Redetermination and absolute configuration of (+)-7-epiclusianone.

The absolute configuration of 3-benzoyl-4-hy-droxy-6,6-dimethyl-1,5,7-tris-(3-methyl-but-2-en-yl)bicyclo-[3.3.1]non-3-ene-2,9-dione, C(33)H(42)O(4), isolated from Hypericum hypericoides, has been determined. The previous study [Xiao et al. (2007 ▶). J. Nat. Prod.70, 1779-1782] gave only the established relative configuration. The three stereogenic centers are now established as 1R, 5R and 7S on the basis of the refinement of the Flack absolute structure parameter against Cu Kα data and correspond to a specific rotation of [α](D) (20) = +66°. The enol-hy-droxy group forms an intra-molecular O-H⋯O hydrogen bond to close an S(6) ring.

Related literature

For a review of polycyclic polyprenylated acyl­phloroglucinols, see: Ciochina & Grossman (2006 ▶). For background to Clusiaceae metabolites, see: Garnsey et al. (2011 ▶); Zhang et al. (2010 ▶); Christian et al. (2008 ▶); Wu et al. (2008 ▶). For relative-configuration structure determinatons, see: Santos et al. (1998 ▶); Xiao et al. (2007 ▶); Martins et al. (2009 ▶). For related structures, see: McCandlish et al. (1976 ▶); Fronczek et al. (2012 ▶). For optical rotation results for the title compound, see: Piccinelli et al. (2005 ▶) and for related compounds, see: Tanaka et al. (2004 ▶). For keto–enol tautomerism in related compounds, see: Martins et al. (2007 ▶). For absolute configuration based on resonant scattering from light atoms, see: Hooft et al. (2008 ▶)

Experimental

Crystal data

C33H42O4

M = 502.67

Orthorhombic,

a = 8.6177 (4) Å

b = 12.4157 (6) Å

c = 26.8632 (13) Å

V = 2874.2 (2) Å3

Z = 4

Cu Kα radiation

μ = 0.59 mm−1

T = 90 K

0.25 × 0.24 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD DUO diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.824, T max = 0.889

17192 measured reflections

5171 independent reflections

5131 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.074

S = 1.03

5171 reflections

345 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.14 e Å−3

Absolute structure: Flack (1983 ▶), 2200 Friedel pairs

Flack parameter: 0.04 (12)

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812043784/hb6978sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043784/hb6978Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812043784/hb6978Isup3.cml

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

C33H42O4	F(000) = 1088
Mr = 502.67	Dx = 1.162 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9866 reflections
a = 8.6177 (4) Å	θ = 6.1–68.7°
b = 12.4157 (6) Å	µ = 0.59 mm−1
c = 26.8632 (13) Å	T = 90 K
V = 2874.2 (2) Å3	Fragment, colourless
Z = 4	0.25 × 0.24 × 0.16 mm

Bruker Kappa APEXII CCD DUO diffractometer	5171 independent reflections
Radiation source: IµS microfocus	5131 reflections with I > 2σ(I)
QUAZAR multilayer optics monochromator	Rint = 0.029
φ and ω scans	θmax = 69.0°, θmin = 6.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −7→10
Tmin = 0.824, Tmax = 0.889	k = −14→14
17192 measured reflections	l = −26→32

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)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.074	w = 1/[σ2(Fo2) + (0.0421P)2 + 0.5041P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
5171 reflections	Δρmax = 0.22 e Å−3
345 parameters	Δρmin = −0.14 e Å−3
0 restraints	Absolute structure: Flack (1983), 2200 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.04 (12)

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
O1	0.38204 (9)	0.57722 (6)	0.55937 (3)	0.02174 (17)
O2	0.19699 (9)	0.30231 (6)	0.66019 (3)	0.02165 (18)
H2O	0.1128 (18)	0.3151 (13)	0.6345 (6)	0.032*
O3	0.55907 (10)	0.53739 (7)	0.71815 (3)	0.02443 (18)
O4	0.02182 (10)	0.37865 (7)	0.59833 (3)	0.02514 (19)
C1	0.53797 (13)	0.53245 (9)	0.62906 (4)	0.0180 (2)
C2	0.38730 (13)	0.52889 (8)	0.59874 (4)	0.0171 (2)
C3	0.26005 (13)	0.46092 (9)	0.61697 (4)	0.0180 (2)
C4	0.29307 (13)	0.38075 (9)	0.65168 (4)	0.0177 (2)
C5	0.43928 (13)	0.37919 (9)	0.68338 (4)	0.0190 (2)
C6	0.56654 (13)	0.29794 (9)	0.66112 (4)	0.0209 (2)
C7	0.61814 (14)	0.33294 (9)	0.60776 (4)	0.0204 (2)
H7	0.7201	0.2961	0.6026	0.024*
C8	0.65687 (13)	0.45420 (9)	0.60513 (4)	0.0205 (2)
H8A	0.6689	0.4742	0.5697	0.025*
H8B	0.7585	0.4656	0.6215	0.025*
C9	0.51344 (13)	0.49077 (9)	0.68128 (4)	0.0184 (2)
C10	0.10833 (13)	0.45927 (9)	0.59317 (4)	0.0197 (2)
C11	0.04524 (13)	0.55219 (10)	0.56511 (4)	0.0218 (2)
C12	−0.05267 (14)	0.53185 (12)	0.52473 (5)	0.0291 (3)
H12	−0.0719	0.4599	0.5144	0.035*
C13	−0.12146 (17)	0.61707 (14)	0.49996 (5)	0.0397 (4)
H13	−0.1865	0.6034	0.4721	0.048*
C14	−0.09644 (17)	0.72184 (14)	0.51530 (6)	0.0431 (4)
H14	−0.1446	0.7799	0.4982	0.052*
C15	−0.00110 (17)	0.74202 (12)	0.55568 (6)	0.0399 (3)
H15	0.0150	0.8140	0.5665	0.048*
C16	0.07115 (15)	0.65772 (10)	0.58051 (5)	0.0288 (3)
H16	0.1379	0.6720	0.6079	0.035*
C17	0.50800 (15)	0.18136 (9)	0.66151 (4)	0.0245 (3)
H17A	0.5839	0.1349	0.6449	0.037*
H17B	0.4085	0.1773	0.6439	0.037*
H17C	0.4942	0.1574	0.6960	0.037*
C18	0.71138 (14)	0.30162 (11)	0.69510 (5)	0.0268 (3)
H18A	0.6842	0.2745	0.7282	0.040*
H18B	0.7482	0.3761	0.6978	0.040*
H18C	0.7934	0.2566	0.6808	0.040*
C19	0.39058 (15)	0.35180 (10)	0.73731 (4)	0.0241 (3)
H19A	0.3508	0.2770	0.7384	0.029*
H19B	0.4828	0.3557	0.7592	0.029*
C20	0.26812 (16)	0.42675 (11)	0.75676 (4)	0.0268 (3)
H20	0.2918	0.5014	0.7552	0.032*
C21	0.13033 (16)	0.40148 (11)	0.77591 (4)	0.0282 (3)
C22	0.02230 (18)	0.48786 (12)	0.79411 (6)	0.0406 (3)
H22A	0.0692	0.5587	0.7883	0.061*
H22B	0.0035	0.4781	0.8298	0.061*
H22C	−0.0763	0.4831	0.7761	0.061*
C23	0.07067 (16)	0.28880 (12)	0.78242 (5)	0.0350 (3)
H23A	0.1448	0.2378	0.7680	0.052*
H23B	−0.0297	0.2816	0.7656	0.052*
H23C	0.0579	0.2734	0.8180	0.052*
C24	0.51574 (14)	0.29320 (9)	0.56401 (4)	0.0210 (2)
H24A	0.5060	0.2138	0.5656	0.025*
H24B	0.4105	0.3245	0.5672	0.025*
C25	0.58384 (15)	0.32466 (9)	0.51460 (4)	0.0241 (3)
H25	0.6906	0.3082	0.5102	0.029*
C26	0.51463 (16)	0.37244 (9)	0.47629 (4)	0.0251 (3)
C27	0.34689 (16)	0.40573 (10)	0.47428 (5)	0.0288 (3)
H27A	0.2939	0.3815	0.5046	0.043*
H27B	0.2974	0.3730	0.4451	0.043*
H27C	0.3401	0.4843	0.4718	0.043*
C28	0.60348 (19)	0.39918 (11)	0.42989 (5)	0.0356 (3)
H28A	0.7113	0.3754	0.4336	0.053*
H28B	0.6010	0.4772	0.4244	0.053*
H28C	0.5562	0.3624	0.4014	0.053*
C29	0.60306 (14)	0.64717 (9)	0.62838 (4)	0.0211 (2)
H29A	0.6948	0.6507	0.6505	0.025*
H29B	0.6378	0.6647	0.5942	0.025*
C30	0.48630 (14)	0.72998 (9)	0.64493 (4)	0.0213 (2)
H30	0.4012	0.7045	0.6641	0.026*
C31	0.48995 (14)	0.83484 (9)	0.63557 (4)	0.0218 (2)
C32	0.36423 (15)	0.90856 (10)	0.65404 (5)	0.0280 (3)
H32A	0.2827	0.8659	0.6701	0.042*
H32B	0.3199	0.9483	0.6259	0.042*
H32C	0.4080	0.9595	0.6781	0.042*
C33	0.62042 (16)	0.88899 (10)	0.60776 (5)	0.0275 (3)
H33A	0.6857	0.9288	0.6313	0.041*
H33B	0.5772	0.9389	0.5831	0.041*
H33C	0.6831	0.8344	0.5908	0.041*

	U11	U22	U33	U12	U13	U23
O1	0.0240 (4)	0.0205 (4)	0.0207 (4)	−0.0005 (3)	0.0017 (3)	0.0040 (3)
O2	0.0212 (4)	0.0193 (4)	0.0244 (4)	−0.0034 (3)	0.0001 (3)	0.0034 (3)
O3	0.0267 (4)	0.0254 (4)	0.0211 (4)	−0.0026 (3)	−0.0026 (3)	−0.0038 (3)
O4	0.0198 (4)	0.0214 (4)	0.0342 (5)	−0.0033 (3)	−0.0018 (3)	0.0030 (4)
C1	0.0181 (5)	0.0161 (5)	0.0198 (5)	0.0000 (4)	0.0021 (4)	−0.0011 (4)
C2	0.0205 (5)	0.0139 (5)	0.0170 (5)	0.0028 (4)	0.0026 (4)	−0.0016 (4)
C3	0.0190 (5)	0.0169 (5)	0.0181 (5)	0.0008 (4)	0.0013 (4)	−0.0013 (4)
C4	0.0200 (5)	0.0158 (5)	0.0173 (5)	0.0002 (4)	0.0037 (4)	−0.0032 (4)
C5	0.0213 (5)	0.0193 (5)	0.0165 (5)	0.0002 (5)	−0.0002 (4)	0.0002 (4)
C6	0.0222 (5)	0.0195 (6)	0.0212 (6)	0.0024 (4)	−0.0023 (4)	0.0013 (5)
C7	0.0197 (5)	0.0187 (5)	0.0227 (6)	0.0034 (5)	0.0019 (5)	−0.0009 (4)
C8	0.0191 (5)	0.0210 (6)	0.0214 (5)	−0.0003 (4)	0.0028 (4)	−0.0003 (5)
C9	0.0156 (5)	0.0196 (5)	0.0198 (5)	0.0027 (4)	0.0003 (4)	−0.0015 (4)
C10	0.0195 (5)	0.0192 (5)	0.0203 (5)	0.0009 (4)	0.0037 (4)	−0.0025 (4)
C11	0.0163 (5)	0.0257 (6)	0.0233 (5)	0.0022 (4)	0.0039 (4)	0.0043 (5)
C12	0.0228 (6)	0.0431 (7)	0.0215 (6)	0.0035 (6)	0.0029 (5)	0.0037 (6)
C13	0.0300 (7)	0.0636 (10)	0.0256 (6)	0.0093 (7)	0.0022 (6)	0.0168 (7)
C14	0.0304 (7)	0.0518 (9)	0.0472 (9)	0.0132 (7)	0.0101 (6)	0.0325 (7)
C15	0.0291 (7)	0.0271 (7)	0.0635 (10)	0.0057 (5)	0.0101 (7)	0.0162 (7)
C16	0.0216 (6)	0.0248 (6)	0.0400 (7)	0.0033 (5)	0.0026 (5)	0.0040 (5)
C17	0.0304 (6)	0.0203 (6)	0.0229 (6)	0.0016 (5)	−0.0007 (5)	0.0033 (5)
C18	0.0252 (6)	0.0275 (6)	0.0276 (6)	0.0040 (5)	−0.0057 (5)	0.0025 (5)
C19	0.0296 (6)	0.0254 (6)	0.0173 (5)	−0.0037 (5)	−0.0003 (5)	0.0027 (4)
C20	0.0349 (7)	0.0270 (6)	0.0187 (5)	−0.0057 (5)	0.0047 (5)	−0.0014 (5)
C21	0.0327 (7)	0.0335 (7)	0.0183 (5)	−0.0045 (6)	0.0007 (5)	−0.0006 (5)
C22	0.0412 (8)	0.0408 (8)	0.0398 (8)	−0.0073 (7)	0.0164 (6)	−0.0087 (6)
C23	0.0298 (7)	0.0398 (8)	0.0352 (7)	−0.0082 (6)	0.0003 (6)	0.0082 (6)
C24	0.0255 (6)	0.0166 (5)	0.0210 (5)	0.0017 (4)	0.0018 (5)	−0.0013 (4)
C25	0.0290 (6)	0.0191 (6)	0.0241 (6)	0.0045 (5)	0.0052 (5)	−0.0028 (5)
C26	0.0364 (7)	0.0168 (5)	0.0222 (6)	−0.0001 (5)	0.0029 (5)	−0.0041 (5)
C27	0.0358 (7)	0.0252 (6)	0.0253 (6)	−0.0022 (5)	−0.0072 (5)	−0.0009 (5)
C28	0.0514 (9)	0.0308 (7)	0.0245 (6)	0.0054 (6)	0.0077 (6)	0.0029 (5)
C29	0.0206 (6)	0.0185 (6)	0.0242 (6)	−0.0031 (4)	0.0021 (5)	−0.0006 (4)
C30	0.0226 (6)	0.0211 (6)	0.0202 (5)	−0.0031 (5)	0.0012 (4)	−0.0032 (4)
C31	0.0267 (6)	0.0209 (5)	0.0177 (5)	−0.0014 (5)	−0.0042 (5)	−0.0019 (4)
C32	0.0327 (7)	0.0215 (6)	0.0297 (6)	0.0034 (5)	−0.0037 (5)	−0.0008 (5)
C33	0.0338 (7)	0.0187 (6)	0.0300 (6)	−0.0027 (5)	−0.0014 (5)	0.0031 (5)

O1—C2	1.2169 (13)	C18—H18B	0.9800
O2—C4	1.2986 (14)	C18—H18C	0.9800
O2—H2O	1.014 (16)	C19—C20	1.5009 (18)
O3—C9	1.2126 (14)	C19—H19A	0.9900
O4—C10	1.2558 (15)	C19—H19B	0.9900
O4—H2O	1.477 (16)	C20—C21	1.3316 (19)
C1—C9	1.5103 (15)	C20—H20	0.9500
C1—C29	1.5309 (15)	C21—C23	1.5007 (19)
C1—C2	1.5333 (15)	C21—C22	1.5019 (19)
C1—C8	1.5515 (15)	C22—H22A	0.9800
C2—C3	1.4679 (15)	C22—H22B	0.9800
C3—C4	1.3932 (16)	C22—H22C	0.9800
C3—C10	1.4556 (16)	C23—H23A	0.9800
C4—C5	1.5208 (16)	C23—H23B	0.9800
C5—C9	1.5267 (16)	C23—H23C	0.9800
C5—C19	1.5464 (15)	C24—C25	1.5028 (16)
C5—C6	1.6055 (16)	C24—H24A	0.9900
C6—C17	1.5329 (16)	C24—H24B	0.9900
C6—C18	1.5471 (16)	C25—C26	1.3291 (18)
C6—C7	1.5624 (16)	C25—H25	0.9500
C7—C8	1.5437 (16)	C26—C28	1.5002 (18)
C7—C24	1.5504 (16)	C26—C27	1.5044 (19)
C7—H7	1.0000	C27—H27A	0.9800
C8—H8A	0.9900	C27—H27B	0.9800
C8—H8B	0.9900	C27—H27C	0.9800
C10—C11	1.4815 (16)	C28—H28A	0.9800
C11—C16	1.3920 (18)	C28—H28B	0.9800
C11—C12	1.3972 (18)	C28—H28C	0.9800
C12—C13	1.383 (2)	C29—C30	1.5057 (16)
C12—H12	0.9500	C29—H29A	0.9900
C13—C14	1.381 (3)	C29—H29B	0.9900
C13—H13	0.9500	C30—C31	1.3264 (17)
C14—C15	1.384 (2)	C30—H30	0.9500
C14—H14	0.9500	C31—C32	1.5025 (17)
C15—C16	1.3886 (19)	C31—C33	1.5080 (17)
C15—H15	0.9500	C32—H32A	0.9800
C16—H16	0.9500	C32—H32B	0.9800
C17—H17A	0.9800	C32—H32C	0.9800
C17—H17B	0.9800	C33—H33A	0.9800
C17—H17C	0.9800	C33—H33B	0.9800
C18—H18A	0.9800	C33—H33C	0.9800
C4—O2—H2O	102.7 (9)	H18A—C18—H18C	109.5
C10—O4—H2O	100.6 (6)	H18B—C18—H18C	109.5
C9—C1—C29	112.40 (9)	C20—C19—C5	112.37 (10)
C9—C1—C2	111.41 (9)	C20—C19—H19A	109.1
C29—C1—C2	109.32 (9)	C5—C19—H19A	109.1
C9—C1—C8	105.23 (9)	C20—C19—H19B	109.1
C29—C1—C8	109.62 (9)	C5—C19—H19B	109.1
C2—C1—C8	108.74 (9)	H19A—C19—H19B	107.9
O1—C2—C3	123.07 (10)	C21—C20—C19	127.98 (12)
O1—C2—C1	118.62 (10)	C21—C20—H20	116.0
C3—C2—C1	118.16 (9)	C19—C20—H20	116.0
C4—C3—C10	117.87 (10)	C20—C21—C23	124.76 (13)
C4—C3—C2	118.78 (10)	C20—C21—C22	120.69 (12)
C10—C3—C2	122.18 (10)	C23—C21—C22	114.54 (12)
O2—C4—C3	121.56 (10)	C21—C22—H22A	109.5
O2—C4—C5	114.85 (10)	C21—C22—H22B	109.5
C3—C4—C5	123.57 (10)	H22A—C22—H22B	109.5
C4—C5—C9	108.34 (9)	C21—C22—H22C	109.5
C4—C5—C19	107.61 (9)	H22A—C22—H22C	109.5
C9—C5—C19	110.34 (9)	H22B—C22—H22C	109.5
C4—C5—C6	111.44 (9)	C21—C23—H23A	109.5
C9—C5—C6	105.69 (9)	C21—C23—H23B	109.5
C19—C5—C6	113.34 (9)	H23A—C23—H23B	109.5
C17—C6—C18	106.82 (10)	C21—C23—H23C	109.5
C17—C6—C7	111.26 (9)	H23A—C23—H23C	109.5
C18—C6—C7	107.67 (9)	H23B—C23—H23C	109.5
C17—C6—C5	111.47 (9)	C25—C24—C7	111.38 (10)
C18—C6—C5	108.23 (9)	C25—C24—H24A	109.4
C7—C6—C5	111.18 (9)	C7—C24—H24A	109.4
C8—C7—C24	113.50 (9)	C25—C24—H24B	109.4
C8—C7—C6	112.01 (9)	C7—C24—H24B	109.4
C24—C7—C6	116.42 (9)	H24A—C24—H24B	108.0
C8—C7—H7	104.5	C26—C25—C24	128.65 (12)
C24—C7—H7	104.5	C26—C25—H25	115.7
C6—C7—H7	104.5	C24—C25—H25	115.7
C7—C8—C1	116.67 (9)	C25—C26—C28	120.87 (13)
C7—C8—H8A	108.1	C25—C26—C27	125.57 (12)
C1—C8—H8A	108.1	C28—C26—C27	113.56 (11)
C7—C8—H8B	108.1	C26—C27—H27A	109.5
C1—C8—H8B	108.1	C26—C27—H27B	109.5
H8A—C8—H8B	107.3	H27A—C27—H27B	109.5
O3—C9—C1	123.35 (10)	C26—C27—H27C	109.5
O3—C9—C5	122.61 (10)	H27A—C27—H27C	109.5
C1—C9—C5	113.81 (9)	H27B—C27—H27C	109.5
O4—C10—C3	119.73 (10)	C26—C28—H28A	109.5
O4—C10—C11	117.33 (10)	C26—C28—H28B	109.5
C3—C10—C11	122.84 (10)	H28A—C28—H28B	109.5
C16—C11—C12	119.85 (12)	C26—C28—H28C	109.5
C16—C11—C10	121.52 (11)	H28A—C28—H28C	109.5
C12—C11—C10	118.42 (11)	H28B—C28—H28C	109.5
C13—C12—C11	119.60 (14)	C30—C29—C1	112.76 (9)
C13—C12—H12	120.2	C30—C29—H29A	109.0
C11—C12—H12	120.2	C1—C29—H29A	109.0
C14—C13—C12	120.65 (14)	C30—C29—H29B	109.0
C14—C13—H13	119.7	C1—C29—H29B	109.0
C12—C13—H13	119.7	H29A—C29—H29B	107.8
C13—C14—C15	119.81 (13)	C31—C30—C29	126.76 (11)
C13—C14—H14	120.1	C31—C30—H30	116.6
C15—C14—H14	120.1	C29—C30—H30	116.6
C14—C15—C16	120.41 (15)	C30—C31—C32	121.22 (12)
C14—C15—H15	119.8	C30—C31—C33	123.31 (11)
C16—C15—H15	119.8	C32—C31—C33	115.44 (10)
C15—C16—C11	119.66 (13)	C31—C32—H32A	109.5
C15—C16—H16	120.2	C31—C32—H32B	109.5
C11—C16—H16	120.2	H32A—C32—H32B	109.5
C6—C17—H17A	109.5	C31—C32—H32C	109.5
C6—C17—H17B	109.5	H32A—C32—H32C	109.5
H17A—C17—H17B	109.5	H32B—C32—H32C	109.5
C6—C17—H17C	109.5	C31—C33—H33A	109.5
H17A—C17—H17C	109.5	C31—C33—H33B	109.5
H17B—C17—H17C	109.5	H33A—C33—H33B	109.5
C6—C18—H18A	109.5	C31—C33—H33C	109.5
C6—C18—H18B	109.5	H33A—C33—H33C	109.5
H18A—C18—H18B	109.5	H33B—C33—H33C	109.5
C6—C18—H18C	109.5
C9—C1—C2—O1	167.02 (10)	C29—C1—C9—C5	176.44 (9)
C29—C1—C2—O1	42.19 (13)	C2—C1—C9—C5	53.35 (12)
C8—C1—C2—O1	−77.45 (12)	C8—C1—C9—C5	−64.32 (11)
C9—C1—C2—C3	−17.26 (14)	C4—C5—C9—O3	133.48 (11)
C29—C1—C2—C3	−142.09 (10)	C19—C5—C9—O3	15.92 (15)
C8—C1—C2—C3	98.26 (11)	C6—C5—C9—O3	−106.98 (12)
O1—C2—C3—C4	157.56 (11)	C4—C5—C9—C1	−51.93 (12)
C1—C2—C3—C4	−17.96 (15)	C19—C5—C9—C1	−169.49 (9)
O1—C2—C3—C10	−9.79 (17)	C6—C5—C9—C1	67.62 (11)
C1—C2—C3—C10	174.70 (9)	C4—C3—C10—O4	−10.85 (16)
C10—C3—C4—O2	4.87 (16)	C2—C3—C10—O4	156.60 (11)
C2—C3—C4—O2	−163.02 (10)	C4—C3—C10—C11	165.27 (11)
C10—C3—C4—C5	−173.26 (10)	C2—C3—C10—C11	−27.28 (16)
C2—C3—C4—C5	18.85 (16)	O4—C10—C11—C16	139.12 (12)
O2—C4—C5—C9	−162.55 (9)	C3—C10—C11—C16	−37.08 (17)
C3—C4—C5—C9	15.69 (15)	O4—C10—C11—C12	−35.60 (16)
O2—C4—C5—C19	−43.25 (13)	C3—C10—C11—C12	148.19 (11)
C3—C4—C5—C19	135.00 (11)	C16—C11—C12—C13	0.88 (18)
O2—C4—C5—C6	81.58 (12)	C10—C11—C12—C13	175.69 (11)
C3—C4—C5—C6	−100.17 (12)	C11—C12—C13—C14	−1.2 (2)
C4—C5—C6—C17	−63.20 (12)	C12—C13—C14—C15	0.3 (2)
C9—C5—C6—C17	179.32 (9)	C13—C14—C15—C16	0.8 (2)
C19—C5—C6—C17	58.35 (12)	C14—C15—C16—C11	−1.1 (2)
C4—C5—C6—C18	179.61 (10)	C12—C11—C16—C15	0.22 (19)
C9—C5—C6—C18	62.13 (11)	C10—C11—C16—C15	−174.43 (12)
C19—C5—C6—C18	−58.83 (12)	C4—C5—C19—C20	−54.58 (13)
C4—C5—C6—C7	61.56 (12)	C9—C5—C19—C20	63.43 (13)
C9—C5—C6—C7	−55.92 (11)	C6—C5—C19—C20	−178.26 (10)
C19—C5—C6—C7	−176.89 (9)	C5—C19—C20—C21	125.34 (13)
C17—C6—C7—C8	172.43 (9)	C19—C20—C21—C23	0.8 (2)
C18—C6—C7—C8	−70.84 (12)	C19—C20—C21—C22	179.41 (13)
C5—C6—C7—C8	47.55 (13)	C8—C7—C24—C25	52.17 (12)
C17—C6—C7—C24	39.50 (13)	C6—C7—C24—C25	−175.58 (10)
C18—C6—C7—C24	156.23 (10)	C7—C24—C25—C26	−130.54 (13)
C5—C6—C7—C24	−85.38 (12)	C24—C25—C26—C28	179.04 (12)
C24—C7—C8—C1	87.10 (12)	C24—C25—C26—C27	−0.3 (2)
C6—C7—C8—C1	−47.26 (13)	C9—C1—C29—C30	−70.74 (12)
C9—C1—C8—C7	52.49 (12)	C2—C1—C29—C30	53.51 (12)
C29—C1—C8—C7	173.57 (10)	C8—C1—C29—C30	172.61 (9)
C2—C1—C8—C7	−66.97 (12)	C1—C29—C30—C31	−159.64 (11)
C29—C1—C9—O3	−9.02 (15)	C29—C30—C31—C32	179.38 (11)
C2—C1—C9—O3	−132.11 (11)	C29—C30—C31—C33	−2.82 (19)
C8—C1—C9—O3	110.23 (12)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O4	1.014 (16)	1.477 (16)	2.4368 (12)	155.7 (15)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O4	1.014 (16)	1.477 (16)	2.4368 (12)	155.7 (15)