The first spontaneous resolution of a sulfoxide: Dianin's compound analogue, (R)-4-(4-hy­droxy­phen­yl)-2,2,4-tri­methyl­thia­chroman-1-oxide

Gall, J.H.; White, J.D.; MacNicol, D.D.; Frampton, C.S.

doi:10.1107/S2056989018014366

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Volume 74| Part 11| November 2018| Pages 1633-1636

https://doi.org/10.1107/S2056989018014366

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The first spontaneous resolution of a sulfoxide: Dianin's compound analogue, (R)-4-(4-hydroxyphenyl)-2,2,4-trimethylthiachroman-1-oxide

James H. Gall,^a J. Derek White,^a David D. MacNicol ^a and Christopher S. Frampton ^b ^*

^aSchool of Chemistry, Joseph Black Building, University Avenue, University of Glasgow, Glasgow, G12 8QQ, Scotland, and ^bExperimental Techniques Centre, Brunel University London, Kingston Lane, Uxbridge, UB8 3PH, England
^*Correspondence e-mail: chris.frampton@brunel.ac.uk

Edited by V. Khrustalev, Russian Academy of Sciences, Russia (Received 12 September 2018; accepted 11 October 2018; online 19 October 2018)

The title sulfoxide, C₁₈H₂₀O₂S, was prepared by controlled oxidation of thia-Dianin's compound using hydrogen peroxide in glacial acetic acid. On recrystallization from glacial acetic acid, it was found to form unsolvated, spontaneously resolved crystals, the initial crystal structure analysis revealing the presence of both sulfoxide epimers in the crystal. On multiple recrystallization a single epimer was observed, with crystallization occurring in the unchanged orthorhombic space group P2₁2₁2₁, with Z′ = 1. The molecule possesses a distal conformation, referring to the juxtaposition of the p-hydoxyphenyl substituent with respect to its syn-related methyl group, with the sulfoxide oxygen atom anti to the aromatic substituent. The molecular packing features O—H⋯O hydrogen bond chains running parallel to the b axis of the unit cell.

Keywords: crystal structure; thia-Dianin's compound; hydrogen bonding; spontaneous resolution.

CCDC reference: 1872666

1. Chemical context

A significant body of work in the literature relates to specifically targeted structural modification of Dianin's compound, 4-(4-hydroxyphenyl)-2,2,4-trimethylchroman 2, (MacNicol, 1984 ; Finocchiaro & Failla, 1996 ; Collet & Jacques, 1976 ; Frampton et al., 2017a ,b ,c ). Crystallization of the new compounds has normally resulted in one of two outcomes: formation of clathrates in the space group R $[\overline{3}]$ (or R3) or spontaneous resolution, also a subject of much current interest (Pérez-García & Amabilino, 2007 ), to form an unsolvated conglomerate in space group P2₁2₁2₁, with Z′ = 1, in which the individual crystals are formed by supramolecular assembly of a single enantiomer. A notable departure from the above crystallization modes has, however, been found in the case of Dianin's sulfone 4, (Frampton et al., 1992 ), which crystallizes unsolvated in the polar monoclinic space group Cc, with Z′ = 1, and these crystals exhibited a significant SHG effect. The present work was undertaken to establish if the corresponding sulfoxide 1 would retain the clathrating ability of its immediate progenitor thia-Dianin's compound 3, or would undergo spontaneous resolution, alternative possibilities being the formation of a polar monoclinic crystal or crystallization in a more frequently encountered space group. Interestingly, the achiral bis-sulfoxide trans-(R,S)-α,α′-di-tert-butylsulfinyl-para-xylene undergoes conformational spontaneous resolution in the space group P2₁2₁2₁: on dissolution, rapid conformational racemization occurs at room temperature; however, the authors make the point that at 173 K, from calculations, it could be possible to obtain one chiral conformation from a single crystal (Xu et al., 2014 ). Accordingly, the sulfoxide 1 was prepared by controlled oxidation of 3 as described in Section 5, and its crystal structure determined.

2. Structural commentary

Initial attempts to determine the crystal structure of 1 revealed the presence of both sulfoxide epimers in the crystal in a ratio of approximately 90:10. It was found that multiple recrystallization of 1 from glacial acetic acid yielded a single epimer, the structure of which is presented here. The crystal structure of 1 is orthorhombic, space group P2₁2₁2₁ with a single independent molecule in the asymmetric unit, (Z′ = 1), Fig. 1. The molecule possesses a distal conformation, this referring to the juxtaposition of the p-hydroxyphenyl substituent with respect to the syn-related methyl group. The C2—C3—C4—C11 torsion angle is 154.0 (2)°, the corresponding torsion angle for racemic Dianin's compound 2 has a magnitude of 80.67° (Lee et al., 2014 ) and for 4-(4-hydroxyphenyl)-2,2,4-trimethylchroman-1,1-dioxide 4, it is 76.8° (Frampton et al., 1992). The expected torsional angle value for a distal conformation is 160° whereas that for a proximal conformation is 80°. The torsion angle S1—C2—C3—C4, defining the heterocyclic ring chirality, has a value of −67.3 (2)°. Fig. 2 shows an overlay of 1 (brown) with sulfone 4 (cyan). In this figure, the six aromatic atoms of the chroman unit for each structure have been overlaid using the standard molecule overlay routine in Mercury (Macrae et al., 2008 ), resulting in an r.m.s. displacement of 0.0147 Å, and this clearly demonstrates the difference between the distal and proximal conformations of 1 and 4, respectively. The absolute configuration of 1, was determined as being R at the chiral centre C4 by anomalous dispersion methods, (Parsons et al. 2013 ), the Flack x parameter was determined as −0.002 (7) using 1246 quotients [(I⁺) − (I⁻)]/[(I⁺) + (I⁻)].

Figure 1
View of molecule 1 with the atom-labelling scheme. Ellipsoids are drawn at the 50% probability level.

Figure 2
View of the structure overlay of 1 (brown) and 4 (cyan).

3. Supramolecular features

The structure of 1 is isostructural with the enantiomerically pure amine counterparts of Dianin's and thia-Dianin's compound, (R)-4-(4-aminophenyl)-2,2,4-trimethylchroman and (S)-4-(4-aminophenyl)-2,2,4-trimethylthiachroman, both of which were obtained by spontaneous resolution (Frampton et al., 2011 ), and also surprisingly isostructural with the enantiomerically pure forms of 4-(4-hydroxyphenyl)-2,2,4-trimethylchroman, 2 (Lloyd & Bredenkamp, 2005 ) and 4-(2,4-dihydroxyphenyl)-2,2,4-trimethylchroman, 5 (Beresford et al., 1999 ). The crystal packing is dominated by the formation of an extended linear hydroxy –OH to sulfoxide O, hydrogen-bonded O—H⋯O chain along the [010] direction of the unit cell, Figs. 3 and 4, Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.77 (3)	1.92 (3)	2.685 (3)	169 (3)
Symmetry code: (i) x, y-1, z.

Figure 3
A partial view of the crystal packing down the a axis showing the hydrogen-bonded chain. The intermolecular O—H⋯O hydrogen bond is shown as a dotted line.

Figure 4
View of the crystal packing of 1 down the b axis.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.39 update August 2018; Groom et al., 2016 ) for the thia-Dianin's framework, 3, yielded 15 hits, all of which were genuine examples of analogues of the material under investigation. Although there are no entries for the empty racemic R $[\overline{3}]$ host of thia-Dianin's compound, there are seven entries for the following host–guest clathrates: ethanol (HPTHCR; MacNicol et al., 1969 ), 2,5,5-trimethylhex-3-yn-2-ol (TCHHXO; MacNicol & Wilson, 1971 ), cyclopentane (METCCP; Hardy et al., 1979 ) and isopropanol at four different temperatures demonstrating three commensurate phase changes in the host lattice (VANFOI, 371 K, VANFOI01, 295 K, VANFOI02, 200 K and VANFUO, 90 K; Frampton et al., 2017a). Thia-Dianin's compound, 3, was also found in the 1:1 quasi-racemic R3 host with Dianin's compound, 2, in the following three entries: apohost (BIBNAD and BIBNAD01), CCl₄/H₂O host–guest clathrate (HIDQAO) (Frampton et al., 2013 ). The structure and absolute stereochemistry determination of the resolved S-enantiomer of thia-Dianin's compound used in the formation of the quasi-racemates above (BIBNEH: Frampton et al., 2013). Four further examples demonstrating a slightly modified framework include the 6-methyl analogue (HPMTCM; Hardy et al., 1977 ), the cycloctane host–guest clathrate of the 8-methyl analogue (MSOCYO10; Hardy et al., 1979), the oxidized sulfone, 4, (KUTDUY; Frampton et al., 1992) and 4-(4-hydroxyphenyl)-2,2,4-trimethyl-7,8-benzothiachroman 6, a fused-ring counterpart of thia-Dianin's compound (JELROK; Frampton et al., 2017c).

5. Synthesis and crystallization

Preparation of 1: 4-(4-hydroxyphenyl)-2,2,4-trimethylthiachroman 3 (MacNicol, 1969 ) (0.25 g, 0.88 mmol) was dissolved in glacial acetic acid (10 mL) and a 50% excess of 30% hydrogen peroxide (0.15 mL, 1.32 mmol) added. After the reaction was left overnight at ca 278 K, the precipitated white solid was filtered off, washed several times with ether, and initially recrystallized from aqueous dimethyl sulfoxide yielding 0.168 g, (63%) of product. A further recrystallization from glacial acetic acid gave colourless crystals which were analysed by X-ray diffraction as described in the text. The crystals were obtained by spontaneous resolution on crystallization, yielding a 50:50 mixture of the pure enantiomers. These crystals also incorporated both spontaneously resolved sulfoxide epimers, four further recrystallizations were performed giving a single epimer of purity greater than 99% [500 MHz ¹H NMR, DMSO-d₆ solution analysis gave 99.5 (2)% purity] and the very minor residual second epimer was undetectable in the subsequent X-ray analysis. These crystals melted over a wide range, ca 513–536 K, possibly arising from sulfoxide epimerization, along with decomposition, at high temperature. MS [EI⁺]: 300.1178, C₁₈H₂₀O₂S, calculated 300.1184; ¹H NMR (400 MHz, DMSO-d₆) : δ 0.94 (s, 3H), 1.31 (s, 3H), 1.67 (s, 3H), 2.26 (q, 2H, δ_AB = 0.45 ppm, J_AB = 15.1 Hz), 6.6–7.7 (aromatic, 8H), 9.27(s, 1H); FT–IR (ν_max, ATR, cm⁻¹): 3176 (br), 3197 (minor) [ν(O—H)]; 1017 [ν(S—O)].

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₈H₂₀O₂S
M_r	300.40
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	10.4311 (3), 11.0892 (3), 12.8868 (3)
V (Å³)	1490.65 (7)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.94
Crystal size (mm)	0.18 × 0.12 × 0.10

Data collection
Diffractometer	Rigaku Oxford Diffraction SuperNova, Dualflex, AtlasS2
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.786, 0.844
No. of measured, independent and observed [I > 2σ(I)] reflections	5735, 3046, 2982
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.075, 1.03
No. of reflections	3046
No. of parameters	197
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.29
Absolute structure	Flack x determined using 1246 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)
Absolute structure parameter	−0.002 (7)
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXD2014/6 (Schneider & Sheldrick, 2002 ), SHELXL2014/6 (Sheldrick, 2015 ), SHELXTL (Sheldrick, 2008 ), Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010 ).

The hydrogen atom of the OH group was localized in the difference-Fourier map and refined isotropically. The other hydrogen atoms were placed in calculated positions and refined within the riding model with C—H = 0.95–0.99 Å and fixed isotropic displacement parameters [U_iso(H) = 1.5U_eq(C) for the methyl groups and 1.2U_eq(C) for the other groups].

Supporting information

CCDC reference: 1872666

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018014366/kq2023sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018014366/kq2023Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018014366/kq2023Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXD2014/6 (Schneider & Sheldrick, 2002); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).

(R)-4-(4-Hydroxyphenyl)-2,2,4-trimethyl-3H-1λ⁴-benzothiopyran-1-one top

Crystal data top

C₁₈H₂₀O₂S	D_x = 1.339 Mg m⁻³
M_r = 300.40	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 3948 reflections
a = 10.4311 (3) Å	θ = 5.3–74.2°
b = 11.0892 (3) Å	µ = 1.94 mm⁻¹
c = 12.8868 (3) Å	T = 100 K
V = 1490.65 (7) Å³	Block, colourless
Z = 4	0.18 × 0.12 × 0.10 mm
F(000) = 640

Data collection top

Rigaku Oxford Diffraction SuperNova, Dualflex, AtlasS2 diffractometer	3046 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source	2982 reflections with I > 2σ(I)
Detector resolution: 5.2921 pixels mm^-1	R_int = 0.016
ω scans	θ_max = 74.5°, θ_min = 5.3°
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2015)	h = −12→13
T_min = 0.786, T_max = 0.844	k = −12→13
5735 measured reflections	l = −16→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0407P)² + 0.434P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3046 reflections	Δρ_max = 0.27 e Å⁻³
197 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints	Absolute structure: Flack x determined using 1246 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: difference Fourier map	Absolute structure parameter: −0.002 (7)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
S1	0.17202 (5)	0.62246 (5)	0.63136 (4)	0.01942 (13)
O1	0.10168 (17)	−0.05587 (16)	0.74216 (15)	0.0286 (4)
H1	0.120 (3)	−0.115 (3)	0.713 (2)	0.031 (8)*
O2	0.19457 (17)	0.75661 (14)	0.63392 (14)	0.0290 (4)
C2	0.1359 (2)	0.5775 (2)	0.49805 (16)	0.0213 (5)
C3	0.1350 (2)	0.4390 (2)	0.50523 (16)	0.0203 (4)
H3A	0.1008	0.4077	0.4388	0.024*
H3B	0.0729	0.4164	0.5600	0.024*
C4	0.2625 (2)	0.3703 (2)	0.52807 (15)	0.0183 (4)
C5	0.3535 (2)	0.4405 (2)	0.59971 (15)	0.0191 (4)
C6	0.4737 (2)	0.3919 (2)	0.62341 (17)	0.0229 (4)
H6	0.4947	0.3139	0.5981	0.027*
C7	0.5633 (2)	0.4536 (2)	0.68256 (18)	0.0261 (5)
H7	0.6437	0.4175	0.6977	0.031*
C8	0.5354 (2)	0.5688 (2)	0.71980 (18)	0.0246 (5)
H8	0.5973	0.6126	0.7585	0.030*
C9	0.4163 (2)	0.6183 (2)	0.69968 (15)	0.0211 (4)
H9	0.3956	0.6962	0.7255	0.025*
C10	0.3267 (2)	0.55413 (19)	0.64149 (15)	0.0190 (4)
C11	0.2254 (2)	0.2522 (2)	0.58256 (16)	0.0178 (4)
C12	0.1659 (2)	0.25810 (19)	0.67999 (16)	0.0195 (4)
H12	0.1519	0.3348	0.7109	0.023*
C13	0.1269 (2)	0.1558 (2)	0.73240 (16)	0.0201 (4)
H13	0.0890	0.1629	0.7991	0.024*
C14	0.1431 (2)	0.04203 (19)	0.68765 (17)	0.0206 (4)
C15	0.2012 (2)	0.0339 (2)	0.59057 (18)	0.0224 (4)
H15	0.2127	−0.0427	0.5589	0.027*
C16	0.2426 (2)	0.1379 (2)	0.53978 (16)	0.0207 (4)
H16	0.2836	0.1306	0.4743	0.025*
C17	0.3331 (2)	0.3456 (2)	0.42483 (16)	0.0237 (4)
H17A	0.4110	0.2988	0.4386	0.036*
H17B	0.3563	0.4224	0.3922	0.036*
H17C	0.2769	0.3000	0.3782	0.036*
C18	0.2289 (2)	0.6345 (2)	0.42175 (17)	0.0290 (5)
H18A	0.2208	0.7225	0.4249	0.044*
H18B	0.2091	0.6067	0.3514	0.044*
H18C	0.3167	0.6112	0.4398	0.044*
C19	−0.0004 (2)	0.6226 (2)	0.47748 (17)	0.0261 (5)
H19A	−0.0595	0.5856	0.5273	0.039*
H19B	−0.0261	0.6006	0.4068	0.039*
H19C	−0.0030	0.7105	0.4851	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0224 (2)	0.0180 (2)	0.0179 (2)	0.0006 (2)	−0.00050 (19)	−0.00088 (18)
O1	0.0335 (9)	0.0175 (8)	0.0347 (9)	−0.0018 (7)	0.0080 (7)	0.0026 (7)
O2	0.0354 (9)	0.0181 (7)	0.0335 (9)	0.0019 (7)	−0.0041 (8)	−0.0025 (7)
C2	0.0268 (11)	0.0212 (11)	0.0159 (9)	0.0007 (8)	−0.0021 (8)	0.0008 (8)
C3	0.0235 (10)	0.0205 (10)	0.0169 (9)	0.0001 (9)	−0.0028 (8)	0.0003 (8)
C4	0.0214 (9)	0.0186 (10)	0.0150 (9)	−0.0011 (9)	0.0001 (7)	−0.0018 (9)
C5	0.0210 (10)	0.0217 (10)	0.0146 (8)	−0.0036 (8)	0.0026 (7)	0.0013 (8)
C6	0.0229 (10)	0.0221 (10)	0.0238 (10)	0.0015 (8)	0.0011 (8)	−0.0022 (9)
C7	0.0215 (10)	0.0308 (12)	0.0261 (11)	0.0015 (9)	0.0001 (9)	0.0005 (10)
C8	0.0215 (10)	0.0292 (12)	0.0231 (10)	−0.0053 (9)	−0.0024 (8)	−0.0021 (9)
C9	0.0263 (10)	0.0194 (10)	0.0177 (9)	−0.0020 (9)	0.0006 (8)	0.0000 (8)
C10	0.0200 (9)	0.0218 (9)	0.0151 (8)	−0.0032 (9)	0.0014 (9)	0.0028 (7)
C11	0.0183 (9)	0.0186 (10)	0.0166 (9)	0.0001 (8)	−0.0020 (8)	−0.0009 (8)
C12	0.0202 (9)	0.0188 (9)	0.0194 (9)	−0.0016 (9)	−0.0008 (9)	−0.0034 (8)
C13	0.0199 (9)	0.0217 (11)	0.0188 (9)	−0.0009 (8)	0.0019 (8)	−0.0003 (8)
C14	0.0187 (10)	0.0184 (10)	0.0247 (10)	−0.0017 (8)	−0.0017 (8)	0.0023 (9)
C15	0.0258 (11)	0.0168 (10)	0.0246 (10)	0.0005 (8)	−0.0016 (9)	−0.0039 (9)
C16	0.0236 (10)	0.0193 (10)	0.0191 (9)	0.0006 (9)	−0.0001 (8)	−0.0016 (9)
C17	0.0296 (11)	0.0253 (11)	0.0161 (9)	0.0002 (9)	0.0033 (9)	−0.0008 (7)
C18	0.0387 (13)	0.0280 (12)	0.0204 (10)	−0.0003 (11)	0.0040 (10)	0.0048 (10)
C19	0.0291 (11)	0.0270 (12)	0.0220 (10)	0.0052 (11)	−0.0055 (8)	0.0010 (10)

Geometric parameters (Å, º) top

S1—O2	1.5064 (16)	C9—C10	1.394 (3)
S1—C10	1.788 (2)	C9—H9	0.9500
S1—C2	1.828 (2)	C11—C16	1.394 (3)
O1—C14	1.363 (3)	C11—C12	1.402 (3)
O1—H1	0.77 (3)	C12—C13	1.381 (3)
C2—C18	1.519 (3)	C12—H12	0.9500
C2—C19	1.530 (3)	C13—C14	1.398 (3)
C2—C3	1.539 (3)	C13—H13	0.9500
C3—C4	1.560 (3)	C14—C15	1.393 (3)
C3—H3A	0.9900	C15—C16	1.395 (3)
C3—H3B	0.9900	C15—H15	0.9500
C4—C11	1.535 (3)	C16—H16	0.9500
C4—C5	1.536 (3)	C17—H17A	0.9800
C4—C17	1.545 (3)	C17—H17B	0.9800
C5—C10	1.398 (3)	C17—H17C	0.9800
C5—C6	1.399 (3)	C18—H18A	0.9800
C6—C7	1.387 (3)	C18—H18B	0.9800
C6—H6	0.9500	C18—H18C	0.9800
C7—C8	1.395 (4)	C19—H19A	0.9800
C7—H7	0.9500	C19—H19B	0.9800
C8—C9	1.383 (3)	C19—H19C	0.9800
C8—H8	0.9500

O2—S1—C10	106.02 (10)	C9—C10—S1	115.34 (17)
O2—S1—C2	108.79 (10)	C5—C10—S1	122.27 (16)
C10—S1—C2	98.01 (10)	C16—C11—C12	117.0 (2)
C14—O1—H1	110 (2)	C16—C11—C4	124.22 (19)
C18—C2—C19	110.19 (19)	C12—C11—C4	118.76 (19)
C18—C2—C3	117.26 (19)	C13—C12—C11	122.0 (2)
C19—C2—C3	109.35 (18)	C13—C12—H12	119.0
C18—C2—S1	111.29 (16)	C11—C12—H12	119.0
C19—C2—S1	105.39 (15)	C12—C13—C14	120.26 (19)
C3—C2—S1	102.53 (14)	C12—C13—H13	119.9
C2—C3—C4	119.60 (18)	C14—C13—H13	119.9
C2—C3—H3A	107.4	O1—C14—C15	123.3 (2)
C4—C3—H3A	107.4	O1—C14—C13	117.9 (2)
C2—C3—H3B	107.4	C15—C14—C13	118.8 (2)
C4—C3—H3B	107.4	C14—C15—C16	120.2 (2)
H3A—C3—H3B	107.0	C14—C15—H15	119.9
C11—C4—C5	108.25 (16)	C16—C15—H15	119.9
C11—C4—C17	111.28 (18)	C11—C16—C15	121.8 (2)
C5—C4—C17	108.20 (17)	C11—C16—H16	119.1
C11—C4—C3	106.76 (17)	C15—C16—H16	119.1
C5—C4—C3	113.09 (18)	C4—C17—H17A	109.5
C17—C4—C3	109.29 (17)	C4—C17—H17B	109.5
C10—C5—C6	116.23 (19)	H17A—C17—H17B	109.5
C10—C5—C4	124.4 (2)	C4—C17—H17C	109.5
C6—C5—C4	119.3 (2)	H17A—C17—H17C	109.5
C7—C6—C5	122.3 (2)	H17B—C17—H17C	109.5
C7—C6—H6	118.9	C2—C18—H18A	109.5
C5—C6—H6	118.9	C2—C18—H18B	109.5
C6—C7—C8	120.0 (2)	H18A—C18—H18B	109.5
C6—C7—H7	120.0	C2—C18—H18C	109.5
C8—C7—H7	120.0	H18A—C18—H18C	109.5
C9—C8—C7	119.2 (2)	H18B—C18—H18C	109.5
C9—C8—H8	120.4	C2—C19—H19A	109.5
C7—C8—H8	120.4	C2—C19—H19B	109.5
C8—C9—C10	120.0 (2)	H19A—C19—H19B	109.5
C8—C9—H9	120.0	C2—C19—H19C	109.5
C10—C9—H9	120.0	H19A—C19—H19C	109.5
C9—C10—C5	122.3 (2)	H19B—C19—H19C	109.5

O2—S1—C2—C18	45.94 (19)	C6—C5—C10—C9	2.8 (3)
C10—S1—C2—C18	−64.08 (18)	C4—C5—C10—C9	−175.00 (19)
O2—S1—C2—C19	−73.49 (17)	C6—C5—C10—S1	−172.93 (15)
C10—S1—C2—C19	176.50 (15)	C4—C5—C10—S1	9.3 (3)
O2—S1—C2—C3	172.10 (14)	O2—S1—C10—C9	31.70 (18)
C10—S1—C2—C3	62.09 (15)	C2—S1—C10—C9	143.96 (16)
C18—C2—C3—C4	54.9 (3)	O2—S1—C10—C5	−152.32 (17)
C19—C2—C3—C4	−178.82 (18)	C2—S1—C10—C5	−40.06 (19)
S1—C2—C3—C4	−67.3 (2)	C5—C4—C11—C16	−124.3 (2)
C2—C3—C4—C11	152.40 (17)	C17—C4—C11—C16	−5.6 (3)
C2—C3—C4—C5	33.5 (2)	C3—C4—C11—C16	113.6 (2)
C2—C3—C4—C17	−87.1 (2)	C5—C4—C11—C12	58.2 (2)
C11—C4—C5—C10	−117.8 (2)	C17—C4—C11—C12	176.96 (19)
C17—C4—C5—C10	121.5 (2)	C3—C4—C11—C12	−63.9 (2)
C3—C4—C5—C10	0.3 (3)	C16—C11—C12—C13	0.7 (3)
C11—C4—C5—C6	64.5 (2)	C4—C11—C12—C13	178.3 (2)
C17—C4—C5—C6	−56.2 (2)	C11—C12—C13—C14	−1.7 (3)
C3—C4—C5—C6	−177.41 (19)	C12—C13—C14—O1	−179.3 (2)
C10—C5—C6—C7	−1.7 (3)	C12—C13—C14—C15	1.2 (3)
C4—C5—C6—C7	176.2 (2)	O1—C14—C15—C16	−179.3 (2)
C5—C6—C7—C8	−0.6 (4)	C13—C14—C15—C16	0.3 (3)
C6—C7—C8—C9	2.0 (4)	C12—C11—C16—C15	0.8 (3)
C7—C8—C9—C10	−1.0 (3)	C4—C11—C16—C15	−176.7 (2)
C8—C9—C10—C5	−1.5 (3)	C14—C15—C16—C11	−1.3 (3)
C8—C9—C10—S1	174.49 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.77 (3)	1.92 (3)	2.685 (3)	169 (3)

Symmetry code: (i) x, y−1, z.

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