B0.97
C14—C151.346 (4)
C15—S11—C1292.29 (13)C16—C17—H17C109.5
C25—S21—C2292.73 (13)H17A—C17—H17C109.5
C35—O31—C32107.7 (2)H17B—C17—H17C109.5
C34—O33—C32106.6 (3)C23—C22—C26130.5 (2)
C42—O41—C45106.9 (2)C23—C22—S21110.2 (2)
C44—O43—C42109.6 (2)C26—C22—S21119.2 (2)
C2—C1—C13131.2 (2)C22—C23—C24112.8 (2)
C2—C1—C5110.3 (2)C22—C23—C2124.2 (2)
C13—C1—C5118.4 (2)C24—C23—C2122.8 (2)
C1—C2—C23129.8 (2)C25—C24—C23113.2 (2)
C1—C2—C3110.9 (2)C25—C24—H24123.4
C23—C2—C3119.3 (2)C23—C24—H24123.4
F31—C3—F32104.5 (3)C24—C25—C42128.0 (3)
F31—C3—C2112.3 (2)C24—C25—S21111.1 (2)
F32—C3—C2113.3 (2)C42—C25—S21120.9 (2)
F31—C3—C4'119.9 (3)C22—C26—C27114.3 (3)
F32—C3—C4'100.2 (3)C22—C26—H26A108.7
C2—C3—C4'106.1 (4)C27—C26—H26A108.7
F31—C3—C4102.1 (3)C22—C26—H26B108.7
F32—C3—C4119.5 (3)C27—C26—H26B108.7
C2—C3—C4104.7 (4)H26A—C26—H26B107.6
F42—C4—F41104.46 (11)C26—C27—H27A109.5
F42—C4—C5117.9 (8)C26—C27—H27B109.5
F41—C4—C5111.5 (7)H27A—C27—H27B109.5
F42—C4—C3109.5 (8)C26—C27—H27C109.5
F41—C4—C3108.2 (7)H27A—C27—H27C109.5
C5—C4—C3105.0 (3)H27B—C27—H27C109.5
F42'—C4'—F41'104.52 (11)O31—C32—O33106.5 (2)
F42'—C4'—C3113.7 (7)O31—C32—C15110.7 (2)
F41'—C4'—C3117.0 (8)O33—C32—C15110.9 (2)
F42'—C4'—C5108.2 (7)O31—C32—H32109.6
F41'—C4'—C5109.5 (8)O33—C32—H32109.6
C3—C4'—C5103.7 (3)C15—C32—H32109.6
F52—C5—F51104.7 (3)O33—C34—C35106.9 (3)
F52—C5—C4120.6 (3)O33—C34—H34A110.3
F51—C5—C4100.7 (3)C35—C34—H34A110.3
F52—C5—C1111.8 (2)O33—C34—H34B110.3
F51—C5—C1113.1 (2)C35—C34—H34B110.3
C4—C5—C1105.6 (4)H34A—C34—H34B108.6
F52—C5—C4'101.8 (3)O31—C35—C34107.0 (3)
F51—C5—C4'119.3 (3)O31—C35—H35A110.3
C1—C5—C4'105.7 (4)C34—C35—H35A110.3
C13—C12—C16129.2 (2)O31—C35—H35B110.3
C13—C12—S11110.8 (2)C34—C35—H35B110.3
C16—C12—S11119.9 (2)H35A—C35—H35B108.6
C12—C13—C14112.2 (2)O41—C42—O43106.7 (2)
C12—C13—C1124.6 (2)O41—C42—C25111.6 (2)
C14—C13—C1123.1 (2)O43—C42—C25111.3 (3)
C15—C14—C13113.3 (2)O41—C42—H42109.1
C15—C14—H14123.4O43—C42—H42109.1
C13—C14—H14123.4C25—C42—H42109.1
C14—C15—C32127.8 (3)O43—C44—C45106.2 (3)
C14—C15—S11111.4 (2)O43—C44—H44A110.5
C32—C15—S11120.7 (2)C45—C44—H44A110.5
C17—C16—C12115.3 (3)O43—C44—H44B110.5
C17—C16—H16A108.4C45—C44—H44B110.5
C12—C16—H16A108.4H44A—C44—H44B108.7
C17—C16—H16B108.4O41—C45—C44105.0 (2)
C12—C16—H16B108.4O41—C45—H45A110.7
H16A—C16—H16B107.5C44—C45—H45A110.7
C16—C17—H17A109.5O41—C45—H45B110.7
C16—C17—H17B109.5C44—C45—H45B110.7
H17A—C17—H17B109.5H45A—C45—H45B108.8
C13—C1—C2—C236.9 (5)S21—C22—C23—C241.0 (3)
C5—C1—C2—C23175.8 (2)C26—C22—C23—C20.3 (5)
C13—C1—C2—C3175.7 (2)S21—C22—C23—C2175.78 (19)
C5—C1—C2—C31.7 (3)C1—C2—C23—C2250.2 (4)
C1—C2—C3—C4'10.0 (3)C3—C2—C23—C22127.0 (3)
C23—C2—C3—C4'172.3 (3)C1—C2—C23—C24135.5 (3)
C1—C2—C3—C412.8 (3)C3—C2—C23—C2447.2 (3)
C23—C2—C3—C4164.9 (3)C22—C23—C24—C250.9 (3)
C2—C3—C4—C518.5 (4)C2—C23—C24—C25175.7 (2)
C2—C3—C4'—C516.8 (3)C23—C24—C25—C42177.0 (3)
C3—C4—C5—C117.6 (4)C23—C24—C25—S210.3 (3)
C2—C1—C5—C410.4 (3)C22—S21—C25—C240.3 (2)
C13—C1—C5—C4171.8 (3)C22—S21—C25—C42176.7 (2)
C2—C1—C5—C4'12.6 (3)C23—C22—C26—C27120.8 (4)
C13—C1—C5—C4'165.1 (3)S21—C22—C26—C2763.4 (3)
C3—C4'—C5—C117.7 (3)C35—O31—C32—O3321.7 (4)
C15—S11—C12—C130.6 (2)C35—O31—C32—C15142.3 (3)
C15—S11—C12—C16179.3 (3)C34—O33—C32—O3123.2 (4)
C16—C12—C13—C14179.2 (3)C34—O33—C32—C15143.7 (3)
S11—C12—C13—C140.8 (3)C14—C15—C32—O31102.0 (3)
C16—C12—C13—C15.0 (5)S11—C15—C32—O3173.1 (3)
S11—C12—C13—C1175.0 (2)C14—C15—C32—O33140.0 (3)
C2—C1—C13—C1256.1 (4)S11—C15—C32—O3344.9 (3)
C5—C1—C13—C12121.0 (3)C32—O33—C34—C3516.0 (5)
C2—C1—C13—C14128.5 (3)C32—O31—C35—C3411.6 (5)
C5—C1—C13—C1454.3 (3)O33—C34—C35—O312.7 (6)
C12—C13—C14—C150.6 (3)C45—O41—C42—O4323.5 (3)
C1—C13—C14—C15175.3 (2)C45—O41—C42—C25145.3 (3)
C13—C14—C15—C32175.3 (3)C44—O43—C42—O4114.8 (4)
C13—C14—C15—S110.1 (3)C44—O43—C42—C25136.8 (3)
C12—S11—C15—C140.3 (2)C24—C25—C42—O41120.4 (3)
C12—S11—C15—C32176.1 (2)S21—C25—C42—O4163.2 (3)
C13—C12—C16—C17139.8 (4)C24—C25—C42—O43120.5 (3)
S11—C12—C16—C1740.2 (5)S21—C25—C42—O4355.9 (3)
C25—S21—C22—C230.8 (2)C42—O43—C44—C450.5 (4)
C25—S21—C22—C26175.8 (2)C42—O41—C45—C4422.7 (4)
C26—C22—C23—C24175.1 (3)O43—C44—C45—O4113.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C35—H35A···F52i0.972.453.361 (5)157
Symmetry code: (i) x+3/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC23H22F6O4S2
Mr540.53
Crystal system, space groupMonoclinic, P21/n
Temperature (K)295
a, b, c (Å)13.353 (2), 13.370 (2), 13.600 (3)
β (°) 96.796 (11)
V3)2411.0 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.30
Crystal size (mm)0.5 × 0.5 × 0.4
Data collection
DiffractometerBruker P4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5323, 4231, 3377
Rint0.026
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.144, 1.05
No. of reflections4231
No. of parameters340
No. of restraints6
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.39, 0.29

Computer programs: XSCANS (Bruker, 1997), XSCANS, SHELXTL (Bruker, 1997), SHELXTL.

Selected bond lengths (Å) top
S11—C151.713 (3)C2—C231.472 (3)
S11—C121.719 (3)C2—C31.496 (3)
S21—C251.717 (3)C3—C4'1.523 (11)
S21—C221.724 (3)C3—C41.528 (12)
C1—C21.344 (3)C4—C51.498 (11)
C1—C131.467 (3)C4'—C51.529 (12)
C1—C51.505 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C35—H35A···F52i0.972.453.361 (5)157
Symmetry code: (i) x+3/2, y+1/2, z+1/2.
 

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