Absolute configuration of xerophenone A.

The title compound, C(33)H(42)O(5), known as xerophenone A {systematic name: (1R,3R,4R,6S,8E,10R)-10-hy-droxy-8-[hy-droxy(phen-yl)methyl-ene]-4-methyl-1,6-bis-(3-methyl-but-2-en-1-yl)-3-(3-methyl-but-3-en-1-yl)-11-oxatricyclo-[4.3.1.1(4,10)]undecane-7,9-dione} is a naturally occurring rearranged benzophenone compound which was isolated from the twigs of Garcinia propinqua. The absolute configuration was determined by refining the Flack parameter to 0.18 (16). The absolute configurations at positions 1, 3, 4, 6 and 10 of the xerophenone A are R, R, R, S and R. In the mol-ecule, the cyclo-hexane-1,3-dione, tetra-hydro-2H-pyran and tetra-hydro-furan rings adopt twisted boat, standard chair and envelope conformations, respectively. The 3-methyl-but-3-en-1-yl substituent is disordered over two sets of sites in a 0.771 (11):0.229 (11) ratio. An intra-molecular O-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, mol-ecules are linked by O-H⋯O and weak C-H⋯O inter-actions into a chain along the a axis. A very weak C-H⋯π inter-action and C⋯O short contact [2.989 (2) Å] are also present.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For background to plants in the Clusiaceae family, bioactive metabolites and their biological and pharmacological activities, see: Castardo et al. (2008 ▶); Henry & Jacobs (1995 ▶); Nguyen et al. (2011 ▶); Phongpaichit et al. (1994 ▶); Suksamrarn et al. (2006 ▶); Thoison et al. (2005 ▶); Xu et al. (2010 ▶); Yu et al. (2007 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C33H42O5

M = 518.67

Monoclinic,

a = 6.1984 (2) Å

b = 17.0998 (4) Å

c = 13.7007 (3) Å

β = 91.036 (1)°

V = 1451.92 (7) Å3

Z = 2

Cu Kα radiation

μ = 0.62 mm−1

T = 100 K

0.31 × 0.13 × 0.09 mm

Data collection

Bruker APEX Duo CCD area detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.830, T max = 0.944

11622 measured reflections

4746 independent reflections

4661 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.099

S = 1.07

4746 reflections

369 parameters

7 restraints

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.20 e Å−3

Absolute structure: Flack (1983 ▶), 2079 Friedel pairs

Flack parameter: 0.18 (16)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812015267/is5112sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812015267/is5112Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812015267/is5112Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C33H42O5	F(000) = 560
Mr = 518.67	Dx = 1.186 Mg m−3
Monoclinic, P21	Melting point = 451.0–452.4 K
Hall symbol: P 2yb	Cu Kα radiation, λ = 1.54178 Å
a = 6.1984 (2) Å	Cell parameters from 4746 reflections
b = 17.0998 (4) Å	θ = 3.2–67.5°
c = 13.7007 (3) Å	µ = 0.62 mm−1
β = 91.036 (1)°	T = 100 K
V = 1451.92 (7) Å3	Plate, colorless
Z = 2	0.31 × 0.13 × 0.09 mm

Bruker APEX Duo CCD area detector diffractometer	4746 independent reflections
Radiation source: sealed tube	4661 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
φ and ω scans	θmax = 67.5°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→7
Tmin = 0.830, Tmax = 0.944	k = −19→20
11622 measured reflections	l = −16→16

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H-atom parameters constrained
wR(F2) = 0.099	w = 1/[σ2(Fo2) + (0.0526P)2 + 0.4822P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
4746 reflections	Δρmax = 0.24 e Å−3
369 parameters	Δρmin = −0.20 e Å−3
7 restraints	Absolute structure: Flack (1983), 2079 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.18 (16)

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	−0.2134 (2)	0.52353 (8)	0.24048 (11)	0.0296 (3)
H1O1	−0.1378	0.5351	0.2881	0.084 (13)*
O2	0.0272 (2)	0.50870 (8)	0.38262 (10)	0.0262 (3)
O3	−0.2215 (2)	0.27900 (8)	0.24870 (9)	0.0200 (3)
O4	0.4496 (2)	0.36790 (8)	0.32243 (9)	0.0208 (3)
H1O4	0.5236	0.3382	0.2901	0.031*
O5	0.4021 (2)	0.26998 (8)	0.43398 (9)	0.0198 (3)
C1	0.1716 (3)	0.38478 (11)	0.43458 (13)	0.0191 (4)
C2	0.0072 (3)	0.33858 (11)	0.49672 (13)	0.0191 (4)
H2A	−0.0471	0.3725	0.5474	0.023*
H2B	−0.1140	0.3231	0.4553	0.023*
C3	0.1071 (3)	0.26536 (11)	0.54423 (13)	0.0212 (4)
H3A	0.2122	0.2833	0.5936	0.025*
C4	0.2327 (3)	0.21824 (11)	0.46743 (14)	0.0205 (4)
C5	0.1006 (3)	0.20180 (11)	0.37297 (13)	0.0193 (4)
H5A	−0.0517	0.1970	0.3867	0.023*
H5B	0.1491	0.1541	0.3421	0.023*
C6	0.1428 (3)	0.27366 (11)	0.30699 (13)	0.0184 (4)
C7	−0.0628 (3)	0.31594 (11)	0.27620 (12)	0.0192 (4)
C8	−0.0625 (3)	0.40194 (12)	0.28183 (13)	0.0210 (4)
C9	0.0452 (3)	0.43657 (12)	0.36486 (14)	0.0212 (4)
C10	0.2965 (3)	0.32512 (11)	0.37240 (13)	0.0189 (4)
C11	0.3343 (3)	0.43234 (12)	0.49784 (14)	0.0229 (4)
H11A	0.4442	0.3969	0.5228	0.027*
H11B	0.4050	0.4699	0.4561	0.027*
C12	0.2397 (3)	0.47577 (11)	0.58299 (14)	0.0236 (4)
H12A	0.0954	0.4903	0.5773	0.028*
C13	0.3434 (3)	0.49531 (12)	0.66554 (14)	0.0251 (4)
C14	0.2342 (4)	0.53943 (14)	0.74493 (15)	0.0340 (5)
H14A	0.0824	0.5428	0.7303	0.051*
H14B	0.2938	0.5912	0.7495	0.051*
H14C	0.2563	0.5127	0.8059	0.051*
C15	0.5786 (4)	0.47874 (14)	0.68566 (16)	0.0320 (5)
H15A	0.6407	0.4549	0.6293	0.048*
H15B	0.5926	0.4439	0.7404	0.048*
H15C	0.6525	0.5268	0.7002	0.048*
C16	−0.0659 (3)	0.21819 (12)	0.59759 (14)	0.0262 (4)
H16A	−0.0041	0.1691	0.6200	0.031*
H16B	−0.1835	0.2062	0.5524	0.031*
C17	−0.1550 (4)	0.26321 (14)	0.68556 (17)	0.0355 (5)
H17A	−0.0353	0.2846	0.7222	0.043*
H17B	−0.2138	0.3120	0.6628	0.043*	0.771 (12)
H17C	−0.2384	0.3065	0.6610	0.043*	0.229 (12)
C18A	−0.3256 (9)	0.2211 (3)	0.7408 (5)	0.0243 (12)	0.771 (12)
C19A	−0.5160 (5)	0.2548 (3)	0.7573 (2)	0.0322 (9)	0.771 (12)
H19A	−0.6209	0.2279	0.7916	0.038 (9)*	0.771 (12)
H19B	−0.5436	0.3051	0.7345	0.051 (11)*	0.771 (12)
C20A	−0.2778 (9)	0.1407 (2)	0.7766 (3)	0.0546 (17)	0.771 (12)
H20A	−0.3932	0.1230	0.8168	0.082*	0.771 (12)
H20B	−0.1454	0.1410	0.8141	0.082*	0.771 (12)
H20C	−0.2637	0.1060	0.7219	0.082*	0.771 (12)
C18B	−0.289 (2)	0.2169 (14)	0.7528 (18)	0.036 (7)*	0.229 (12)
C19B	−0.500 (2)	0.2237 (11)	0.7641 (10)	0.035 (4)*	0.229 (12)
H19C	−0.5694	0.1940	0.8110	0.043*	0.229 (12)
H19D	−0.5794	0.2582	0.7250	0.043*	0.229 (12)
C20B	−0.162 (2)	0.1622 (9)	0.8146 (11)	0.052 (4)*	0.229 (12)
H20D	−0.2429	0.1489	0.8714	0.078*	0.229 (12)
H20E	−0.0289	0.1866	0.8343	0.078*	0.229 (12)
H20F	−0.1321	0.1156	0.7781	0.078*	0.229 (12)
C21	0.2596 (3)	0.25027 (11)	0.21211 (14)	0.0206 (4)
H21A	0.2787	0.2968	0.1727	0.025*
H21B	0.4020	0.2307	0.2296	0.025*
C22	0.1440 (3)	0.18912 (12)	0.15065 (14)	0.0223 (4)
H22A	−0.0018	0.1809	0.1619	0.027*
C23	0.2358 (3)	0.14645 (12)	0.08194 (13)	0.0230 (4)
C24	0.4683 (3)	0.15337 (14)	0.05475 (15)	0.0299 (5)
H24A	0.5413	0.1878	0.0997	0.045*
H24B	0.4776	0.1740	−0.0102	0.045*
H24C	0.5348	0.1027	0.0574	0.045*
C25	0.1098 (4)	0.08582 (15)	0.02536 (17)	0.0353 (5)
H25A	−0.0395	0.0887	0.0425	0.053*
H25B	0.1649	0.0348	0.0408	0.053*
H25C	0.1235	0.0954	−0.0433	0.053*
C26	0.3406 (3)	0.14549 (12)	0.50876 (14)	0.0245 (4)
H26A	0.4467	0.1271	0.4640	0.037*
H26B	0.2341	0.1056	0.5182	0.037*
H26C	0.4093	0.1578	0.5702	0.037*
C27	−0.1913 (3)	0.44964 (11)	0.22138 (14)	0.0222 (4)
C28	−0.3061 (3)	0.42365 (12)	0.13087 (14)	0.0239 (4)
C29	−0.5102 (4)	0.45424 (13)	0.11046 (16)	0.0297 (5)
H29A	−0.5735	0.4887	0.1539	0.036*
C30	−0.6192 (4)	0.43302 (14)	0.02479 (17)	0.0358 (5)
H30A	−0.7562	0.4530	0.0116	0.043*
C31	−0.5257 (4)	0.38254 (15)	−0.04068 (17)	0.0389 (6)
H31A	−0.5993	0.3686	−0.0978	0.047*
C32	−0.3208 (4)	0.35257 (14)	−0.02083 (16)	0.0345 (5)
H32A	−0.2572	0.3186	−0.0649	0.041*
C33	−0.2112 (3)	0.37321 (13)	0.06458 (14)	0.0277 (4)
H33A	−0.0740	0.3533	0.0775	0.033*

	U11	U22	U33	U12	U13	U23
O1	0.0378 (9)	0.0196 (7)	0.0313 (8)	0.0031 (6)	−0.0018 (6)	0.0021 (6)
O2	0.0342 (8)	0.0176 (7)	0.0269 (7)	−0.0002 (6)	0.0027 (6)	−0.0030 (5)
O3	0.0167 (6)	0.0210 (6)	0.0224 (6)	−0.0012 (5)	0.0026 (5)	−0.0013 (5)
O4	0.0187 (7)	0.0196 (6)	0.0243 (6)	−0.0022 (5)	0.0074 (5)	−0.0035 (5)
O5	0.0166 (6)	0.0207 (7)	0.0223 (6)	0.0002 (5)	0.0019 (5)	−0.0005 (5)
C1	0.0195 (9)	0.0175 (9)	0.0204 (8)	−0.0018 (7)	0.0036 (7)	−0.0037 (7)
C2	0.0202 (9)	0.0171 (9)	0.0201 (8)	−0.0001 (7)	0.0051 (6)	−0.0024 (7)
C3	0.0223 (10)	0.0205 (9)	0.0210 (9)	−0.0002 (7)	0.0017 (7)	−0.0001 (7)
C4	0.0201 (10)	0.0197 (9)	0.0218 (9)	−0.0013 (7)	0.0016 (7)	0.0000 (7)
C5	0.0205 (10)	0.0164 (9)	0.0209 (8)	−0.0004 (7)	0.0019 (7)	−0.0020 (7)
C6	0.0172 (9)	0.0184 (9)	0.0198 (8)	−0.0014 (7)	0.0038 (6)	−0.0007 (7)
C7	0.0199 (10)	0.0234 (9)	0.0145 (8)	−0.0001 (7)	0.0053 (7)	0.0013 (7)
C8	0.0174 (9)	0.0232 (9)	0.0228 (9)	−0.0007 (7)	0.0060 (7)	0.0013 (7)
C9	0.0186 (9)	0.0210 (9)	0.0244 (9)	−0.0015 (7)	0.0092 (7)	0.0007 (8)
C10	0.0181 (10)	0.0190 (9)	0.0196 (8)	−0.0005 (7)	0.0031 (7)	−0.0011 (7)
C11	0.0214 (10)	0.0221 (9)	0.0252 (9)	−0.0027 (8)	0.0019 (7)	−0.0052 (8)
C12	0.0235 (10)	0.0188 (10)	0.0284 (10)	0.0026 (7)	0.0032 (8)	−0.0027 (8)
C13	0.0316 (11)	0.0196 (10)	0.0243 (10)	0.0016 (8)	0.0016 (8)	0.0009 (8)
C14	0.0441 (14)	0.0328 (12)	0.0251 (10)	0.0078 (10)	−0.0014 (9)	−0.0042 (9)
C15	0.0347 (12)	0.0320 (12)	0.0292 (11)	0.0016 (9)	−0.0029 (8)	−0.0030 (9)
C16	0.0297 (11)	0.0235 (10)	0.0255 (10)	0.0005 (8)	0.0059 (8)	0.0035 (8)
C17	0.0407 (13)	0.0322 (12)	0.0339 (11)	−0.0022 (10)	0.0106 (9)	−0.0004 (9)
C18A	0.031 (2)	0.025 (2)	0.0165 (18)	−0.0018 (15)	0.0026 (18)	−0.0019 (11)
C19A	0.0319 (18)	0.038 (3)	0.0267 (16)	−0.0004 (15)	0.0072 (11)	−0.0064 (16)
C20A	0.087 (4)	0.037 (2)	0.041 (2)	0.011 (2)	0.033 (2)	0.0124 (16)
C21	0.0172 (9)	0.0237 (9)	0.0210 (9)	−0.0006 (7)	0.0048 (7)	−0.0036 (7)
C22	0.0203 (10)	0.0227 (9)	0.0240 (9)	−0.0014 (7)	0.0041 (7)	−0.0022 (8)
C23	0.0240 (10)	0.0250 (10)	0.0201 (9)	0.0006 (8)	0.0005 (7)	0.0000 (8)
C24	0.0273 (11)	0.0349 (12)	0.0277 (10)	0.0016 (9)	0.0058 (8)	−0.0083 (9)
C25	0.0318 (12)	0.0401 (13)	0.0342 (11)	−0.0028 (10)	0.0039 (9)	−0.0155 (10)
C26	0.0242 (10)	0.0239 (10)	0.0255 (9)	0.0009 (8)	0.0017 (7)	0.0006 (8)
C27	0.0227 (10)	0.0204 (10)	0.0238 (9)	−0.0027 (7)	0.0080 (7)	0.0024 (7)
C28	0.0262 (10)	0.0213 (10)	0.0243 (9)	−0.0018 (8)	0.0029 (7)	0.0065 (8)
C29	0.0303 (11)	0.0275 (11)	0.0313 (11)	0.0010 (8)	0.0029 (8)	0.0084 (8)
C30	0.0304 (12)	0.0370 (12)	0.0396 (12)	−0.0026 (10)	−0.0070 (9)	0.0169 (10)
C31	0.0451 (14)	0.0426 (14)	0.0286 (10)	−0.0095 (10)	−0.0082 (9)	0.0071 (10)
C32	0.0458 (14)	0.0330 (12)	0.0248 (10)	−0.0021 (10)	0.0010 (9)	0.0008 (9)
C33	0.0300 (11)	0.0273 (10)	0.0258 (9)	−0.0016 (8)	0.0034 (8)	0.0035 (8)

O1—C27	1.298 (2)	C17—C18A	1.497 (4)
O1—H1O1	0.8200	C17—H17A	0.9602
O2—C9	1.262 (2)	C17—H17B	0.9603
O3—C7	1.223 (2)	C17—H17C	0.9603
O4—C10	1.389 (2)	C18A—C19A	1.336 (6)
O4—H1O4	0.8200	C18A—C20A	1.488 (6)
O5—C10	1.417 (2)	C19A—H19A	0.9300
O5—C4	1.454 (2)	C19A—H19B	0.9300
C1—C9	1.511 (3)	C20A—H20A	0.9600
C1—C10	1.546 (2)	C20A—H20B	0.9600
C1—C11	1.549 (2)	C20A—H20C	0.9600
C1—C2	1.555 (2)	C18B—C19B	1.324 (12)
C2—C3	1.536 (3)	C18B—C20B	1.479 (12)
C2—H2A	0.9700	C19B—H19C	0.9300
C2—H2B	0.9700	C19B—H19D	0.9300
C3—C16	1.537 (3)	C20B—H20D	0.9600
C3—C4	1.546 (3)	C20B—H20E	0.9600
C3—H3A	0.9800	C20B—H20F	0.9600
C4—C26	1.517 (3)	C21—C22	1.515 (3)
C4—C5	1.544 (2)	C21—H21A	0.9700
C5—C6	1.551 (3)	C21—H21B	0.9700
C5—H5A	0.9700	C22—C23	1.327 (3)
C5—H5B	0.9700	C22—H22A	0.9300
C6—C7	1.519 (3)	C23—C24	1.499 (3)
C6—C21	1.552 (2)	C23—C25	1.505 (3)
C6—C10	1.566 (2)	C24—H24A	0.9600
C7—C8	1.473 (3)	C24—H24B	0.9600
C8—C27	1.402 (3)	C24—H24C	0.9600
C8—C9	1.436 (3)	C25—H25A	0.9600
C11—C12	1.510 (3)	C25—H25B	0.9600
C11—H11A	0.9700	C25—H25C	0.9600
C11—H11B	0.9700	C26—H26A	0.9600
C12—C13	1.333 (3)	C26—H26B	0.9600
C12—H12A	0.9300	C26—H26C	0.9600
C13—C14	1.496 (3)	C27—C28	1.487 (3)
C13—C15	1.506 (3)	C28—C33	1.391 (3)
C14—H14A	0.9600	C28—C29	1.393 (3)
C14—H14B	0.9600	C29—C30	1.392 (3)
C14—H14C	0.9600	C29—H29A	0.9300
C15—H15A	0.9600	C30—C31	1.380 (4)
C15—H15B	0.9600	C30—H30A	0.9300
C15—H15C	0.9600	C31—C32	1.392 (4)
C16—C17	1.541 (3)	C31—H31A	0.9300
C16—H16A	0.9700	C32—C33	1.388 (3)
C16—H16B	0.9700	C32—H32A	0.9300
C17—C18B	1.483 (11)	C33—H33A	0.9300
C27—O1—H1O1	109.5	H16A—C16—H16B	107.9
C10—O4—H1O4	109.5	C18B—C17—C16	115.6 (12)
C10—O5—C4	105.31 (13)	C18A—C17—C16	114.9 (3)
C9—C1—C10	107.31 (14)	C18B—C17—H17A	108.5
C9—C1—C11	111.77 (16)	C18A—C17—H17A	117.7
C10—C1—C11	109.10 (15)	C16—C17—H17A	108.3
C9—C1—C2	107.87 (15)	C18B—C17—H17B	116.8
C10—C1—C2	107.82 (14)	C18A—C17—H17B	108.4
C11—C1—C2	112.76 (15)	C16—C17—H17B	108.6
C3—C2—C1	112.52 (15)	H17A—C17—H17B	97.1
C3—C2—H2A	109.1	C18B—C17—H17C	108.9
C1—C2—H2A	109.1	C18A—C17—H17C	99.7
C3—C2—H2B	109.1	C16—C17—H17C	108.0
C1—C2—H2B	109.1	H17A—C17—H17C	107.2
H2A—C2—H2B	107.8	C19A—C18A—C20A	121.0 (3)
C2—C3—C16	110.48 (16)	C19A—C18A—C17	120.8 (4)
C2—C3—C4	109.89 (15)	C20A—C18A—C17	118.2 (4)
C16—C3—C4	114.47 (16)	C18A—C19A—H19A	120.0
C2—C3—H3A	107.2	C18A—C19A—H19B	120.0
C16—C3—H3A	107.2	H19A—C19A—H19B	120.0
C4—C3—H3A	107.2	C19B—C18B—C20B	120.4 (12)
O5—C4—C26	107.49 (15)	C19B—C18B—C17	126.3 (12)
O5—C4—C5	102.80 (14)	C20B—C18B—C17	113.1 (10)
C26—C4—C5	112.76 (16)	C18B—C19B—H19C	120.0
O5—C4—C3	105.83 (14)	C18B—C19B—H19D	120.0
C26—C4—C3	113.40 (15)	H19C—C19B—H19D	120.0
C5—C4—C3	113.54 (15)	C18B—C20B—H20D	109.5
C4—C5—C6	104.59 (14)	C18B—C20B—H20E	109.5
C4—C5—H5A	110.8	H20D—C20B—H20E	109.5
C6—C5—H5A	110.8	C18B—C20B—H20F	109.5
C4—C5—H5B	110.8	H20D—C20B—H20F	109.5
C6—C5—H5B	110.8	H20E—C20B—H20F	109.5
H5A—C5—H5B	108.9	C22—C21—C6	114.87 (15)
C7—C6—C5	112.93 (15)	C22—C21—H21A	108.6
C7—C6—C21	106.98 (14)	C6—C21—H21A	108.6
C5—C6—C21	111.73 (16)	C22—C21—H21B	108.6
C7—C6—C10	112.97 (15)	C6—C21—H21B	108.6
C5—C6—C10	102.64 (14)	H21A—C21—H21B	107.5
C21—C6—C10	109.64 (14)	C23—C22—C21	124.69 (18)
O3—C7—C8	122.18 (17)	C23—C22—H22A	117.7
O3—C7—C6	120.41 (17)	C21—C22—H22A	117.7
C8—C7—C6	117.41 (16)	C22—C23—C24	124.00 (18)
C27—C8—C9	118.67 (18)	C22—C23—C25	121.25 (19)
C27—C8—C7	123.35 (17)	C24—C23—C25	114.76 (17)
C9—C8—C7	116.96 (17)	C23—C24—H24A	109.5
O2—C9—C8	120.92 (18)	C23—C24—H24B	109.5
O2—C9—C1	119.83 (17)	H24A—C24—H24B	109.5
C8—C9—C1	119.16 (17)	C23—C24—H24C	109.5
O4—C10—O5	109.37 (15)	H24A—C24—H24C	109.5
O4—C10—C1	106.11 (15)	H24B—C24—H24C	109.5
O5—C10—C1	109.97 (14)	C23—C25—H25A	109.5
O4—C10—C6	115.32 (14)	C23—C25—H25B	109.5
O5—C10—C6	103.67 (14)	H25A—C25—H25B	109.5
C1—C10—C6	112.36 (14)	C23—C25—H25C	109.5
C12—C11—C1	115.64 (16)	H25A—C25—H25C	109.5
C12—C11—H11A	108.4	H25B—C25—H25C	109.5
C1—C11—H11A	108.4	C4—C26—H26A	109.5
C12—C11—H11B	108.4	C4—C26—H26B	109.5
C1—C11—H11B	108.4	H26A—C26—H26B	109.5
H11A—C11—H11B	107.4	C4—C26—H26C	109.5
C13—C12—C11	126.22 (18)	H26A—C26—H26C	109.5
C13—C12—H12A	116.9	H26B—C26—H26C	109.5
C11—C12—H12A	116.9	O1—C27—C8	120.55 (18)
C12—C13—C14	121.73 (19)	O1—C27—C28	114.10 (17)
C12—C13—C15	123.94 (19)	C8—C27—C28	125.31 (18)
C14—C13—C15	114.29 (18)	C33—C28—C29	119.70 (19)
C13—C14—H14A	109.5	C33—C28—C27	121.89 (19)
C13—C14—H14B	109.5	C29—C28—C27	118.34 (18)
H14A—C14—H14B	109.5	C30—C29—C28	119.8 (2)
C13—C14—H14C	109.5	C30—C29—H29A	120.1
H14A—C14—H14C	109.5	C28—C29—H29A	120.1
H14B—C14—H14C	109.5	C31—C30—C29	120.5 (2)
C13—C15—H15A	109.5	C31—C30—H30A	119.7
C13—C15—H15B	109.5	C29—C30—H30A	119.7
H15A—C15—H15B	109.5	C30—C31—C32	119.7 (2)
C13—C15—H15C	109.5	C30—C31—H31A	120.1
H15A—C15—H15C	109.5	C32—C31—H31A	120.1
H15B—C15—H15C	109.5	C33—C32—C31	120.2 (2)
C3—C16—C17	111.89 (17)	C33—C32—H32A	119.9
C3—C16—H16A	109.2	C31—C32—H32A	119.9
C17—C16—H16A	109.2	C32—C33—C28	120.1 (2)
C3—C16—H16B	109.2	C32—C33—H33A	120.0
C17—C16—H16B	109.2	C28—C33—H33A	119.9
C9—C1—C2—C3	160.42 (15)	C2—C1—C10—C6	56.49 (19)
C10—C1—C2—C3	44.83 (19)	C7—C6—C10—O4	−91.58 (18)
C11—C1—C2—C3	−75.68 (19)	C5—C6—C10—O4	146.50 (15)
C1—C2—C3—C16	−175.28 (15)	C21—C6—C10—O4	27.6 (2)
C1—C2—C3—C4	−48.0 (2)	C7—C6—C10—O5	148.89 (14)
C10—O5—C4—C26	163.91 (14)	C5—C6—C10—O5	26.98 (17)
C10—O5—C4—C5	44.74 (17)	C21—C6—C10—O5	−91.90 (17)
C10—O5—C4—C3	−74.61 (16)	C7—C6—C10—C1	30.2 (2)
C2—C3—C4—O5	61.30 (18)	C5—C6—C10—C1	−91.72 (17)
C16—C3—C4—O5	−173.72 (15)	C21—C6—C10—C1	149.40 (16)
C2—C3—C4—C26	178.88 (16)	C9—C1—C11—C12	78.7 (2)
C16—C3—C4—C26	−56.1 (2)	C10—C1—C11—C12	−162.80 (16)
C2—C3—C4—C5	−50.7 (2)	C2—C1—C11—C12	−43.0 (2)
C16—C3—C4—C5	74.3 (2)	C1—C11—C12—C13	153.3 (2)
O5—C4—C5—C6	−25.42 (17)	C11—C12—C13—C14	179.2 (2)
C26—C4—C5—C6	−140.85 (15)	C11—C12—C13—C15	2.0 (3)
C3—C4—C5—C6	88.42 (18)	C2—C3—C16—C17	−66.0 (2)
C4—C5—C6—C7	−122.38 (16)	C4—C3—C16—C17	169.32 (16)
C4—C5—C6—C21	116.96 (16)	C3—C16—C17—C18B	−168.3 (8)
C4—C5—C6—C10	−0.44 (18)	C3—C16—C17—C18A	179.6 (3)
C5—C6—C7—O3	−44.1 (2)	C18B—C17—C18A—C19A	137 (8)
C21—C6—C7—O3	79.2 (2)	C16—C17—C18A—C19A	−126.4 (5)
C10—C6—C7—O3	−160.05 (15)	C18B—C17—C18A—C20A	−43 (7)
C5—C6—C7—C8	135.35 (16)	C16—C17—C18A—C20A	53.4 (6)
C21—C6—C7—C8	−101.31 (18)	C18A—C17—C18B—C19B	−21 (5)
C10—C6—C7—C8	19.4 (2)	C16—C17—C18B—C19B	−110 (3)
O3—C7—C8—C27	−28.6 (3)	C18A—C17—C18B—C20B	163 (9)
C6—C7—C8—C27	151.94 (17)	C16—C17—C18B—C20B	74 (2)
O3—C7—C8—C9	139.71 (18)	C7—C6—C21—C22	−67.3 (2)
C6—C7—C8—C9	−39.8 (2)	C5—C6—C21—C22	56.8 (2)
C27—C8—C9—O2	−1.0 (3)	C10—C6—C21—C22	169.87 (15)
C7—C8—C9—O2	−169.84 (17)	C6—C21—C22—C23	−161.87 (19)
C27—C8—C9—C1	175.66 (16)	C21—C22—C23—C24	−0.6 (3)
C7—C8—C9—C1	6.8 (2)	C21—C22—C23—C25	178.91 (19)
C10—C1—C9—O2	−141.69 (17)	C9—C8—C27—O1	−0.3 (3)
C11—C1—C9—O2	−22.1 (2)	C7—C8—C27—O1	167.77 (18)
C2—C1—C9—O2	102.38 (19)	C9—C8—C27—C28	177.48 (17)
C10—C1—C9—C8	41.6 (2)	C7—C8—C27—C28	−14.4 (3)
C11—C1—C9—C8	161.21 (16)	O1—C27—C28—C33	137.03 (19)
C2—C1—C9—C8	−74.29 (19)	C8—C27—C28—C33	−40.9 (3)
C4—O5—C10—O4	−168.82 (14)	O1—C27—C28—C29	−39.7 (3)
C4—O5—C10—C1	75.03 (16)	C8—C27—C28—C29	142.3 (2)
C4—O5—C10—C6	−45.31 (16)	C33—C28—C29—C30	1.2 (3)
C9—C1—C10—O4	67.41 (17)	C27—C28—C29—C30	177.98 (19)
C11—C1—C10—O4	−53.85 (18)	C28—C29—C30—C31	−0.7 (3)
C2—C1—C10—O4	−176.63 (14)	C29—C30—C31—C32	0.1 (3)
C9—C1—C10—O5	−174.40 (15)	C30—C31—C32—C33	0.1 (4)
C11—C1—C10—O5	64.34 (18)	C31—C32—C33—C28	0.3 (3)
C2—C1—C10—O5	−58.44 (18)	C29—C28—C33—C32	−1.0 (3)
C9—C1—C10—C6	−59.47 (19)	C27—C28—C33—C32	−177.67 (19)
C11—C1—C10—C6	179.27 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2	0.82	1.70	2.4446 (19)	151
O4—H1O4···O3i	0.82	1.97	2.7499 (18)	159
C21—H21B···O3i	0.97	2.48	3.283 (2)	139
C25—H25B···Cg4ii	0.96	2.99	3.786 (3)	142

Table 1

Hydrogen-bond geometry (Å, °)

Cg4 is the centroid of the C28–C33 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O2	0.82	1.70	2.4446 (19)	151
O4—H1O4⋯O3i	0.82	1.97	2.7499 (18)	159
C21—H21B⋯O3i	0.97	2.48	3.283 (2)	139
C25—H25B⋯Cg4ii	0.96	2.99	3.786 (3)	142

Symmetry codes: (i) ; (ii) .