ent-7α,18-Hydroxy­kaur-16-ene ethanol solvate

The ent-kaurene diterpene in the title compound, 7-epican­dicandiol ethanol solvate, C₂₀H₃₂O₂·C₂H₆O, was isolated from the aerial parts of Sideritis ozturkii Aytaç & Aksoy. The mol­ecule has the usual conformation and stereochemistry found in related ent-kaurene derivatives. The methyl-substituted ring junction has a trans arrangement and the other junction is cis. The six-membered rings have chair or slightly distorted chair conformations and the five-membered ring has an envelope conformation. Inter­molecular hydrogen bonds link the 7-epicandicandiol and ethanol mol­ecules into two-dimensional networks, part of which comprise co-operative O—H...O—H...O—H... chains.

S1. Comment

The genus Sideritis L., of which 46 species are found in Turkey (Huber-Morath, 1982; Davis et al., 1988; Aytaç & Aksoy, 2000; Duman, 2000), is recognized as a rich source of biologically active diterpenoids and flavonoids. Our previous chemical studies of the aerial parts of a local endemic species, Sideritis ozturkii Aytaç & Aksoy, led to the isolation of ent-kaurene-type diterpenoids and flavonoids, as well as phenylethanoid glycosides. Among these, two diterpenes were identified on the basis of their spectroscopic data (MS, and one- and two-dimensional NMR) as the known compounds linearol and 7-epicandicandiol (Şahin et al., 2004, 2005). The crystal structure of linearol has been reported previously (Ergin et al., 1993; Hökelek et al., 1999), although in the latter report the inverse enantiomer was employed for the structure refinement model and the chemical diagram shows the incorrect stereochemistry at atom C4. The crystal structure of 7-epicandicandiol, (I), reported here, was determined in order to confirm the stereochemistry and molecular structure of the compound.

The molecular structure of compound (I) is shown in Fig. 1. The compound crystallizes from ethanol as its 1:1 e thanol solvate. All bond lengths and angles fall within normal ranges. The absolute configuration has not been determined, but was assigned to correspond with that usually depicted for 7-epicandicandiol and related ent-kaurenes. The crystal structures of 57 kaurene derivatives are reported in the Cambridge Structural Database (CSD; Release 5.27 with January 2006 updates; Allen, 2002). Of these, only the structure of (4α)-kaur-16-en-18-carbonyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside (Mora et al., 2004) represents a definitive absolute configuration determination because of the known configuration of the α-D-glucopyranoside substituent. It is assumed that this structure establishes the absolute configuration of the core of this class of compounds. Although the configuration at the glucopyranoside-substituted C atom is opposite to that of the corresponding C atom in (I) and the hydroxy group at the 7-position is absent, the configurations of the remainder of the stereogenic centres correspond with those hitherto depicted for ent-kaurenes and also with those in (I).

The reported crystal structures of compounds most similar to (I) are those of epicandicandiol diacetate (ent-7α,18-diacetoxykaur-16-ene), which was synthesized directly from epicandicandiol (Hökelek et al., 2001), methyl ent-7α-hydroxykaur-16-en-19-oate (Le Quesne et al., 1985; Baynham et al., 1988) and (-)-ent-3β,7α-dihydroxy-18-acetoxykaur-16-ene (linearol; Ergin et al., 1993; Hökelek et al., 1999). The ring conformations in each of these structures are very similar to those observed in the structure of (I). The ring junction A–B in (I) is trans, while B–C is cis (see scheme). Rings A and B have almost normal chair conformations, with ring B being the more distorted, as shown by the puckering parameter (Cremer & Pople, 1975), θ, which has values of 176.7 (3) and 167.3 (3)° for the atom sequences C1–C5/C10 and C5–C10, respectively. The hydroxymethyl substituent at C4 in ring A lies in an equatorial position, while the hydroxy substituent at C7 ring B adopts an axial position. The conformation of ring C is that of a slightly more twisted chair, as a result of atoms C8, C13 and C14 also being part of the five-membered ring. For ring C, the puckering parameter Q is 0.631 (3) Å, θ is 23.7 (3)° and ϕ₂ is 287.8 (8)° for the atom sequence C8–C10/C12–C14. The five-membered ring, D, has an envelope conformation, with atom C14 as the envelope flap and a value for the ϕ₂ puckering parameter of 29.4 (4)° for the atom sequence C8/C14/C13/C16/C15. Atom C14 lies 0.687 (3) Å from the plane defined by the remaining four atoms of the ring.

It has been noted previously (Karle, 1972) that steric crowding of the methyl substituent at the A–B ring junction by other substituents in axial or pseudo-axial positions, namely atoms C12, C14 and C19 in (I), causes convex buckling of the molecular plane so as to allow these substituents more room. Similar to the observations of Karle and the corresponding intramolecular distances quoted for the above-mentioned related compounds, the buckling has relieved the crowding at C20 in (I) and there are no intramolecular distances involving C20 that are less than 3.2 Å [C19···C20 = 3.214 (4) Å].

The H atom of the hydroxy substituent on the central six-membered ring, B, forms an intermolecular hydrogen bond with the O atom of the ethanol molecule (Table 1). In turn, the hydroxy H atom of the ethanol molecule forms an intermolecular hydrogen bond with the O atom of the hydroxymethyl substituent in ring A of a different neighbouring 7-epicandicandiol molecule. These two interactions link the ethanol and 7-epicandicandiol molecules in an alternating fashion into extended chains which run parallel to the [100] direction and can be described by a binary graph-set motif (Bernstein et al., 1995) of C₂²(10). The hydroxy H atom of the hydroxymethyl substituent forms its own intermolecular hydrogen bond with the hydroxy O atom on ring B of another neighbouring molecule. This interaction links the 7-epicandicandiol molecules into extended chains which also run parallel to the [100] direction and can be described by a graph-set motif of C(8). The combination of all hydrogen-bonding interactions links all the moieties in the structure into two-dimensional networks which lie parallel to the (001) plane. In addition, the three structurally different hydroxy groups form a cooperative O—H···O—H···O—H··· chain which runs parallel to the [010] direction (Fig. 2) and can be described by a ternary graph-set motif of C₃³(6).

S2. Experimental

The title compound was isolated from Sideritis ozturkii Aytaç & Aksoy as described by Şahin et al. (2004, 2005). Suitable crystals were obtained by slow evaporation of a solution of the compound in ethanol (m.p. 316 K).

S3. Refinement

The hydroxy H atoms were located in a difference Fourier map and their positions were refined freely along with individual isotropic displacement parameters. The methyl H atoms were constrained to an ideal geometry (C—H = 0.98 Å) with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the C—C bonds. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.99–1.00 Å and with U_iso(H) = 1.2U_eq(C). As there are no significant anomalous dispersion effects with this compound, Friedel opposites were merged prior to the final cycles of refinement. The enantiomer used in the refinement model was chosen so as to correspond with that usually depicted for 7-epicandicandiol, although there does not appear to have been a definitive determination of the absolute configuration of this compound. Two low-angle reflections were omitted from the final cycles of refinement because their observed intensities were much lower than the calculated values, as a result of being partially obscured by the beam stop.

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary size.
	Fig. 2. The crystal packing in (I), viewed along the a axis, showing the cooperative O—H···O—H···O—H.. chain. Most of the H atoms have been omitted for clarity. Hydrogen bonds are represented by thin lines.

ent-7α,18-hydroxykaur-16-ene ethanol solvate

Crystal data

C20H32O2·C2H6O	Dx = 1.153 Mg m^−3
Mr = 350.54	Melting point: 316 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3806 reflections
a = 12.3391 (2) Å	θ = 2.0–25.0°
b = 7.1780 (1) Å	µ = 0.07 mm^−1
c = 22.8065 (4) Å	T = 160 K
V = 2019.97 (6) Å^3	Needle, colourless
Z = 4	0.30 × 0.12 × 0.12 mm
F(000) = 776

Data collection

Nonius KappaCCD area-detector diffractometer	1714 reflections with I > 2σ(I)
Radiation source: Nonius FR590 sealed tube generator	Rint = 0.062
Horizontally mounted graphite crystal monochromator	θmax = 25.0°, θmin = 3.2°
Detector resolution: 9 pixels mm^-1	h = −14→14
ϕ and ω scans with κ offsets	k = −8→8
20732 measured reflections	l = −27→27
2049 independent reflections

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)] = 0.042	Hydrogen site location: geom & difmap
wR(F^2) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0544P)^2 + 0.8216P] where P = (Fo^2 + 2Fc^2)/3
2047 reflections	(Δ/σ)max = 0.001
241 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Experimental. Solvent used: EtOH Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.430 (1) Frames collected: 1259 Seconds exposure per frame: 12 Degrees rotation per frame: 0.6 Crystal-Detector distance (mm): 60.0

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O7	0.28434 (17)	0.4568 (3)	0.45928 (9)	0.0302 (5)
H7	0.297 (3)	0.547 (6)	0.4802 (16)	0.052 (12)*
O18	0.73419 (18)	0.3827 (3)	0.49115 (11)	0.0396 (6)
H18	0.744 (3)	0.280 (6)	0.5079 (16)	0.046 (11)*
C1	0.4736 (2)	−0.0177 (4)	0.36140 (13)	0.0281 (7)
H11	0.4359	−0.0633	0.3969	0.034*
H12	0.4520	−0.0984	0.3282	0.034*
C2	0.5957 (2)	−0.0346 (4)	0.37061 (13)	0.0317 (7)
H21	0.6140	−0.1657	0.3797	0.038*
H22	0.6335	0.0000	0.3339	0.038*
C3	0.6351 (3)	0.0899 (4)	0.42019 (13)	0.0314 (7)
H31	0.7149	0.0799	0.4230	0.038*
H32	0.6042	0.0443	0.4576	0.038*
C4	0.6041 (2)	0.2968 (4)	0.41226 (12)	0.0275 (7)
C5	0.4798 (2)	0.3087 (4)	0.39962 (12)	0.0237 (6)
H5	0.4443	0.2584	0.4357	0.028*
C6	0.4363 (2)	0.5080 (4)	0.39359 (12)	0.0259 (6)
H61	0.4700	0.5882	0.4238	0.031*
H62	0.4563	0.5582	0.3546	0.031*
C7	0.3136 (2)	0.5123 (4)	0.40054 (11)	0.0248 (6)
H71	0.2881	0.6430	0.3941	0.030*
C8	0.2562 (2)	0.3857 (4)	0.35657 (12)	0.0266 (6)
C9	0.3097 (2)	0.1889 (4)	0.35231 (11)	0.0252 (6)
H9	0.2920	0.1270	0.3904	0.030*
C10	0.4365 (2)	0.1842 (4)	0.34865 (11)	0.0240 (6)
C11	0.2507 (3)	0.0704 (4)	0.30520 (13)	0.0325 (7)
H111	0.3005	−0.0298	0.2924	0.039*
H112	0.1875	0.0098	0.3240	0.039*
C12	0.2107 (3)	0.1736 (5)	0.25040 (14)	0.0402 (8)
H121	0.1563	0.0960	0.2299	0.048*
H122	0.2723	0.1938	0.2233	0.048*
C13	0.1599 (3)	0.3623 (4)	0.26623 (14)	0.0401 (8)
H13	0.1280	0.4262	0.2313	0.048*
C14	0.2466 (3)	0.4805 (4)	0.29611 (13)	0.0332 (7)
H141	0.2232	0.6119	0.2999	0.040*
H142	0.3161	0.4757	0.2744	0.040*
C15	0.1345 (2)	0.3606 (4)	0.37099 (14)	0.0352 (7)
H151	0.1237	0.2504	0.3964	0.042*
H152	0.1063	0.4719	0.3916	0.042*
C16	0.0778 (3)	0.3351 (5)	0.31455 (15)	0.0396 (8)
C17	−0.0271 (3)	0.2887 (5)	0.30631 (19)	0.0555 (10)
H171	−0.0730	0.2686	0.3391	0.067*
H172	−0.0549	0.2760	0.2677	0.067*
C18	0.6243 (2)	0.3944 (4)	0.47127 (13)	0.0345 (7)
H181	0.6041	0.5273	0.4675	0.041*
H182	0.5764	0.3381	0.5013	0.041*
C19	0.6766 (2)	0.3900 (5)	0.36582 (14)	0.0348 (7)
H191	0.6451	0.5101	0.3545	0.052*
H192	0.6815	0.3094	0.3312	0.052*
H193	0.7491	0.4099	0.3821	0.052*
C20	0.4787 (2)	0.2393 (4)	0.28739 (12)	0.0303 (7)
H201	0.5542	0.1990	0.2832	0.045*
H202	0.4745	0.3749	0.2828	0.045*
H203	0.4343	0.1791	0.2572	0.045*
O23	0.3378 (2)	0.7829 (4)	0.51716 (12)	0.0541 (7)
H23	0.311 (3)	0.884 (7)	0.5087 (19)	0.067 (14)*
C21	0.4442 (5)	0.6650 (8)	0.5941 (2)	0.104 (2)
H211	0.3838	0.6600	0.6219	0.155*
H212	0.5118	0.6886	0.6153	0.155*
H213	0.4495	0.5460	0.5732	0.155*
C22	0.4260 (4)	0.8097 (6)	0.5534 (2)	0.0819 (15)
H221	0.4158	0.9276	0.5752	0.098*
H222	0.4916	0.8238	0.5288	0.098*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O7	0.0406 (12)	0.0252 (11)	0.0248 (10)	−0.0022 (10)	0.0072 (9)	−0.0034 (10)
O18	0.0406 (13)	0.0267 (12)	0.0515 (14)	−0.0024 (10)	−0.0157 (11)	0.0040 (11)
C1	0.0396 (16)	0.0174 (14)	0.0273 (15)	0.0021 (13)	0.0020 (13)	−0.0004 (12)
C2	0.0398 (17)	0.0193 (14)	0.0361 (16)	0.0054 (13)	0.0036 (14)	−0.0001 (14)
C3	0.0324 (16)	0.0261 (15)	0.0357 (17)	0.0050 (14)	−0.0012 (13)	0.0026 (13)
C4	0.0327 (16)	0.0213 (14)	0.0284 (15)	−0.0002 (13)	0.0025 (12)	0.0007 (12)
C5	0.0306 (15)	0.0176 (13)	0.0229 (14)	0.0002 (12)	0.0035 (12)	0.0006 (12)
C6	0.0340 (16)	0.0178 (14)	0.0260 (14)	−0.0019 (12)	0.0015 (12)	0.0006 (12)
C7	0.0299 (15)	0.0199 (14)	0.0246 (14)	0.0016 (12)	0.0046 (12)	0.0011 (12)
C8	0.0309 (15)	0.0211 (14)	0.0278 (15)	0.0008 (13)	0.0019 (12)	−0.0018 (12)
C9	0.0341 (15)	0.0178 (14)	0.0237 (14)	−0.0003 (12)	0.0024 (12)	0.0007 (12)
C10	0.0306 (15)	0.0173 (14)	0.0243 (14)	0.0030 (12)	0.0041 (12)	−0.0008 (12)
C11	0.0366 (16)	0.0239 (15)	0.0371 (17)	0.0008 (14)	−0.0009 (14)	−0.0059 (13)
C12	0.0447 (19)	0.0364 (18)	0.0395 (18)	−0.0010 (16)	−0.0075 (15)	−0.0082 (16)
C13	0.0485 (19)	0.0345 (18)	0.0373 (18)	0.0029 (16)	−0.0113 (15)	−0.0011 (15)
C14	0.0432 (17)	0.0251 (15)	0.0312 (16)	0.0041 (14)	−0.0034 (14)	0.0016 (13)
C15	0.0345 (17)	0.0269 (16)	0.0441 (18)	0.0043 (14)	0.0007 (14)	−0.0054 (14)
C16	0.0397 (18)	0.0293 (17)	0.050 (2)	0.0045 (14)	−0.0070 (16)	−0.0044 (16)
C17	0.040 (2)	0.048 (2)	0.079 (3)	0.0033 (19)	−0.0157 (19)	−0.011 (2)
C18	0.0357 (16)	0.0296 (16)	0.0381 (18)	0.0001 (14)	−0.0054 (14)	−0.0013 (14)
C19	0.0326 (16)	0.0293 (16)	0.0424 (18)	−0.0020 (14)	0.0050 (14)	0.0026 (15)
C20	0.0402 (16)	0.0237 (15)	0.0270 (15)	0.0020 (13)	0.0037 (13)	0.0001 (13)
O23	0.0654 (17)	0.0310 (14)	0.0658 (18)	0.0079 (13)	−0.0160 (14)	−0.0134 (13)
C21	0.142 (5)	0.107 (4)	0.061 (3)	−0.037 (4)	−0.036 (3)	0.025 (3)
C22	0.079 (3)	0.052 (3)	0.115 (4)	0.012 (2)	−0.042 (3)	−0.019 (3)

Geometric parameters (Å, º)

O7—C7	1.444 (3)	C11—H111	0.9900
O7—H7	0.82 (4)	C11—H112	0.9900
O18—C18	1.433 (4)	C12—C13	1.535 (4)
O18—H18	0.84 (4)	C12—H121	0.9900
C1—C2	1.525 (4)	C12—H122	0.9900
C1—C10	1.548 (4)	C13—C16	1.510 (5)
C1—H11	0.9900	C13—C14	1.526 (4)
C1—H12	0.9900	C13—H13	1.0000
C2—C3	1.521 (4)	C14—H141	0.9900
C2—H21	0.9900	C14—H142	0.9900
C2—H22	0.9900	C15—C16	1.476 (4)
C3—C4	1.544 (4)	C15—H151	0.9900
C3—H31	0.9900	C15—H152	0.9900
C3—H32	0.9900	C16—C17	1.349 (5)
C4—C18	1.537 (4)	C17—H171	0.9500
C4—C19	1.539 (4)	C17—H172	0.9500
C4—C5	1.564 (4)	C18—H181	0.9900
C5—C6	1.534 (4)	C18—H182	0.9900
C5—C10	1.560 (4)	C19—H191	0.9800
C5—H5	1.0000	C19—H192	0.9800
C6—C7	1.523 (4)	C19—H193	0.9800
C6—H61	0.9900	C20—H201	0.9800
C6—H62	0.9900	C20—H202	0.9800
C7—C8	1.528 (4)	C20—H203	0.9800
C7—H71	1.0000	O23—C22	1.380 (5)
C8—C14	1.542 (4)	O23—H23	0.82 (5)
C8—C15	1.548 (4)	C21—C22	1.410 (6)
C8—C9	1.563 (4)	C21—H211	0.9800
C9—C11	1.552 (4)	C21—H212	0.9800
C9—C10	1.567 (4)	C21—H213	0.9800
C9—H9	1.0000	C22—H221	0.9900
C10—C20	1.543 (4)	C22—H222	0.9900
C11—C12	1.535 (4)
C7—O7—H7	106 (3)	C12—C11—H112	108.1
C18—O18—H18	110 (2)	C9—C11—H112	108.1
C2—C1—C10	113.1 (2)	H111—C11—H112	107.3
C2—C1—H11	109.0	C11—C12—C13	111.5 (3)
C10—C1—H11	109.0	C11—C12—H121	109.3
C2—C1—H12	109.0	C13—C12—H121	109.3
C10—C1—H12	109.0	C11—C12—H122	109.3
H11—C1—H12	107.8	C13—C12—H122	109.3
C3—C2—C1	111.8 (2)	H121—C12—H122	108.0
C3—C2—H21	109.3	C16—C13—C14	102.5 (3)
C1—C2—H21	109.3	C16—C13—C12	109.3 (3)
C3—C2—H22	109.3	C14—C13—C12	108.0 (3)
C1—C2—H22	109.3	C16—C13—H13	112.2
H21—C2—H22	107.9	C14—C13—H13	112.2
C2—C3—C4	113.5 (2)	C12—C13—H13	112.2
C2—C3—H31	108.9	C13—C14—C8	102.0 (2)
C4—C3—H31	108.9	C13—C14—H141	111.4
C2—C3—H32	108.9	C8—C14—H141	111.4
C4—C3—H32	108.9	C13—C14—H142	111.4
H31—C3—H32	107.7	C8—C14—H142	111.4
C18—C4—C19	108.1 (2)	H141—C14—H142	109.2
C18—C4—C3	107.2 (2)	C16—C15—C8	106.8 (3)
C19—C4—C3	110.8 (3)	C16—C15—H151	110.4
C18—C4—C5	107.2 (2)	C8—C15—H151	110.4
C19—C4—C5	114.8 (2)	C16—C15—H152	110.4
C3—C4—C5	108.5 (2)	C8—C15—H152	110.4
C6—C5—C10	110.3 (2)	H151—C15—H152	108.6
C6—C5—C4	114.2 (2)	C17—C16—C15	127.3 (3)
C10—C5—C4	116.2 (2)	C17—C16—C13	125.0 (3)
C6—C5—H5	104.9	C15—C16—C13	107.6 (3)
C10—C5—H5	104.9	C16—C17—H171	120.0
C4—C5—H5	104.9	C16—C17—H172	120.0
C7—C6—C5	110.9 (2)	H171—C17—H172	120.0
C7—C6—H61	109.5	O18—C18—C4	113.8 (2)
C5—C6—H61	109.5	O18—C18—H181	108.8
C7—C6—H62	109.5	C4—C18—H181	108.8
C5—C6—H62	109.5	O18—C18—H182	108.8
H61—C6—H62	108.0	C4—C18—H182	108.8
O7—C7—C6	109.8 (2)	H181—C18—H182	107.7
O7—C7—C8	109.2 (2)	C4—C19—H191	109.5
C6—C7—C8	112.4 (2)	C4—C19—H192	109.5
O7—C7—H71	108.4	H191—C19—H192	109.5
C6—C7—H71	108.4	C4—C19—H193	109.5
C8—C7—H71	108.4	H191—C19—H193	109.5
C7—C8—C14	111.1 (2)	H192—C19—H193	109.5
C7—C8—C15	112.3 (2)	C10—C20—H201	109.5
C14—C8—C15	99.6 (2)	C10—C20—H202	109.5
C7—C8—C9	112.5 (2)	H201—C20—H202	109.5
C14—C8—C9	112.1 (2)	C10—C20—H203	109.5
C15—C8—C9	108.6 (2)	H201—C20—H203	109.5
C11—C9—C8	109.9 (2)	H202—C20—H203	109.5
C11—C9—C10	114.8 (2)	C22—O23—H23	110 (3)
C8—C9—C10	116.4 (2)	C22—C21—H211	109.5
C11—C9—H9	104.8	C22—C21—H212	109.5
C8—C9—H9	104.8	H211—C21—H212	109.5
C10—C9—H9	104.8	C22—C21—H213	109.5
C20—C10—C1	108.1 (2)	H211—C21—H213	109.5
C20—C10—C5	114.3 (2)	H212—C21—H213	109.5
C1—C10—C5	107.1 (2)	O23—C22—C21	114.6 (4)
C20—C10—C9	112.3 (2)	O23—C22—H221	108.6
C1—C10—C9	107.8 (2)	C21—C22—H221	108.6
C5—C10—C9	106.9 (2)	O23—C22—H222	108.6
C12—C11—C9	116.8 (2)	C21—C22—H222	108.6
C12—C11—H111	108.1	H221—C22—H222	107.6
C9—C11—H111	108.1
C10—C1—C2—C3	57.3 (3)	C6—C5—C10—C1	−174.1 (2)
C1—C2—C3—C4	−55.3 (3)	C4—C5—C10—C1	53.8 (3)
C2—C3—C4—C18	166.6 (2)	C6—C5—C10—C9	−58.8 (3)
C2—C3—C4—C19	−75.7 (3)	C4—C5—C10—C9	169.1 (2)
C2—C3—C4—C5	51.2 (3)	C11—C9—C10—C20	54.5 (3)
C18—C4—C5—C6	61.8 (3)	C8—C9—C10—C20	−75.9 (3)
C19—C4—C5—C6	−58.2 (3)	C11—C9—C10—C1	−64.5 (3)
C3—C4—C5—C6	177.3 (2)	C8—C9—C10—C1	165.1 (2)
C18—C4—C5—C10	−167.9 (2)	C11—C9—C10—C5	−179.3 (2)
C19—C4—C5—C10	72.1 (3)	C8—C9—C10—C5	50.3 (3)
C3—C4—C5—C10	−52.4 (3)	C8—C9—C11—C12	36.5 (3)
C10—C5—C6—C7	64.6 (3)	C10—C9—C11—C12	−97.0 (3)
C4—C5—C6—C7	−162.2 (2)	C9—C11—C12—C13	−41.8 (4)
C5—C6—C7—O7	64.8 (3)	C11—C12—C13—C16	−50.2 (3)
C5—C6—C7—C8	−57.0 (3)	C11—C12—C13—C14	60.6 (3)
O7—C7—C8—C14	157.5 (2)	C16—C13—C14—C8	42.6 (3)
C6—C7—C8—C14	−80.3 (3)	C12—C13—C14—C8	−72.8 (3)
O7—C7—C8—C15	46.9 (3)	C7—C8—C14—C13	−163.3 (2)
C6—C7—C8—C15	169.1 (2)	C15—C8—C14—C13	−44.8 (3)
O7—C7—C8—C9	−75.9 (3)	C9—C8—C14—C13	69.9 (3)
C6—C7—C8—C9	46.2 (3)	C7—C8—C15—C16	148.6 (3)
C7—C8—C9—C11	−177.7 (2)	C14—C8—C15—C16	31.0 (3)
C14—C8—C9—C11	−51.6 (3)	C9—C8—C15—C16	−86.3 (3)
C15—C8—C9—C11	57.4 (3)	C8—C15—C16—C17	172.3 (3)
C7—C8—C9—C10	−45.0 (3)	C8—C15—C16—C13	−5.3 (3)
C14—C8—C9—C10	81.1 (3)	C14—C13—C16—C17	159.2 (3)
C15—C8—C9—C10	−169.9 (2)	C12—C13—C16—C17	−86.3 (4)
C2—C1—C10—C20	69.2 (3)	C14—C13—C16—C15	−23.1 (3)
C2—C1—C10—C5	−54.5 (3)	C12—C13—C16—C15	91.4 (3)
C2—C1—C10—C9	−169.1 (2)	C19—C4—C18—O18	−60.2 (3)
C6—C5—C10—C20	66.1 (3)	C3—C4—C18—O18	59.3 (3)
C4—C5—C10—C20	−66.0 (3)	C5—C4—C18—O18	175.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O23	0.82 (4)	1.96 (4)	2.767 (3)	169 (4)
O18—H18···O7^i	0.84 (4)	1.92 (4)	2.757 (3)	173 (4)
O23—H23···O18^ii	0.82 (5)	1.92 (5)	2.726 (3)	166 (4)

Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1/2, −y+3/2, −z+1.