(4aR,8aS,9aR,10aS)-8a,9a-Difluoro-1,4,4a,5,8,8a,9,9a,10,10a-deca­hydro­anthracene-4a,10a-diol hemihydrate

The title compound, C₁₄H₁₈F₂O₂·0.5H₂O, a hemihydrate of a C_s-symmetric unsaturated difluoro­diol, crystallizes in the centrosymmetric space group P2/m (Z = 4). The asymmetric unit contains two crystallographically independent difluoro­diol half-mol­ecules, occupying the mirror planes at (x, 0, z) and (x, , z), and half a mol­ecule of water, lying on the twofold axis at (0, y, 0). Four difluoro­diol mol­ecules self-assemble around each solvent water mol­ecule via O—H...O hydrogen bonds in a near tetra­hedral symmetry to generate a cylindrical column-like architecture.

S1. Comment

As a part of our ongoing research, we have been actively involved in unravelling the interplay of various non-covalent interactions that build up the crystal structure of functionalized trans-decalins (Mehta et al., 2007; Mehta & Sen, 2009a,b, 2010). The primary focus of this investigation has been the O—H···O hydrogen-bonding networks in cyclitols (Posternak, 1962; Hudlicky & Cebulak, 1993) and their designer variants (polycyclitols) fashioned from a prototypical rigid 4a,8a-dihydroxy-trans-decalin backbone (Mehta & Ramesh, 2000, 2001; Nangia, 2010). In a recent endeavour along these lines, we reported the synthesis of the fluorinated polycyclitols (I) and (II), the solid-state self-assemblies of which were probed to elucidate the role of organic fluorine in crystal structures laden with O—H···O hydrogen bonds (Mehta & Sen, 2010).

The motivation for undertaking this study came from one of the well known scientific debates of the recent past – does organic fluorine engage in hydrogen bonding? (Howard et al., 1996; Dunitz & Taylor, 1997; Dunitz, 2004; Reichenbaecher et al., 2005; Dunitz & Schweizer, 2006; Cozzi et al., 2007). Being the most electronegative element and nearly isosteric with a hydroxy group (Bondi, 1964), covalently bonded fluorine might appear capable of mimicking an OH functionality as a potential hydrogen-bond acceptor. While a large body of scientific evidence points towards organic fluorine being a weak hydrogen-bond acceptor, capable of engaging in C—F···H—X (X is O, N or C) interactions (Madhavi et al., 2000; Nangia, 2000; Vangala et al., 2002; Desiraju, 2002; Mountford et al., 2003; Li et al., 2005; Bernet & Vasella, 2007; Borho & Xu, 2008; Chopra & Guru Row, 2011), other studies conclude that fluorine may not be involved in hydrogen bonding at all (Dunitz & Taylor, 1997; Dunitz, 2004; Dunitz & Schweizer, 2006; Cozzi et al., 2007).

Interestingly, weak Csp³—F···H—Csp³ interactions were observed and supramolecular recognition units, involving such interactions, were found to be conserved in the crystal structures of (I) and (II). Much in the way of a comparative study, inspired by a similar analysis carried out on the solid-state self-assemblies of (III) and (IV) (Mehta, Sen & Venkatesan, 2005), we report here the molecular packing of the title compound, (V). The fluorinated polycyclitol (V) formed the common synthetic precursor to both (I) and (II), and was obtained as a single diastereomer in a one-pot regio- and stereoselective epoxide ring opening of the syn-diepoxide, (VI) (Mehta et al., 2007) with pyridine poly(hydrogen fluoride) (see reaction scheme).

The unsaturated difluorodiol (V) crystallizes as a hemihydrate in the centrosymmetric monoclinic space group P2/m (Z = 2). Analysis of the crystal packing in (V) revealed that the asymmetric unit contains two C_s-symmetric molecules, occupying the mirror planes at (x,0,z) and (x,1/2,z), and a molecule of water, lying on the twofold axis at (0,y,0). The symmetry constraints thus imposed on the molecules of water by their occupancy at the special positions introduce a disorder in the positions of atoms H1W and H2W bonded to them. In addition, the H atoms bonded to the hydroxy atoms O1 and O2 in the asymmetric unit were also found to be disordered over two sites, A and B (Fig. 1).

Physically, this disorder in the H-atom positions can be viewed as a statistical average of the two possible modes in which the 1,3-syndiaxial hydroxy groups in (V) can participate in intramolecular O—H···O hydrogen bonding while being linked to the water molecules through intermolecular O—H···O hydrogen bonds (Fig. 2). Thus, each water molecule exhibits a near tetrahedral coordination around the O atom and is hydrogen-bonded to four molecules of (V) in a cyclindrical channel-like architecture, consisting of a hydrophilic interior and a hydrophobic exterior. The translationally related channels are held together primarily via van der Waals interactions, though soft C—H···F contacts (C2—H2B···F2 = 2.55 Å and = 131°) can also be discerned between them.

While understandably bearing very little resemblance to the molecular packing in anhydrous (I), the water-directed solid-state self-assembly of (V) displays an uncanny similarity to that observed for the crystalline monohydrate of the C_2h symmetric diol (VII) (Mehta, Sen & Ramesh, 2005). Crystallizing in the centrosymmetric tetragonal space group P4₂/m (Z = 2), the C_2h symmetric diol molecules of (VII) occupy centres of symmetry at (1/2, 0, 0) and (0, 1/2, 1/2) (site symmetry 2/m), while the water molecules are located on the 4₂ axis at special positions (1/2, 1/2, 1/4) and (1/2, 1/2, 3/4) (site symmetry 4). Consequently, a disorder in the positions of the O-bound H atoms – nearly identical to that observed in (V) – and a highly symmetric tetrahedral arrangement of the diol molecules around each molecule of water are also noted in the crystal structure of (VII). A possible rationale for the observed similarities in the water-directed self-assemblies of (V) and (VII) might lie in (a) a compatible matching between the hydroxy group and water as being able to function as both a hydrogen-bond donor and acceptor, and (b) the maximization of the hydrogen bonding and the formation of infinite hydrogen-bonding chains by allowing water molecules to act as bridges between the less accessible axially locked tertiary hydroxy groups.

Related literature

For related literature, see: Bernet & Vasella (2007); Bondi (1964); Borho & Xu (2008); Chopra & Guru Row (2011); Cozzi et al. (2007); Desiraju (2002); Dunitz (2004); Dunitz & Schweizer (2006); Dunitz & Taylor (1997); Howard et al. (1996); Hudlicky & Cebulak (1993); Li et al. (2005); Madhavi et al. (2000); Mehta & Ramesh (2000, 2001); Mehta & Sen (2009a, 2009b, 2010); Mehta et al. (2007); Mehta, Sen & Ramesh (2005); Mehta, Sen & Venkatesan (2005); Mountford et al. (2003); Nangia (2000, 2010); Posternak (1962); Reichenbaecher et al. (2005); Sheldrick (2008); Vangala et al. (2002).

S2. Experimental

Details pertaining to the synthesis and spectroscopic characterization of (V) have already been reported (Mehta & Sen, 2010). Single crystals of (V), suitable for X-ray diffraction studies, were grown by slow solvent evaporation of a solution in dichloromethane under ambient temperature and pressure.

S3. Refinement

The methine (CH) and methylene (CH₂) H atoms were placed in geometrically idealized positions and allowed to ride on their parent atoms, with C—H = 0.93 and 0.97 Å respectively, and U_iso(H) = 1.2U_eq(C). All O-bound H atoms were located in the difference Fourier map. Their positions were refined freely, along with an isotropic displacement parameter. However, a DFIX restraint (SHELXL97; Sheldrick, 2008) was applied to the O—H distances (target value 0.84 Å with an s.u. of 0.02 Å) for each of the two H atoms of the water molecule while refining their positions.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

Fig. 1. Molecular structure of the difluorodiol hemihydrate, (V), showing the atom-numbering scheme of the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level. For the sake of clarity, the two crystallographically independent difluorodiol molecules have been labelled A and B. Unlabelled atoms are related to labelled atoms by the symmetry operators (x, -y + 1, z) and (x, -y, z) for molecules A and B, respectively.

Fig. 2. The molecular packing of (V), showing the tetrahedral coordination of the difluorodiol molecules around the solvent water molecules. The disorder in the positions of the water H atoms and the hydroxy groups can be modelled as the statistical average of the O—H···O hydrogen-bonding modes (a) and (b). Non-interacting H atoms have been removed for clarity. Dotted lines indicate O—H···O hydrogen bonds. (In the electronic version of the paper, difluorodiol molecules A and B are shown in blue and orange, respectively.)

(4aR,8aS,9aR,10aS)-8a,9a-Difluoro- 1,4,4a,5,8,8a,9,9a,10,10a-decahydroanthracene-4a,10a-diol hemihydrate

Crystal data

C14H18F2O2·0.5H2O	F(000) = 564
Mr = 265.29	Dx = 1.285 Mg m^−3
Monoclinic, P2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2y	Cell parameters from 796 reflections
a = 10.812 (2) Å	θ = 2.6–22.7°
b = 11.942 (2) Å	µ = 0.10 mm^−1
c = 10.868 (2) Å	T = 291 K
β = 102.274 (3)°	Block, colourless
V = 1371.2 (4) Å^3	0.12 × 0.09 × 0.08 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2677 independent reflections
Radiation source: fine-focus sealed tube	1857 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ϕ and ω scans	θmax = 25.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −13→13
Tmin = 0.988, Tmax = 0.992	k = −14→14
10273 measured reflections	l = −11→13

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0626P)^2 + 0.2432P] where P = (Fo^2 + 2Fc^2)/3
2677 reflections	(Δ/σ)max < 0.001
198 parameters	Δρmax = 0.26 e Å^−3
2 restraints	Δρmin = −0.14 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)
F1	0.43342 (9)	0.38588 (9)	0.79892 (11)	0.0568 (3)
F2	0.32511 (10)	0.11385 (8)	0.48237 (9)	0.0505 (3)
O1	0.11812 (12)	0.38847 (14)	0.85580 (13)	0.0461 (3)
O1W	0.0000	0.25119 (19)	0.0000	0.0471 (5)
O2	0.16704 (13)	0.11056 (14)	0.15644 (11)	0.0468 (3)
C1	0.29829 (16)	0.39274 (15)	0.76426 (16)	0.0455 (4)
C2	0.2523 (2)	0.28900 (17)	0.68771 (19)	0.0597 (6)
C3	0.2673 (2)	0.18496 (19)	0.7653 (3)	0.0772 (7)
C4	0.2900 (2)	0.18499 (19)	0.8885 (3)	0.0731 (7)
C5	0.30519 (18)	0.28861 (16)	0.96581 (18)	0.0525 (5)
C6	0.25576 (15)	0.39308 (15)	0.89030 (16)	0.0419 (4)
C7	0.2982 (2)	0.5000	0.9641 (2)	0.0412 (6)
C8	0.2639 (2)	0.5000	0.6905 (2)	0.0462 (6)
C9	0.17503 (15)	0.10696 (15)	0.29121 (15)	0.0413 (4)
C10	0.11317 (18)	0.21183 (16)	0.33123 (18)	0.0539 (5)
C11	0.1874 (2)	0.31554 (18)	0.3219 (2)	0.0668 (6)
C12	0.3075 (2)	0.31499 (18)	0.3147 (2)	0.0670 (6)
C13	0.38237 (18)	0.21105 (16)	0.31331 (19)	0.0540 (5)
C14	0.31788 (16)	0.10719 (15)	0.34975 (15)	0.0408 (4)
C15	0.3824 (2)	0.0000	0.3233 (2)	0.0420 (6)
C16	0.1130 (2)	0.0000	0.3264 (2)	0.0420 (6)
H1AO	0.091 (3)	0.452 (3)	0.846 (3)	0.044 (12)*	0.50
H1BO	0.090 (4)	0.348 (3)	0.897 (4)	0.046 (13)*	0.50
H1W	0.036 (4)	0.298 (3)	−0.039 (4)	0.076 (16)*	0.50
H2A	0.1636	0.2985	0.6482	0.072*
H2AO	0.122 (3)	0.157 (3)	0.124 (3)	0.034 (10)*	0.50
H2B	0.2991	0.2810	0.6214	0.072*
H2BO	0.158 (3)	0.043 (3)	0.133 (3)	0.052 (13)*	0.50
H2W	0.052 (3)	0.209 (3)	0.048 (3)	0.059 (12)*	0.50
H3	0.2601	0.1163	0.7239	0.093*
H4	0.2970	0.1164	0.9299	0.088*
H5A	0.3942	0.2990	1.0034	0.063*
H5B	0.2604	0.2796	1.0336	0.063*
H7A	0.3899	0.5000	0.9891	0.049*
H7B	0.2648	0.5000	1.0402	0.049*
H8A	0.3056	0.5000	0.6198	0.055*
H8B	0.1733	0.5000	0.6565	0.055*
H10A	0.0292	0.2200	0.2785	0.065*
H10B	0.1039	0.2028	0.4175	0.065*
H11	0.1468	0.3843	0.3211	0.080*
H12	0.3474	0.3834	0.3103	0.080*
H13A	0.4636	0.2199	0.3710	0.065*
H13B	0.3983	0.2006	0.2295	0.065*
H15A	0.3883	0.0000	0.2354	0.050*
H15B	0.4681	0.0000	0.3735	0.050*
H16A	0.0244	0.0000	0.2843	0.050*
H16B	0.1171	0.0000	0.4165	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0423 (6)	0.0616 (7)	0.0711 (7)	0.0091 (5)	0.0225 (5)	0.0029 (6)
F2	0.0629 (6)	0.0512 (6)	0.0337 (5)	−0.0002 (5)	0.0015 (4)	−0.0056 (5)
O1	0.0355 (7)	0.0464 (9)	0.0566 (9)	−0.0029 (6)	0.0104 (6)	0.0039 (7)
O1W	0.0449 (11)	0.0487 (13)	0.0467 (12)	0.000	0.0078 (9)	0.000
O2	0.0571 (8)	0.0461 (9)	0.0340 (7)	0.0040 (7)	0.0026 (6)	0.0051 (7)
C1	0.0450 (10)	0.0487 (11)	0.0442 (10)	0.0024 (8)	0.0124 (7)	−0.0030 (9)
C2	0.0730 (13)	0.0538 (13)	0.0563 (12)	−0.0023 (10)	0.0230 (10)	−0.0132 (10)
C3	0.1022 (18)	0.0417 (13)	0.0942 (19)	−0.0005 (12)	0.0358 (15)	−0.0113 (13)
C4	0.0889 (16)	0.0434 (13)	0.0922 (18)	0.0081 (11)	0.0308 (14)	0.0116 (13)
C5	0.0475 (10)	0.0553 (12)	0.0555 (12)	0.0055 (9)	0.0125 (9)	0.0157 (9)
C6	0.0379 (9)	0.0466 (11)	0.0412 (10)	0.0013 (8)	0.0086 (7)	0.0046 (8)
C7	0.0377 (12)	0.0538 (16)	0.0322 (12)	0.000	0.0077 (10)	0.000
C8	0.0543 (15)	0.0533 (16)	0.0323 (13)	0.000	0.0120 (11)	0.000
C9	0.0414 (9)	0.0440 (10)	0.0374 (9)	0.0049 (8)	0.0059 (7)	0.0008 (8)
C10	0.0561 (11)	0.0533 (12)	0.0505 (11)	0.0139 (9)	0.0075 (9)	−0.0033 (9)
C11	0.0897 (17)	0.0386 (12)	0.0680 (14)	0.0114 (11)	0.0075 (12)	−0.0028 (10)
C12	0.0853 (16)	0.0411 (12)	0.0701 (14)	−0.0091 (11)	0.0062 (12)	0.0021 (10)
C13	0.0533 (11)	0.0498 (12)	0.0554 (12)	−0.0116 (9)	0.0035 (9)	0.0051 (9)
C14	0.0436 (9)	0.0432 (10)	0.0347 (9)	−0.0024 (8)	0.0060 (7)	−0.0009 (8)
C15	0.0339 (12)	0.0513 (16)	0.0399 (13)	0.000	0.0057 (10)	0.000
C16	0.0342 (12)	0.0520 (16)	0.0400 (13)	0.000	0.0086 (10)	0.000

Geometric parameters (Å, º)

F1—C1	1.431 (2)	C7—H7A	0.97
F2—C14	1.4289 (19)	C7—H7B	0.97
O1—C6	1.456 (2)	C8—H8A	0.97
O1—H1AO	0.82 (3)	C8—H8B	0.97
O1—H1BO	0.77 (4)	C9—C10	1.526 (2)
O1W—H1W	0.843 (19)	C10—C11	1.491 (3)
O1W—H2W	0.846 (19)	C10—H10A	0.97
O2—C9	1.449 (2)	C10—H10B	0.97
O2—H2AO	0.78 (4)	C11—C12	1.316 (3)
O2—H2BO	0.85 (3)	C11—H11	0.93
C1—C2	1.516 (3)	C12—H12	0.93
C1—C8	1.515 (2)	C13—C12	1.484 (3)
C2—C3	1.491 (3)	C13—H13A	0.97
C2—H2A	0.97	C13—H13B	0.97
C2—H2B	0.97	C14—C13	1.516 (2)
C3—H3	0.93	C14—C9	1.540 (2)
C4—C3	1.309 (3)	C15—C14	1.514 (2)
C4—H4	0.93	C15—C14^i	1.514 (2)
C5—C4	1.485 (3)	C15—H15A	0.97
C5—H5A	0.97	C15—H15B	0.97
C5—H5B	0.97	C16—C9	1.529 (2)
C6—C1	1.535 (2)	C16—C9^i	1.529 (2)
C6—C5	1.526 (2)	C16—H16A	0.97
C7—C6	1.526 (2)	C16—H16B	0.97
F1—C1—C2	107.18 (15)	C9—C16—H16A	108.9
F1—C1—C6	104.36 (13)	C9^i—C16—H16A	108.9
F1—C1—C8	108.04 (16)	C9—C16—H16B	108.9
F2—C14—C13	106.76 (14)	C9^i—C16—H16B	108.9
F2—C14—C15	108.07 (15)	C9—O2—H2AO	112 (3)
F2—C14—C9	104.58 (13)	C9—O2—H2BO	105 (2)
O1—C6—C1	104.70 (13)	C10—C11—H11	118.3
O1—C6—C5	109.23 (15)	C10—C9—C14	110.03 (15)
O1—C6—C7	110.12 (15)	C10—C9—C16	111.85 (14)
O2—C9—C10	109.16 (15)	C11—C10—C9	112.79 (16)
O2—C9—C14	104.86 (13)	C11—C10—H10A	109.0
O2—C9—C16	110.04 (15)	C11—C10—H10B	109.0
C1—C2—H2A	109.0	C11—C12—C13	123.49 (19)
C1—C2—H2B	109.0	C11—C12—H12	118.3
C1—C8—H8A	108.4	C12—C11—C10	123.48 (19)
C1—C8—H8B	108.4	C12—C11—H11	118.3
C2—C1—C6	111.48 (16)	C12—C13—C14	113.53 (17)
C2—C3—H3	118.2	C12—C13—H13A	108.9
C3—C2—C1	112.77 (18)	C12—C13—H13B	108.9
C3—C2—H2A	109.0	C13—C12—H12	118.3
C3—C2—H2B	109.0	C13—C14—C9	111.72 (14)
C3—C4—C5	123.6 (2)	C14—C13—H13A	108.9
C3—C4—H4	118.2	C14—C13—H13B	108.9
C4—C3—C2	123.5 (2)	C14^i—C15—C14	115.4 (2)
C4—C3—H3	118.2	C14—C15—H15A	108.4
C4—C5—C6	113.14 (17)	C14^i—C15—H15A	108.4
C4—C5—H5A	109.0	C14—C15—H15B	108.4
C4—C5—H5B	109.0	C14^i—C15—H15B	108.4
C5—C4—H4	118.2	C15—C14—C13	112.70 (15)
C5—C6—C1	109.91 (15)	C15—C14—C9	112.45 (15)
C6—C5—H5A	109.0	C16—C9—C14	110.67 (15)
C6—C5—H5B	109.0	H1AO—O1—H1BO	119 (4)
C6—C7—H7A	108.8	H1W—O1W—H2W	113 (4)
C6—C7—H7B	108.8	H2A—C2—H2B	107.8
C6—O1—H1AO	109 (2)	H2AO—O2—H2BO	122 (4)
C6—O1—H1BO	112 (3)	H5A—C5—H5B	107.8
C7—C6—C1	110.95 (16)	H7A—C7—H7B	107.7
C7—C6—C5	111.69 (15)	H8A—C8—H8B	107.5
C8—C1—C2	112.68 (16)	H10A—C10—H10B	107.8
C8—C1—C6	112.55 (16)	H13A—C13—H13B	107.7
C9—C10—H10A	109.0	H15A—C15—H15B	107.5
C9—C10—H10B	109.0	H16A—C16—H16B	107.7
C9—C16—C9^i	113.34 (19)
F1—C1—C2—C3	70.6 (2)	C7—C6—C5—C4	−167.49 (17)
F2—C14—C13—C12	−72.82 (19)	C8—C1—C2—C3	−170.73 (19)
F2—C14—C9—C10	57.68 (17)	C9—C10—C11—C12	−17.8 (3)
F2—C14—C9—C16	−66.43 (17)	C9—C14—C13—C12	40.9 (2)
F2—C14—C9—O2	174.94 (13)	C9^i—C16—C9—C10	−178.31 (13)
O1—C6—C1—C2	−59.01 (19)	C9^i—C16—C9—C14	−55.2 (2)
O1—C6—C1—C8	68.73 (19)	C9^i—C16—C9—O2	60.2 (2)
O1—C6—C1—F1	−174.38 (13)	C10—C11—C12—C13	0.9 (4)
O1—C6—C5—C4	70.4 (2)	C13—C14—C9—C10	−57.43 (19)
O2—C9—C10—C11	−69.6 (2)	C13—C14—C9—C16	178.46 (15)
C1—C2—C3—C4	14.6 (3)	C13—C14—C9—O2	59.84 (18)
C1—C6—C5—C4	−43.9 (2)	C14—C13—C12—C11	−12.8 (3)
C5—C4—C3—C2	−0.8 (4)	C14^i—C15—C14—C13	−176.26 (13)
C5—C6—C1—C2	58.2 (2)	C14^i—C15—C14—C9	−48.9 (3)
C5—C6—C1—C8	−174.07 (16)	C14^i—C15—C14—F2	66.0 (2)
C5—C6—C1—F1	−57.17 (18)	C14—C9—C10—C11	44.9 (2)
C6—C1—C2—C3	−43.1 (2)	C15—C14—C13—C12	168.69 (17)
C6—C5—C4—C3	16.3 (3)	C15—C14—C9—C10	174.70 (15)
C7—C6—C1—C2	−177.77 (15)	C15—C14—C9—C16	50.6 (2)
C7—C6—C1—C8	−50.0 (2)	C15—C14—C9—O2	−68.04 (18)
C7—C6—C1—F1	66.86 (17)	C16—C9—C10—C11	168.35 (17)

Symmetry code: (i) x, −y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1AO···O1^ii	0.81 (4)	1.93 (4)	2.664 (2)	150 (3)
O1—H1BO···O1W^iii	0.76 (4)	2.00 (4)	2.762 (2)	174 (4)
O2—H2AO···O1W	0.77 (3)	2.02 (3)	2.769 (2)	165 (3)
O2—H2BO···O2^i	0.85 (4)	1.85 (4)	2.641 (2)	155 (3)
O1W—H1W···O1^iv	0.85 (4)	1.92 (4)	2.762 (2)	172 (4)
O1W—H2W···O2	0.85 (3)	1.92 (3)	2.769 (2)	179 (4)

Symmetry codes: (i) x, −y, z; (ii) x, −y+1, z; (iii) x, y, z+1; (iv) x, y, z−1.