6β-Angelo­yloxy-3β,8β-dihydroxy­eremophil-7(11)-en-12,8α-olide

The title compound, C₂₀H₂₈O₆, is an eremophilanolide which was isolated from the roots of Petasites Hybridus. The mol­ecule contains three fused rings, of which two six-membered rings adopt chair conformations and are fused in a cis configuration. In the angeloyl group, the carbonyl and methyl groups display a Z configuration about the C=C bond. The crystal structure is stabilized by O—H...O and C—H...O hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.035
• wR factor = 0.094
• Data-to-parameter ratio = 9.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.93 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.65 Ratio

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.50
           From the CIF: _reflns_number_total               2273
           Count of symmetry unique reflns         2309
           Completeness (_total/calc)             98.44%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C6     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C10    = .          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   7 ALERT level G = General alerts; check

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Petasites Hybridus (L.) is a medical plant belonging to the Compositae family. Its extracts were proved to have activities of anti-migraine (Lipton et al., 2004; Agosti et al., 2006), anti-allergy (Thomet & Simon, 2002; Gray et al., 2004; Jackson et al., 2004) and anti-inflammatory (Thomet et al., 2001; Fiebich et al., 2005). Many sesquiterpenes of the eremophilanolide type have been obtained from P. Hybridus (L.) (Neuenschwander, Neuenschwander & Steinegger, 1979; Neuenschwander, Neuenschwander, Steinegger & Engel, 1979;

Siegenthaler & Neuenschwander, 1997; Saritas et al., 2002; Bodensieck et al., 2007). Our investigation on the roots of this plant for bioactive components resulted in the isolation of the title compound (I), which was previously obtained from another plant P. Japonicus mixed together with its isomer, 6β-angeloyloxy-3β,8α-dihydroxyeremophil-7(11)-en-12,8β-olide (Sugama et al., 1985). The structure elucidations of these two isomers were performed after acetylation because of the difficulty in separating them from each other (Sugama et al., 1985; Yaoita et al., 1992; Yaoita & Kikuchi, 1994). We now report here the isolation and the single-crystal X-ray structure of the title compound, (I).

The molecular struture of (I) is shown in Fig. 1 and the bond lengths and angles are within normal ranges. The structure of (I) contains a fused three-ring system A/B/C. Two six-membered rings, i.e A and B, adopt the chair conformations and are fused in a cis configuration (Cremer & Pople, 1975). Ring C, a five-membered ring, deviates slightly from planarity indicated by the torsion angles C6—C7—C8—O of -173.77 (15)°, C8—C7—C11—C13 of -179.6 (3)°, C8—O4—C12—C11 of 0.8 (2)° and C11—C7—C8—O4 of -1.0 (2)°. The angeloyl group connects to O2 atom, the carbonyl and methyl groups have a Z configuration on the C?C bond. The dihedral angle of planar units in the angeloyl group (between plane defined by atoms O2, O6, C16 and C17 and the plane defined by C16, C17, C18, C19 and C20) is 20.95 (14)°.

The O–H···O and C–H···O hydrogen bonds help to stabilize the molecular conformation and crystal structure (Table 1).

Related literature

For general background, see: Agosti et al. (2006); Bodensieck et al. (2007); Cremer & Pople (1975); Fiebich et al. (2005); Gray et al. (2004); Jackson et al. (2004); Lipton et al. (2004); Neuenschwander, Neuenschwander & Steinegger (1979); Neuenschwander, Neuenschwander, Steinegger & Engel (1979); Saritas et al. (2002); Siegenthaler & Neuenschwander (1997); Sugama et al. (1985); Thomet & Simon (2002); Thomet et al. (2001); Yaoita & Kikuchi (1994); Yaoita et al. (1992).

S2. Experimental

The roots of P. hybridus (L.) were collected from Zhejiang Province of China in March 2006. The identification was carried out by Professor Chuan-Zhuo Qiao at the School of Pharmacy, Second Military Medical University.

The air-dried powdered roots of P. hybridus (L.) (2.5 kg) were extracted with 95% EtOH at room temperature. After evaporation of the solvent under reduced pressure, the residue of the 95% EtOH extract was suspended in H₂O, and then extracted successively with petroleum ether, EtOAc and n-BuOH to give the petroleum ether fraction (30 g), the EtOAc fraction (120 g) and the n-BuOH fraction (55 g), respectively. The EtOAc fraction was subjected to vacuum liquid chromatography on silica gel, eluting with n-hexane-EtOAc in increasing polarity to yield 4 fractions (Fr.1~4). Fr.2 (36 g) was submitted to column chromatography on silica gel eluting with n-hexane-EtOAc in increasing polarity to afford 5 fractions (Fr.A~E). Fr.B (6 g) was purified repeatedly by column chromatography on Sephadex LH-20 and Silica gel affording the title compound (I) (5 mg). X-ray quality crystals were obtained by recrystallization from n-hexane-EtOAc solution (1:1).

S3. Refinement

The hydroxyl H atoms were located in a difference Fourier map and isotropically refined with a constraint O—H distance 0.82 Å. The remaining H atoms were placed in calculated positions with C—H distances in the range 0.93–0.98 Å. The U_iso values were set equal to 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for the remaining H atoms. Friedel pairs were merged before the final refinement as there is no significant anomalous dispersion for the determination of the absolute configuration.

Computing details

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme with displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. The molecular packing of (I), viewed along the b axis.

6β-angeloyloxy-3β,8β-dihydroxyeremophil-7(11)-en-12,8α-olide

Crystal data

C20H28O6	F(000) = 392
Mr = 364.42	Dx = 1.254 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2840 reflections
a = 8.6160 (14) Å	θ = 2.3–27.2°
b = 13.093 (2) Å	µ = 0.09 mm^−1
c = 9.2584 (15) Å	T = 296 K
β = 112.499 (2)°	Prismatic, colorless
V = 964.9 (3) Å^3	0.25 × 0.20 × 0.15 mm
Z = 2

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	2027 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 27.5°, θmin = 2.3°
φ and ω scans	h = −11→10
6181 measured reflections	k = −13→16
2273 independent reflections	l = −11→11

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0598P)^2 + 0.0461P] where P = (Fo^2 + 2Fc^2)/3
2273 reflections	(Δ/σ)max < 0.001
248 parameters	Δρmax = 0.15 e Å^−3
3 restraints	Δρmin = −0.17 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
O1	1.0234 (2)	1.03673 (14)	0.2920 (2)	0.0550 (4)
H1X	1.066 (6)	0.987 (3)	0.347 (5)	0.121 (17)*
O2	0.37308 (15)	0.93739 (11)	0.20428 (14)	0.0371 (3)
O3	0.24117 (18)	1.14429 (14)	0.20077 (19)	0.0489 (4)
H3X	0.173 (3)	1.112 (2)	0.227 (3)	0.067 (9)*
O4	0.3663 (2)	1.22014 (12)	0.4432 (2)	0.0533 (4)
O5	0.4027 (4)	1.20759 (19)	0.6941 (3)	0.0886 (7)
O6	0.27831 (19)	0.86145 (14)	0.37027 (17)	0.0513 (4)
C1	0.7171 (3)	1.1679 (2)	0.1344 (3)	0.0514 (6)
H1A	0.7441	1.1217	0.0656	0.062*
H1B	0.6742	1.2307	0.0776	0.062*
C2	0.8745 (3)	1.19068 (19)	0.2761 (3)	0.0535 (6)
H2A	0.9590	1.2187	0.2420	0.064*
H2B	0.8492	1.2419	0.3396	0.064*
C3	0.9447 (3)	1.09694 (19)	0.3746 (3)	0.0470 (5)
H3	1.0322	1.1192	0.4732	0.056*
C4	0.8132 (2)	1.03547 (16)	0.4139 (2)	0.0382 (4)
H4	0.7841	1.0777	0.4873	0.046*
C5	0.6461 (2)	1.01715 (15)	0.2720 (2)	0.0328 (4)
C6	0.5169 (2)	0.97456 (14)	0.3373 (2)	0.0307 (4)
H6	0.5672	0.9185	0.4105	0.037*
C7	0.4592 (2)	1.05701 (15)	0.4167 (2)	0.0326 (4)
C8	0.3918 (2)	1.15371 (16)	0.3272 (2)	0.0385 (4)
C9	0.5214 (3)	1.19837 (16)	0.2726 (3)	0.0441 (5)
H9A	0.6170	1.2221	0.3623	0.053*
H9B	0.4736	1.2567	0.2057	0.053*
C10	0.5808 (2)	1.11928 (16)	0.1824 (2)	0.0393 (4)
H10	0.4847	1.1028	0.0863	0.047*
C11	0.4737 (3)	1.06644 (18)	0.5636 (3)	0.0430 (5)
C12	0.4125 (3)	1.1694 (2)	0.5809 (3)	0.0550 (6)
C13	0.5344 (4)	0.9937 (2)	0.6964 (3)	0.0689 (8)
H13A	0.6413	1.0161	0.7705	0.103*
H13B	0.5461	0.9270	0.6585	0.103*
H13C	0.4551	0.9908	0.7462	0.103*
C14	0.6657 (3)	0.93699 (18)	0.1583 (2)	0.0446 (5)
H14A	0.6868	0.8713	0.2081	0.067*
H14B	0.7580	0.9556	0.1299	0.067*
H14C	0.5643	0.9342	0.0662	0.067*
C15	0.8943 (3)	0.9388 (2)	0.5040 (3)	0.0560 (6)
H15A	0.9990	0.9560	0.5865	0.084*
H15B	0.9143	0.8911	0.4341	0.084*
H15C	0.8206	0.9085	0.5477	0.084*
C16	0.2616 (2)	0.88123 (16)	0.2383 (2)	0.0355 (4)
C17	0.1146 (3)	0.85431 (18)	0.0947 (2)	0.0451 (5)
C18	0.0138 (3)	0.7783 (2)	0.0942 (3)	0.0618 (7)
H18	−0.0762	0.7679	−0.0002	0.074*
C19	0.0222 (5)	0.7076 (3)	0.2203 (4)	0.0898 (11)
H19A	−0.0892	0.6860	0.2061	0.135*
H19B	0.0730	0.7415	0.3193	0.135*
H19C	0.0883	0.6491	0.2179	0.135*
C20	0.0845 (4)	0.9185 (3)	−0.0477 (3)	0.0704 (8)
H20A	−0.0193	0.8984	−0.1292	0.106*
H20B	0.1751	0.9089	−0.0826	0.106*
H20C	0.0785	0.9891	−0.0225	0.106*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0436 (8)	0.0512 (10)	0.0839 (12)	0.0060 (7)	0.0397 (9)	0.0061 (9)
O2	0.0351 (6)	0.0395 (7)	0.0342 (6)	−0.0078 (6)	0.0106 (5)	−0.0028 (6)
O3	0.0317 (7)	0.0544 (10)	0.0596 (9)	0.0073 (7)	0.0163 (6)	0.0176 (8)
O4	0.0536 (9)	0.0371 (8)	0.0798 (12)	0.0058 (7)	0.0374 (9)	−0.0041 (8)
O5	0.129 (2)	0.0699 (14)	0.0916 (16)	0.0024 (14)	0.0692 (16)	−0.0273 (12)
O6	0.0460 (8)	0.0636 (11)	0.0428 (8)	−0.0186 (8)	0.0154 (6)	0.0009 (8)
C1	0.0532 (12)	0.0454 (13)	0.0675 (14)	0.0025 (10)	0.0363 (11)	0.0173 (11)
C2	0.0448 (12)	0.0397 (12)	0.0898 (18)	−0.0054 (9)	0.0411 (12)	0.0017 (12)
C3	0.0326 (9)	0.0483 (13)	0.0640 (13)	−0.0047 (9)	0.0227 (9)	−0.0042 (11)
C4	0.0301 (8)	0.0431 (12)	0.0422 (9)	−0.0001 (8)	0.0148 (7)	−0.0010 (9)
C5	0.0318 (8)	0.0302 (9)	0.0388 (9)	−0.0002 (8)	0.0159 (7)	0.0017 (8)
C6	0.0295 (8)	0.0290 (9)	0.0327 (8)	−0.0030 (7)	0.0107 (7)	0.0017 (7)
C7	0.0281 (8)	0.0295 (9)	0.0415 (9)	−0.0037 (7)	0.0146 (7)	−0.0015 (8)
C8	0.0329 (9)	0.0340 (10)	0.0512 (11)	0.0036 (8)	0.0188 (8)	0.0024 (9)
C9	0.0378 (10)	0.0333 (10)	0.0656 (13)	0.0040 (8)	0.0249 (10)	0.0108 (10)
C10	0.0354 (9)	0.0372 (11)	0.0475 (10)	0.0006 (8)	0.0184 (8)	0.0097 (9)
C11	0.0471 (11)	0.0411 (11)	0.0439 (10)	−0.0039 (9)	0.0209 (9)	−0.0058 (9)
C12	0.0613 (14)	0.0471 (13)	0.0678 (15)	−0.0048 (11)	0.0372 (12)	−0.0149 (12)
C13	0.101 (2)	0.0663 (18)	0.0436 (12)	0.0057 (15)	0.0318 (14)	0.0025 (12)
C14	0.0519 (11)	0.0432 (11)	0.0458 (10)	−0.0029 (10)	0.0267 (9)	−0.0044 (10)
C15	0.0392 (10)	0.0651 (16)	0.0578 (13)	0.0042 (11)	0.0121 (10)	0.0167 (13)
C16	0.0331 (8)	0.0318 (9)	0.0407 (10)	−0.0016 (7)	0.0132 (7)	−0.0043 (8)
C17	0.0399 (10)	0.0445 (12)	0.0461 (10)	−0.0039 (9)	0.0111 (8)	−0.0129 (10)
C18	0.0541 (13)	0.0620 (16)	0.0614 (14)	−0.0196 (12)	0.0133 (12)	−0.0236 (13)
C19	0.107 (3)	0.063 (2)	0.100 (2)	−0.0419 (19)	0.039 (2)	−0.0163 (18)
C20	0.0734 (16)	0.0700 (19)	0.0439 (12)	−0.0058 (15)	−0.0041 (11)	−0.0050 (13)

Geometric parameters (Å, º)

O1—C3	1.436 (3)	C7—C8	1.503 (3)
O1—H1X	0.82 (2)	C8—C9	1.509 (3)
O2—C16	1.340 (2)	C9—C10	1.536 (3)
O2—C6	1.456 (2)	C9—H9A	0.9700
O3—C8	1.381 (3)	C9—H9B	0.9700
O3—H3X	0.827 (18)	C10—H10	0.9800
O4—C12	1.355 (3)	C11—C12	1.479 (3)
O4—C8	1.462 (3)	C11—C13	1.484 (3)
O5—C12	1.193 (3)	C13—H13A	0.9599
O6—C16	1.203 (2)	C13—H13B	0.9599
C1—C2	1.512 (4)	C13—H13C	0.9599
C1—C10	1.543 (3)	C14—H14A	0.9599
C1—H1A	0.9700	C14—H14B	0.9599
C1—H1B	0.9700	C14—H14C	0.9599
C2—C3	1.510 (4)	C15—H15A	0.9599
C2—H2A	0.9700	C15—H15B	0.9599
C2—H2B	0.9700	C15—H15C	0.9599
C3—C4	1.543 (3)	C16—C17	1.485 (3)
C3—H3	0.9800	C17—C18	1.320 (3)
C4—C15	1.530 (3)	C17—C20	1.500 (4)
C4—C5	1.552 (3)	C18—C19	1.470 (4)
C4—H4	0.9800	C18—H18	0.9300
C5—C14	1.540 (3)	C19—H19A	0.9599
C5—C6	1.559 (2)	C19—H19B	0.9599
C5—C10	1.560 (3)	C19—H19C	0.9599
C6—C7	1.494 (3)	C20—H20A	0.9599
C6—H6	0.9800	C20—H20B	0.9599
C7—C11	1.323 (3)	C20—H20C	0.9599
C3—O1—H1X	107 (3)	C10—C9—H9B	109.4
C16—O2—C6	116.06 (14)	H9A—C9—H9B	108.0
C8—O3—H3X	110 (2)	C9—C10—C1	109.09 (18)
C12—O4—C8	109.08 (16)	C9—C10—C5	114.61 (16)
C2—C1—C10	111.11 (18)	C1—C10—C5	110.31 (16)
C2—C1—H1A	109.4	C9—C10—H10	107.5
C10—C1—H1A	109.4	C1—C10—H10	107.5
C2—C1—H1B	109.4	C5—C10—H10	107.5
C10—C1—H1B	109.4	C7—C11—C12	107.4 (2)
H1A—C1—H1B	108.0	C7—C11—C13	131.1 (2)
C3—C2—C1	112.5 (2)	C12—C11—C13	121.5 (2)
C3—C2—H2A	109.1	O5—C12—O4	121.8 (3)
C1—C2—H2A	109.1	O5—C12—C11	128.7 (3)
C3—C2—H2B	109.1	O4—C12—C11	109.49 (19)
C1—C2—H2B	109.1	C11—C13—H13A	109.5
H2A—C2—H2B	107.8	C11—C13—H13B	109.5
O1—C3—C2	106.65 (19)	H13A—C13—H13B	109.5
O1—C3—C4	112.24 (19)	C11—C13—H13C	109.5
C2—C3—C4	113.94 (17)	H13A—C13—H13C	109.5
O1—C3—H3	107.9	H13B—C13—H13C	109.5
C2—C3—H3	107.9	C5—C14—H14A	109.5
C4—C3—H3	107.9	C5—C14—H14B	109.5
C15—C4—C3	109.66 (17)	H14A—C14—H14B	109.5
C15—C4—C5	114.57 (18)	C5—C14—H14C	109.5
C3—C4—C5	114.05 (17)	H14A—C14—H14C	109.5
C15—C4—H4	105.9	H14B—C14—H14C	109.5
C3—C4—H4	105.9	C4—C15—H15A	109.5
C5—C4—H4	105.9	C4—C15—H15B	109.5
C14—C5—C4	112.04 (16)	H15A—C15—H15B	109.5
C14—C5—C6	107.58 (16)	C4—C15—H15C	109.5
C4—C5—C6	107.18 (14)	H15A—C15—H15C	109.5
C14—C5—C10	109.42 (15)	H15B—C15—H15C	109.5
C4—C5—C10	110.28 (16)	O6—C16—O2	122.63 (17)
C6—C5—C10	110.29 (14)	O6—C16—C17	126.02 (19)
O2—C6—C7	108.78 (14)	O2—C16—C17	111.23 (17)
O2—C6—C5	107.12 (14)	C18—C17—C16	121.1 (2)
C7—C6—C5	110.71 (15)	C18—C17—C20	121.8 (2)
O2—C6—H6	110.1	C16—C17—C20	117.1 (2)
C7—C6—H6	110.1	C17—C18—C19	129.8 (2)
C5—C6—H6	110.1	C17—C18—H18	115.1
C11—C7—C6	130.91 (19)	C19—C18—H18	115.1
C11—C7—C8	110.64 (18)	C18—C19—H19A	109.5
C6—C7—C8	117.95 (15)	C18—C19—H19B	109.5
O3—C8—O4	108.62 (15)	H19A—C19—H19B	109.5
O3—C8—C7	115.58 (17)	C18—C19—H19C	109.5
O4—C8—C7	103.36 (15)	H19A—C19—H19C	109.5
O3—C8—C9	109.06 (17)	H19B—C19—H19C	109.5
O4—C8—C9	110.72 (18)	C17—C20—H20A	109.5
C7—C8—C9	109.36 (15)	C17—C20—H20B	109.5
C8—C9—C10	111.35 (18)	H20A—C20—H20B	109.5
C8—C9—H9A	109.4	C17—C20—H20C	109.5
C10—C9—H9A	109.4	H20A—C20—H20C	109.5
C8—C9—H9B	109.4	H20B—C20—H20C	109.5
C10—C1—C2—C3	56.7 (2)	C6—C7—C8—C9	−55.8 (2)
C1—C2—C3—O1	74.9 (2)	O3—C8—C9—C10	−74.2 (2)
C1—C2—C3—C4	−49.5 (3)	O4—C8—C9—C10	166.32 (16)
O1—C3—C4—C15	54.8 (3)	C7—C8—C9—C10	53.1 (2)
C2—C3—C4—C15	176.2 (2)	C8—C9—C10—C1	−178.10 (17)
O1—C3—C4—C5	−75.2 (2)	C8—C9—C10—C5	−53.9 (2)
C2—C3—C4—C5	46.2 (3)	C2—C1—C10—C9	66.8 (2)
C15—C4—C5—C14	−54.1 (2)	C2—C1—C10—C5	−59.9 (2)
C3—C4—C5—C14	73.5 (2)	C14—C5—C10—C9	168.00 (16)
C15—C4—C5—C6	63.7 (2)	C4—C5—C10—C9	−68.3 (2)
C3—C4—C5—C6	−168.75 (17)	C6—C5—C10—C9	49.8 (2)
C15—C4—C5—C10	−176.21 (17)	C14—C5—C10—C1	−68.4 (2)
C3—C4—C5—C10	−48.7 (2)	C4—C5—C10—C1	55.2 (2)
C16—O2—C6—C7	−71.9 (2)	C6—C5—C10—C1	173.42 (17)
C16—O2—C6—C5	168.37 (16)	C6—C7—C11—C12	173.02 (18)
C14—C5—C6—O2	−47.61 (19)	C8—C7—C11—C12	1.5 (2)
C4—C5—C6—O2	−168.28 (15)	C6—C7—C11—C13	−8.0 (4)
C10—C5—C6—O2	71.66 (19)	C8—C7—C11—C13	−179.6 (3)
C14—C5—C6—C7	−166.08 (15)	C8—O4—C12—O5	−179.7 (2)
C4—C5—C6—C7	73.25 (19)	C8—O4—C12—C11	0.8 (2)
C10—C5—C6—C7	−46.8 (2)	C7—C11—C12—O5	179.1 (3)
O2—C6—C7—C11	124.4 (2)	C13—C11—C12—O5	0.0 (4)
C5—C6—C7—C11	−118.1 (2)	C7—C11—C12—O4	−1.4 (3)
O2—C6—C7—C8	−64.51 (19)	C13—C11—C12—O4	179.5 (2)
C5—C6—C7—C8	52.9 (2)	C6—O2—C16—O6	−0.5 (3)
C12—O4—C8—O3	123.31 (19)	C6—O2—C16—C17	175.72 (16)
C12—O4—C8—C7	0.1 (2)	O6—C16—C17—C18	−22.5 (4)
C12—O4—C8—C9	−116.96 (19)	O2—C16—C17—C18	161.4 (2)
C11—C7—C8—O3	−119.53 (19)	O6—C16—C17—C20	156.3 (3)
C6—C7—C8—O3	67.7 (2)	O2—C16—C17—C20	−19.8 (3)
C11—C7—C8—O4	−1.0 (2)	C16—C17—C18—C19	−1.3 (5)
C6—C7—C8—O4	−173.77 (15)	C20—C17—C18—C19	180.0 (3)
C11—C7—C8—C9	117.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1X···O6^i	0.82 (2)	2.41 (4)	3.066 (3)	137 (4)
O3—H3X···O1^ii	0.83 (2)	1.90 (2)	2.726 (2)	178
C14—H14A···O5^iii	0.96	2.56	3.443 (3)	153
C14—H14B···O1	0.96	2.45	3.133 (3)	128
C19—H19B···O6	0.96	2.28	2.917 (3)	123
C18—H18···O3^iv	0.93	2.46	3.282 (3)	147

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z+1; (iv) −x, y−1/2, −z.