Spiro­[1,3-dioxolane-2,4′-[8]­phenyl­sulfonyl­bi­cyclo­[4.2.0]­octan-1-ol]

The structure of the title compound, C₁₆H₂₀O₅S, has been determined as part of an investigation into the synthesis of fused carbocyclic ring systems with functionality and containing a cyclo­butanol ring. The conformational arrangement of the phenyl ring permits the formation of an infinite chain of intermolecular O—H...O—S hydrogen bonds. The dioxolane ring is removed from and does not participate in the chain of intermolecular hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.045
• wR factor = 0.130
• Data-to-parameter ratio = 17.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

We have recently shown that a novel cyclization reaction between the lithium enolates of simple unfunctionalized ketones and phenyl vinyl sulfoxide provides a simple and convenient route to the preparation of fused carbocyclic ring systems bearing a bridgehead hydroxy group (Loughlin & McCleary, 2003; Loughlin et al., 2002). In the current study, reaction of the lithium enolate of 1,4-cyclohexanedione mono-ethylene ketal (obtained from lithium diisopropylamide, LDA) with phenyl vinyl sulfoxide and subsequent oxidation with m-chloroperoxybenzoic acid (m-CPBA), generated the first representative of a functionalized bicyclo[4.2.0]octan-1-ol, the novel spiro compound, (I).

The spiro compound can be perceived as a synthetic precursor to a bicyclo[4.2.0]octan-3-one which is cognate of key structural components of, for example, benzocyclobutacarbazole antitumor agents (Graf-Christophe et al., 2000; Christophe et al., 1998), taxane precursors (Wender et al., 1997) and products arising from Norrish type II photoreactions (Osuka et al., 1987). Under the present reaction conditions, (I) was formed as the major bicyclo[4.2.0]octan-1-ol isomer in a 42:16:42 ratio of (I):(II):(III) from achiral 1,4-cyclohexanedione mono-ethylene ketal and phenyl vinyl sulfoxide with less than 5% of other products observed. Here we report the synthesis, isolation and structural characterization of the novel bicyclo[4.2.0]octan-1-ol (I).

The crystal structure determination (Fig. 1 and Table 1) shows that the relative stereochemistry about the bicyclo[4.2.0]alkanol ring in (I) is the same as that found for `parent' compound 8-(phenylsulfonyl)bicyclo[4.2.0]octan-1-ol, (IV) (Loughlin et al., 2002), with the C2–S bond cis to the bridgehead hydroxyl group and trans to the fused six-membered ring. As in the structure of (IV), this conformational structure is stabilized by three-centred `bifurcated' intra- and intermolecular hydrogen bonds between the hydroxyl proton and the sulfone O atoms (Fig. 2 and Table 2). These results indicate that the stereochemistry and molecular packing of this molecule is not significantly affected by the addition of the dioxane ring to the system.

S2. Experimental

1,4-Cyclohexanedione mono-ethylene ketal (0.5 g, 3.201 mmol) in THF (2 ml) was added to lithium diisopropylamide (1.4 M, 3.201 mmol, 2.30 ml) in THF (33 ml) at 273 K under nitrogen over 5 min and further reacted at 273 K for 1 h. Upon cooling to 263 K, rapid addition of phenyl vinyl sulfoxide (0.43 ml, 3.201 mmol) at 263 K, with the system shielded from light, a 10 min reaction time and workup as described elsewhere (Loughlin et al., 2002) gave the crude sulfoxide mixture (0.833 g). This was subsequently oxidized with m-CPBA (1 equivalent) in chloroform (30 ml). Work-up of the reaction mixture, as described elsewhere (Loughlin et al., 2002), was followed by silica chromatography (hexane–ethyl acetate, 70:30). A mixture of compounds (I)–(III) (485 mg, 47%) was obtained. An analytically pure sample of compound (I) was obtained by semi-preparative HPLC (hexane–ethyl acetate, 50:50, retention time 12.9 min, 3 ml min⁻¹). Colourless crystals of (I) (m.p. 390.5–392.2 K) were isolated by slow evaporation of a hexane–ethyl acetate (50:50) solution of the compound. Analysis found: C 59.30, H 6.32, S 9.70%; calculated for C₁₆H₂₀O₅S: C 59.24, H 6.21, S 9.88%. /n_max (KBr)/cm⁻¹ 3500 (OH), 1302 (SO₂), 1142 (SO₂). /d_H (400 MHz, CDCl₃, p.p.m.): 7.87–7.95 (2H, m, o-C₆H₅), 7.57–7.65 (1H, m, p-C₆H₅), 7.48–7.57 (2H, m, m-C₆H₅), 3.84–3.94 (4H, m, 2 × 4-H, 2 × 5-H), 3.52 (1H, ddd, J8',7' 9, J8',7' 3, J8',6' 1, 8'-H), 3.03–3.13 (1H, m, 1'-H), 2.32 (1H, ddd, J7',7' 10, J7',6' 10, J7',8' 3, 7'-H), 2.12 (1H, ddd, J7',7' 11, J7',6' 9, J7',8' 9, 7'-H), 1.91–1.98 (2H, m, 2 x 3'-H), 1.85 (1H, dd, J5',5' 15, J5',6' 7, 5'-H), 1.68–1.77 (1H, m, 2'-H), 1.49–1.58 (2H, m, 2'-H, 5'-H), OH not observed. δ_C (50 MHz, CDCl₃) 139.8, (i-C₆H₅), 133.5, (p-C₆H₅), 129.2,(m-C₆H₅), 127.9, (o-C₆H₅), 108.4, (C-2,4'), 72.7, (C-1'), 67.3, (C-8'), 64.4, 63.9, (C-4, C-5), 43.8, (C-6'), 33.4, (C-2'), 32.8, (C-5'), 29.4, (C-3'), 20.4, (C-7'). ESMS⁺ 331 (MLi⁺, 100%), 347 (MNa⁺, 83%).

S3. Refinement

H atoms were located at calculated positions, with C—H set to 0.95 Å. The hydroxy H atom was located from a difference fourier map and the O—H bond length set to 0.85 Å. U_iso values for the H atoms were set at 1.2U_eq of the parent atom. Displacement parameters for atom C9 are indicative of potential disorder for this atom in the dioxane ring.

Computing details

Data collection: MSC/AFC7 Diffractometer Control Software for Windows (Molecular Structure Corporation, 1999); cell refinement: MSC/AFC7 Diffractometer Control; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997-2001); program(s) used to solve structure: TEXSAN for Windows; program(s) used to refine structure: TEXSAN for Windows and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1980-2001) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: TEXSAN for Windows and PLATON.

Figures

	Fig. 1. ORTEP-3 (Farrugia, 1997) plot showing the atomic numbering scheme for a molecule of (I). Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.
	Fig. 2. Hydrogen bonding scheme for (I).

Spiro[1,3-dioxolane-2,4'-[8]phenylsulfonylbicyclo[4.2.0]octan[1]ol]

Crystal data

C16H20O5S	Z = 2
Mr = 324.39	F(000) = 344
Triclinic, P1	Dx = 1.397 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 5.736 (3) Å	Cell parameters from 25 reflections
b = 11.468 (5) Å	θ = 12.7–17.3°
c = 12.095 (4) Å	µ = 0.23 mm^−1
α = 81.1 (6)°	T = 295 K
β = 98.83 (3)°	Needle, colorless
γ = 98.03 (3)°	0.60 × 0.20 × 0.15 mm
V = 771.2 (13) Å^3

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.052
Radiation source: Rigaku rotating anode	θmax = 27.5°, θmin = 2.7°
Graphite monochromator	h = −7→3
ω–2θ scans	k = −14→14
4163 measured reflections	l = −15→15
3537 independent reflections	3 standard reflections every 150 reflections
2637 reflections with I > 2σ(I)	intensity decay: 2.4%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters not refined
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0562P)^2 + 0.277P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3537 reflections	Δρmax = 0.32 e Å^−3
200 parameters	Δρmin = −0.36 e Å^−3
0 restraints	Extinction correction: SHELXL97, FC^*=KFC[1+0.001XFC^2Λ^3/SIN(2Θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.034 (4)

Special details

Experimental. The scan width was (1.52 + 0.30tanθ)° with an ω scan speed of 16° per minute (up to 4 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1.

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
S1	0.01674 (9)	0.29284 (5)	0.91948 (4)	0.0378 (2)
O1	0.4467 (3)	0.37639 (14)	0.77535 (13)	0.0466 (5)
O2	0.2349 (3)	0.31440 (14)	0.99390 (13)	0.0493 (5)
O3	−0.2047 (3)	0.29189 (14)	0.96337 (13)	0.0481 (5)
O4	0.4356 (3)	0.81126 (16)	0.59492 (17)	0.0668 (6)
O5	0.0640 (3)	0.71478 (15)	0.61102 (16)	0.0589 (6)
C1	0.2590 (3)	0.44782 (17)	0.75260 (16)	0.0360 (6)
C2	0.0156 (3)	0.39943 (18)	0.79641 (16)	0.0363 (5)
C3	0.0048 (4)	0.52578 (19)	0.82465 (19)	0.0438 (7)
C4	0.2753 (4)	0.55535 (19)	0.81835 (17)	0.0402 (6)
C5	0.3759 (4)	0.6774 (2)	0.76570 (19)	0.0470 (7)
C6	0.3114 (4)	0.6999 (2)	0.6389 (2)	0.0483 (7)
C7	0.3682 (4)	0.5985 (2)	0.58419 (19)	0.0490 (7)
C8	0.2178 (4)	0.48350 (19)	0.62439 (17)	0.0429 (6)
C9	0.2719 (8)	0.8767 (4)	0.5255 (4)	0.1437 (19)
C10	0.0381 (6)	0.8080 (3)	0.5209 (3)	0.0752 (10)
C11	0.0095 (4)	0.15429 (18)	0.87099 (17)	0.0397 (6)
C12	−0.1990 (4)	0.1071 (2)	0.8101 (2)	0.0500 (7)
C13	−0.2082 (5)	−0.0041 (2)	0.7770 (2)	0.0598 (8)
C14	−0.0150 (6)	−0.0669 (2)	0.8057 (2)	0.0631 (9)
C15	0.1915 (5)	−0.0195 (2)	0.8662 (3)	0.0626 (9)
C16	0.2051 (4)	0.0924 (2)	0.8987 (2)	0.0498 (7)
H1	0.48980	0.36420	0.84650	0.0560*
H2	−0.10510	0.37790	0.73760	0.0440*
H3A	−0.03860	0.52700	0.89710	0.0530*
H3B	−0.09180	0.57280	0.76940	0.0530*
H4	0.36000	0.53710	0.89150	0.0480*
H5A	0.54420	0.68450	0.78270	0.0560*
H5B	0.31680	0.73590	0.79800	0.0560*
H7A	0.53180	0.58900	0.60440	0.0590*
H7B	0.33430	0.61630	0.50440	0.0590*
H8A	0.05490	0.49380	0.60240	0.0520*
H8B	0.25570	0.42130	0.58920	0.0520*
H9A	0.31610	0.89470	0.45170	0.1720*
H9B	0.26710	0.94850	0.55480	0.1720*
H10A	−0.07860	0.85510	0.53090	0.0900*
H10B	−0.00480	0.77760	0.45090	0.0900*
H12	−0.33260	0.15030	0.79150	0.0600*
H13	−0.34840	−0.03710	0.73440	0.0720*
H14	−0.02370	−0.14360	0.78380	0.0760*
H15	0.32400	−0.06350	0.88540	0.0750*
H16	0.34690	0.12580	0.93970	0.0600*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0324 (3)	0.0436 (3)	0.0369 (3)	0.0054 (2)	0.0012 (2)	−0.0068 (2)
O1	0.0325 (7)	0.0541 (9)	0.0545 (9)	0.0136 (6)	0.0040 (6)	−0.0060 (7)
O2	0.0446 (8)	0.0573 (9)	0.0422 (8)	0.0056 (7)	−0.0097 (7)	−0.0110 (7)
O3	0.0409 (8)	0.0570 (9)	0.0501 (8)	0.0085 (7)	0.0170 (7)	−0.0058 (7)
O4	0.0596 (11)	0.0510 (10)	0.0783 (12)	−0.0146 (8)	0.0047 (9)	0.0030 (9)
O5	0.0446 (9)	0.0491 (9)	0.0736 (11)	0.0055 (7)	−0.0040 (8)	0.0085 (8)
C1	0.0269 (9)	0.0408 (10)	0.0400 (10)	0.0047 (7)	−0.0008 (7)	−0.0088 (8)
C2	0.0285 (9)	0.0444 (10)	0.0354 (9)	0.0051 (8)	−0.0003 (7)	−0.0074 (8)
C3	0.0402 (11)	0.0434 (11)	0.0501 (12)	0.0112 (9)	0.0076 (9)	−0.0068 (9)
C4	0.0377 (10)	0.0441 (11)	0.0377 (10)	0.0035 (8)	−0.0028 (8)	−0.0112 (8)
C5	0.0443 (11)	0.0435 (11)	0.0508 (12)	−0.0007 (9)	−0.0026 (9)	−0.0132 (9)
C6	0.0391 (11)	0.0426 (11)	0.0564 (13)	−0.0060 (9)	−0.0008 (10)	−0.0023 (9)
C7	0.0429 (11)	0.0570 (13)	0.0442 (11)	−0.0029 (10)	0.0057 (9)	−0.0061 (10)
C8	0.0417 (11)	0.0474 (11)	0.0387 (10)	0.0002 (9)	0.0024 (8)	−0.0104 (9)
C9	0.096 (3)	0.107 (3)	0.158 (4)	−0.043 (2)	−0.054 (3)	0.079 (3)
C10	0.0748 (19)	0.0597 (16)	0.0745 (18)	0.0024 (14)	−0.0149 (15)	0.0123 (14)
C11	0.0376 (10)	0.0393 (10)	0.0409 (10)	0.0022 (8)	0.0048 (8)	−0.0038 (8)
C12	0.0418 (11)	0.0529 (13)	0.0528 (13)	0.0021 (10)	−0.0006 (10)	−0.0096 (10)
C13	0.0625 (16)	0.0557 (14)	0.0586 (14)	−0.0077 (12)	0.0042 (12)	−0.0168 (12)
C14	0.0768 (18)	0.0446 (13)	0.0717 (17)	0.0037 (12)	0.0209 (14)	−0.0118 (12)
C15	0.0601 (16)	0.0482 (13)	0.0820 (18)	0.0150 (12)	0.0142 (14)	−0.0043 (12)
C16	0.0419 (11)	0.0476 (12)	0.0592 (13)	0.0086 (9)	0.0031 (10)	−0.0055 (10)

Geometric parameters (Å, º)

S1—O2	1.4401 (19)	C13—C14	1.377 (4)
S1—O3	1.448 (2)	C14—C15	1.382 (4)
S1—C2	1.774 (2)	C15—C16	1.388 (3)
S1—C11	1.770 (2)	C2—H2	0.9495
O1—C1	1.411 (3)	C3—H3A	0.9496
O4—C6	1.440 (3)	C3—H3B	0.9501
O4—C9	1.382 (5)	C4—H4	0.9496
O5—C6	1.435 (3)	C5—H5A	0.9503
O5—C10	1.410 (4)	C5—H5B	0.9502
O1—H1	0.8534	C7—H7A	0.9498
C1—C2	1.568 (3)	C7—H7B	0.9504
C1—C8	1.532 (3)	C8—H8A	0.9501
C1—C4	1.552 (3)	C8—H8B	0.9502
C2—C3	1.551 (3)	C9—H9A	0.9495
C3—C4	1.552 (3)	C9—H9B	0.9508
C4—C5	1.520 (3)	C10—H10A	0.9490
C5—C6	1.512 (3)	C10—H10B	0.9499
C6—C7	1.519 (3)	C12—H12	0.9497
C7—C8	1.527 (3)	C13—H13	0.9505
C9—C10	1.455 (6)	C14—H14	0.9498
C11—C16	1.381 (3)	C15—H15	0.9502
C11—C12	1.392 (3)	C16—H16	0.9498
C12—C13	1.386 (3)
S1···H1^i	3.1989	H1···S1	2.9501
S1···H1	2.9501	H1···S1^ii	3.1989
S1···H4	3.1950	H1···O2	2.4278
O1···O2	3.022 (3)	H1···O3^ii	2.2448
O1···O3^ii	2.928 (3)	H1···H4	2.3776
O1···C2^ii	3.211 (3)	H2···O1^i	2.6765
O2···C5^iii	3.388 (3)	H2···C12	3.0884
O2···O1	3.022 (3)	H2···H8A	2.1749
O2···C4	3.218 (3)	H3A···O3	2.7691
O3···O1^i	2.928 (3)	H3A···O2^iv	2.8432
O5···C3	3.134 (3)	H3A···H3A^iv	2.4570
O1···H2^ii	2.6765	H3B···O5	2.5046
O2···H16	2.5449	H3B···C6	3.0711
O2···H4	2.7117	H3B···C8	3.0494
O2···H5A^iii	2.8038	H4···S1	3.1950
O2···H1	2.4278	H4···O2	2.7117
O2···H3A^iv	2.8432	H4···H1	2.3776
O3···H1^i	2.2448	H5A···H7A	2.5529
O3···H12	2.7820	H5A···O2^iii	2.8038
O3···H3A	2.7691	H5B···H14^viii	2.5162
O4···H13^v	2.6588	H7A···H5A	2.5529
O5···H3B	2.5046	H7B···C10	3.0071
O5···H8A	2.5454	H8A···O5	2.5454
C2···O1^i	3.211 (3)	H8A···C3	2.8310
C3···O5	3.134 (3)	H8A···H2	2.1749
C4···O2	3.218 (3)	H8A···C8^vii	2.9350
C5···O2^iii	3.388 (3)	H8A···H8A^vii	2.4474
C11···C15^vi	3.596 (4)	H8B···H10B^vii	2.5923
C15···C11^vi	3.596 (4)	H9A···C13^vii	2.8681
C3···H8A	2.8310	H9A···H13^vii	2.5834
C6···H3B	3.0711	H10B···H8B^vii	2.5923
C8···H8A^vii	2.9350	H12···O3	2.7820
C8···H3B	3.0494	H12···C16^i	3.0743
C10···H7B	3.0071	H13···O4^ix	2.6588
C12···H2	3.0884	H13···H9A^vii	2.5834
C13···H9A^vii	2.8681	H14···H5B^x	2.5162
C16···H12^ii	3.0743	H16···O2	2.5449
O2—S1—O3	117.9 (6)	C2—C3—H3A	114.22
O2—S1—C2	109.7 (6)	C2—C3—H3B	114.27
O2—S1—C11	108.7 (6)	C4—C3—H3A	114.25
O3—S1—C2	107.3 (6)	C4—C3—H3B	114.23
O3—S1—C11	107.3 (6)	H3A—C3—H3B	109.39
C2—S1—C11	105.1 (6)	C1—C4—H4	109.04
C6—O4—C9	108.0 (6)	C3—C4—H4	109.07
C6—O5—C10	108.6 (6)	C5—C4—H4	109.13
C1—O1—H1	109.35	C4—C5—H5A	108.47
O1—C1—C2	119.8 (6)	C4—C5—H5B	108.48
O1—C1—C8	106.8 (6)	C6—C5—H5A	108.43
C2—C1—C4	88.8 (6)	C6—C5—H5B	108.46
C2—C1—C8	109.6 (6)	H5A—C5—H5B	109.39
C4—C1—C8	112.5 (6)	C6—C7—H7A	109.37
O1—C1—C4	118.6 (6)	C6—C7—H7B	109.35
S1—C2—C1	118.1 (6)	C8—C7—H7A	109.45
C1—C2—C3	87.9 (6)	C8—C7—H7B	109.43
S1—C2—C3	111.1 (6)	H7A—C7—H7B	109.41
C2—C3—C4	89.4 (6)	C1—C8—H8A	108.50
C1—C4—C5	119.0 (6)	C1—C8—H8B	108.48
C3—C4—C5	120.5 (6)	C7—C8—H8A	108.52
C1—C4—C3	88.3 (6)	C7—C8—H8B	108.52
C4—C5—C6	113.6 (6)	H8A—C8—H8B	109.51
O4—C6—C5	109.7 (6)	O4—C9—H9A	109.61
O4—C6—C7	110.9 (6)	O4—C9—H9B	109.51
O4—C6—O5	105.1 (6)	C10—C9—H9A	109.49
O5—C6—C7	110.4 (6)	C10—C9—H9B	109.32
C5—C6—C7	110.7 (6)	H9A—C9—H9B	109.52
O5—C6—C5	109.9 (6)	O5—C10—H10A	110.84
C6—C7—C8	109.8 (6)	O5—C10—H10B	110.75
C1—C8—C7	113.3 (6)	C9—C10—H10A	110.90
O4—C9—C10	109.4 (7)	C9—C10—H10B	110.73
O5—C10—C9	104.1 (7)	H10A—C10—H10B	109.42
S1—C11—C12	118.9 (6)	C11—C12—H12	120.62
C12—C11—C16	121.2 (6)	C13—C12—H12	120.56
S1—C11—C16	119.8 (6)	C12—C13—H13	119.89
C11—C12—C13	118.8 (6)	C14—C13—H13	119.90
C12—C13—C14	120.2 (6)	C13—C14—H14	119.68
C13—C14—C15	120.7 (6)	C15—C14—H14	119.66
C14—C15—C16	119.9 (7)	C14—C15—H15	119.98
C11—C16—C15	119.1 (6)	C16—C15—H15	120.08
S1—C2—H2	112.44	C11—C16—H16	120.49
C1—C2—H2	112.50	C15—C16—H16	120.38
C3—C2—H2	112.47
O2—S1—C2—C1	32.2 (6)	C8—C1—C4—C3	93.1 (6)
O2—S1—C2—C3	−67.0 (6)	C8—C1—C4—C5	−31.2 (7)
O3—S1—C2—C1	161.5 (6)	O1—C1—C8—C7	−89.3 (6)
O3—S1—C2—C3	62.2 (6)	O1—C1—C4—C3	−141.3 (6)
C11—S1—C2—C1	−84.5 (6)	C4—C1—C8—C7	42.5 (6)
C11—S1—C2—C3	176.2 (6)	C2—C1—C8—C7	139.6 (6)
O2—S1—C11—C12	171.3 (6)	S1—C2—C3—C4	101.8 (6)
O2—S1—C11—C16	−5.5 (6)	C1—C2—C3—C4	−17.6 (6)
O3—S1—C11—C12	42.7 (6)	C2—C3—C4—C5	140.9 (6)
O3—S1—C11—C16	−134.1 (6)	C2—C3—C4—C1	17.8 (6)
C2—S1—C11—C12	−71.3 (6)	C1—C4—C5—C6	35.8 (7)
C2—S1—C11—C16	111.9 (6)	C3—C4—C5—C6	−70.9 (7)
C9—O4—C6—C7	107.4 (7)	C4—C5—C6—O4	−173.5 (6)
C6—O4—C9—C10	−1.3 (7)	C4—C5—C6—C7	−50.7 (7)
C9—O4—C6—O5	−11.9 (7)	C4—C5—C6—O5	71.5 (6)
C9—O4—C6—C5	−130.0 (7)	O5—C6—C7—C8	−59.0 (6)
C10—O5—C6—O4	21.2 (7)	O4—C6—C7—C8	−175.0 (6)
C10—O5—C6—C5	139.2 (6)	C5—C6—C7—C8	63.0 (6)
C10—O5—C6—C7	−98.4 (6)	C6—C7—C8—C1	−59.6 (6)
C6—O5—C10—C9	−21.6 (7)	O4—C9—C10—O5	14.1 (7)
C4—C1—C2—S1	−95.3 (6)	C12—C11—C16—C15	−0.8 (7)
O1—C1—C2—C3	140.3 (6)	S1—C11—C16—C15	175.9 (6)
C8—C1—C2—C3	−95.9 (6)	S1—C11—C12—C13	−176.8 (6)
C4—C1—C2—C3	17.6 (6)	C16—C11—C12—C13	−0.1 (7)
C8—C1—C2—S1	151.2 (6)	C11—C12—C13—C14	1.0 (7)
O1—C1—C2—S1	27.4 (6)	C12—C13—C14—C15	−1.0 (7)
O1—C1—C4—C5	94.4 (6)	C13—C14—C15—C16	0.1 (7)
C2—C1—C4—C3	−17.6 (6)	C14—C15—C16—C11	0.8 (7)
C2—C1—C4—C5	−142.0 (6)

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+2; (iv) −x, −y+1, −z+2; (v) x+1, y+1, z; (vi) −x, −y, −z+2; (vii) −x, −y+1, −z+1; (viii) x, y+1, z; (ix) x−1, y−1, z; (x) x, y−1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.85	2.43	3.022 (3)	127
O1—H1···O3^ii	0.85	2.25	2.928 (3)	137
C3—H3B···O5	0.95	2.51	3.134 (3)	124
C8—H8A···O5	0.95	2.55	2.884 (3)	101
C16—H16···O2	0.95	2.55	2.926 (3)	104

Symmetry code: (ii) x+1, y, z.