Two drimane lactones, valdiviolide and 11-epivaldiviolide, in the form of a 1:1 cocrystal obtained from Drimys winteri extracts

A cocrystal, C₁₅H₂₂O₃·C₁₅H₂₂O₃, (I), obtained from Drimys winteri, is composed of two isomeric drimane sesquiterpene lactones, namely valdiviolide, (Ia), and 11-epivaldiviolide, (Ib), neither of which has been reported in the crystal form. Both diastereoisomers present three chiral centres at sites 5, 10 and 11, with an SSR sequence in (Ia) and an SSS sequence in (Ib). O-H...O hydrogen bonds bind mol­ecules into chains running along [20] and the chains are in turn linked by [pi]-[pi] stacking inter­actions to define planar weakly inter­acting arrays parallel to (001).

S1. Introduction

The folk medicinal plant Drimys winteri (Winter­aceae) is a slender tree native to the Magellanic and Valdivian temperate rain forests of Chile (where it is locally called "Canelo"). The tree's barks are rich in drimane sesquiterpenoids as secondary metabolites, some of which present intense pungent and potent anti­feedant, anti­microbial, plant growth inhibitory, cytotoxic and piscicidal activities. A paradigmatic example of these multi-functional sesquiterpenoids is polygodial (Kubo et al., 2005; Jansen & de Groot, 2004). It is perhaps worth mentioning that these properties of Canelo barks are not new, and they had been known for long by the native Araucanean people who used them in their ancient medicinal rituals.

Following a well established research line in our laboratory, focused on the study of natural products from the Southern Andean flora we succeeded in extracting from Drimys winteri barks a compound of general formulation C₁₅ H₂₂ O₃ (I). To our surprise, upon crystallization (followed by its structure resolution ) the solid showed to consist of a single phase lodging two molecules of identical formula but diverse stereochemistry, viz., valdiviolide and 11-epivaldiviolide (Scheme).

Valdiviolide ((Ia)) is a drimane sesquiterpene mostly found in a variety of south American plants. It was originally extracted from Drimys winteri by Appel et al., 1963, and subsequently the subject of a large amount of synthetic work (Ley & Mahon, 1983; Nakano et al., 1998, etc.), from which its absolute structure could be envisaged.

For its isomer, 11-epivaldiviolide, (Ib), on the other hand, we could not trace reliable reports of its extraction from botanical sources. It has, however, been found as a metabolite of marine organisms such as the Japanese nudibranch Dendrodoris carbunculosa (Sakio et al., 2001)

In spite of both species being already known for some time, the crystal forms have not been reported, either in isolation or mixed up as in the present compound (I), where they are found to cocrystallize in an orderly fashion in the triclinic space group P1.

Thus, in what follows, we present the structure of valdiviolide–11-epivaldiviolide (1/1) cocrystal, (I).

S2. Experimental

S2.1. Extraction, purification and crystallization

Compound (I) was isolated from the stem bark of Drimys winteri (Canelo) collected in Concepcion, VIII Region of Chile in February 2012. The bark (1 kg) was powdered and extracted by maceration with ethanol for 3 d, giving a crude product (20 g) which was further purified by column chromatography. It afforded as a yellow oil from hexane/ethyl acetate (4:1 v/v) and a white solid from hexane/ethyl acetate (1:1 v/v). This solid was recrystallized from methanol at 277 K, producing colourless crystals suitable for X-ray diffraction analysis.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were identified in an inter­mediate difference map and were treated differently in the refinement. H atoms on C atoms were idealized and allowed to ride both in coordinates as in displacement parameters, the latter taken as U_iso(H) = xU_eq(C), with C—H = 0.93 Å and x = 1.2 for aromatic, C—H = 0.97 Å and x = 1.2 for methyl­ene, and C—H = 0.96 Å and x = 1.5 for methyl H atoms. H atoms attached to O atoms were refined with O—H distance and H···H anti­bump restraints.

The use of Mo Kα radiation for data collection precluded a trustable determination of the absolute structure from diffraction data alone [Flack parameters: 0.2 (6)/0.8 (6) for the reported/inverted configurations, respectively]. The present `handedness', however, defined by C5 (S/S), C10 (S/S), C11 (R/S) for (Ia)/(Ib), respectively, was found to coincide with the assignments reported in the literature.

S3. Results and discussion

Fig. 1 shows a displacement ellipsoid plot of the asymmetric unit of (I), where the two molecules in the cocrystal, i.e. valdiviolide, (Ia), and 11-epivaldiviolide, Ib), are identified by trailing labels A and B. The molecules are almost identical except for the different configuration at site 11 [R in (Ia) and S in (Ib)], and the similarities can be disclosed in Fig. 2, where a superposition of both molecules is presented. (Ia)/Ib) The characteristic rigid backbone of this family of compounds is made up of three fused rings (see Scheme for labelling), where lateral rings A (atoms C1–C5/C10) have a chair conformation (Cremer & Pople, 1975) with puckering parameters θ = 5.2 (4)/2.7 (4)° for (Ia)/Ib), respectively; cf θ = 0.00° for an ideal chair (Boeyens, 1978). The central ring B (atoms C5–C10) presents a quasi-envelope conformation [θ = 48.8 (3)/50.6 (3)° and ϕ = 9.3 (5)/8.3 (5)°; θ = 54.7° and ϕ = 0° for an ideal envelope (Boeyens, 1978)]. The five-membered lactone ring C (atoms C8/C9/C11/C12/O3) is in a nearly planar conformation [mean torsion = 0.9 (3)/1.9 (4)°], a direct consequence of the `inner' location of the C8═ C9 double bond; when the double bond lies outside the lactone ring, viz. C7═C8 (as in Dendocarbin A; Paz Robles et al., 2014, and references therein), the lactone ring is no longer aromatic and adopts an envelope conformation. Another common feature commented on by Paz Robles el al. (2014) is to do with the concentration of electronic density (with the concomitant bond contraction) in the C11/12—O3 bonds neighbouring the carbonyl group, irrespective of its position (either 11 or 12) in the lactone ring. This peculiarity is also found in the two structures reported herein, as well as in isodrimenin [Cambridge Structural Database (CSD, Version 5.34; Allen, 2002) refcode FUXPOL; Escobar & Wittke, 1988; see (II) in the Scheme], the only single structure found in the CSD sharing the same nucleus and double-bond disposition, with the C12═O2 carbonyl group replaced by a methyl­ene group and the C11—OH hy­droxy group replaced by a carbonyl group (see Scheme). Table 2 provides a comparison of corresponding parameters displaying the differences in bond length among all three structures. As already mentioned, the most relevant differences are found around the lactone O3 atom and have to do precisely with the position of the carbonyl group, viz. C12═O2 in (Ia) and (Ib) and C11═O1 in (II). In all cases, the C═O group presents a clear resonance with the neighbouring C12—O3 (C11—O3) group, which is sensibly shorter than its C11—O3 (C12—O3) neighbour (See Table 2).

Regarding the supra­molecular structure, there are two significant inter­molecular hydrogen bonds in (I), involving the hy­droxy groups as donors and the carbonyl groups as acceptors (Table 3). These hydrogen bonds connect neighbouring molecules of different types, in an A···B···A···B sequence, forming C(6) chains [see Bernstein et al. (1995) for graph-set notation] along the [120] direction, in patterns much resembling a `frustrated' 2₁ axis (Fig. 3a). Incidentally, an eventually exact 2₁ sequence would be impossible due to the different configuration of both molecules. Such a 2₁ pattern, however, is usual in related compounds crystallizing in chiral space groups having 2₁ axis (P2₁, P2₁2₁2₁), where the chain appears truly threaded along the real screw (e.g. the already mentioned Dendocarbin A).

These [120] chains are in turn linked by π–π inter­actions connecting lactone rings of opposite types (Table 4 and Fig. 3b) nearly along [100]. The result is the formation of planar arrays parallel to (001). Fig. 4 presents two packing views of (I); Fig. 4(a) is a projection along [100], showing the way in which chains (running from top to bottom) overlap, bound by lactone–lactone stacking inter­actions. Note the way in which molecules of types A and B alternate along the chain. They also alternate along the direction of the stacking inter­action, even if adjacent chains are related by full-cell translations; the explanation is given by the slanted direction of the [120] chains with reference to the unit-cell axis.

Fig. 4(b), in turn, shows a view of the planes along [001], where the [120] direction of the hydrogen-bonded chains is clearly seen. From inspection of Fig. 4(a) it is also apparent that the inter­active (hydro­philic) parts of the molecules are concentrated at c ~0.50; the cell edges (c ~0.00, 1.00) lodge instead the barely inter­active hydro­phobic parts, which face each other in the crystal packing, with what there are almost no inter­actions between adjacent planes.

Related literature

For related literature, see: Allen (2002); Appel et al. (1963); Bernstein et al. (1995); Boeyens (1978); Cremer & Pople (1975); Escobar & Wittke (1988); Jansen & de Groot (2004); Kubo et al. (2005); Ley & Mahon (1983); Nakano et al. (1998); Paz Robles, Burgos, Suarez & Baggio (2014); Sakio et al. (2001).

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2013, PLATON (Spek, 2009).

Figures

	Fig. 1. Displacement ellipsoid plots of the asymmetric units of (Ia) and (Ib), both drawn at the 30% probability level. The dashed line indicates an intrachain hydrogen bond.
	Fig. 2. A schematic view of the least-squares fit of (Ia) (in full lines) and (Ib) (in broken lines). The conformational difference between the two molecules is highlighted.
	Fig. 3. The intermolecular interactions described in Tables 3 and 4. (a) A single chain built up by O—H· O hydrogen bonds (Table 3) and (b) the stacking interaction linking lactone rings (Table 4).
	Fig. 4. Different views of the (001) planes, (a) projected down [100] and (b) projected down [001]. The chains are differentiated by their line shading.

(I)

Crystal data

C30H44O6	Z = 1
Mr = 500.65	F(000) = 272
Triclinic, P1	Dx = 1.217 Mg m^−3
a = 6.6766 (4) Å	Mo Kα radiation, λ = 0.71069 Å
b = 7.1292 (4) Å	Cell parameters from 3755 reflections
c = 16.0995 (10) Å	θ = 3.7–22.1°
α = 78.423 (5)°	µ = 0.08 mm^−1
β = 84.663 (5)°	T = 295 K
γ = 65.460 (5)°	Blocks, colourless
V = 682.88 (7) Å^3	0.30 × 0.22 × 0.22 mm

Data collection

Oxford Diffraction Gemini CCD S Ultra diffractometer	4929 reflections with I > 2σ(I)
ω scans, thick slices	Rint = 0.053
Absorption correction: multi-scan CrysAlis PRO (Oxford Diffraction, 2009)	θmax = 29.3°, θmin = 3.7°
Tmin = 0.96, Tmax = 0.97	h = −9→8
21131 measured reflections	k = −9→9
6463 independent reflections	l = −20→21

Refinement

Refinement on F^2	7 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0657P)^2 + 0.0278P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
6463 reflections	Δρmax = 0.24 e Å^−3
339 parameters	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.

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

	x	y	z	Uiso*/Ueq
C1A	0.8421 (7)	−0.1903 (5)	0.2474 (2)	0.0595 (9)
H1AA	0.9698	−0.3132	0.2705	0.071*
H1AB	0.7116	−0.2126	0.2688	0.071*
C2A	0.8491 (8)	−0.1639 (5)	0.1512 (2)	0.0696 (11)
H2AA	0.9829	−0.1483	0.1297	0.084*
H2AB	0.8504	−0.2879	0.1346	0.084*
C3A	0.6514 (8)	0.0263 (6)	0.1133 (3)	0.0703 (10)
H3AA	0.5192	0.0047	0.1324	0.084*
H3AB	0.6598	0.0388	0.0521	0.084*
C4A	0.6308 (6)	0.2334 (5)	0.1361 (2)	0.0584 (9)
C5A	0.6450 (5)	0.2018 (4)	0.2338 (2)	0.0453 (7)
H5AA	0.5128	0.1799	0.2553	0.054*
C6A	0.6246 (6)	0.3961 (4)	0.2678 (2)	0.0552 (8)
H6AA	0.7623	0.4129	0.2579	0.066*
H6AB	0.5103	0.5198	0.2371	0.066*
C7A	0.5697 (6)	0.3783 (4)	0.3617 (2)	0.0534 (8)
H7AA	0.6128	0.4708	0.3853	0.064*
H7AB	0.4119	0.4225	0.3697	0.064*
C8A	0.6831 (5)	0.1623 (4)	0.40701 (19)	0.0416 (7)
C9A	0.7984 (5)	−0.0069 (4)	0.3714 (2)	0.0463 (7)
C10A	0.8393 (5)	0.0028 (4)	0.2773 (2)	0.0420 (7)
C11A	0.8961 (5)	−0.1959 (4)	0.43973 (19)	0.0428 (6)
H11A	1.0572	−0.2527	0.4360	0.051*
C12A	0.6990 (5)	0.0963 (4)	0.4984 (2)	0.0427 (7)
C13A	0.8045 (8)	0.3023 (6)	0.0870 (3)	0.0751 (11)
H13A	0.9482	0.1918	0.0982	0.113*
H13B	0.7978	0.4256	0.1047	0.113*
H13C	0.7759	0.3327	0.0273	0.113*
C14A	0.4012 (8)	0.4007 (8)	0.1074 (3)	0.0957 (15)
H14A	0.3915	0.5365	0.1119	0.144*
H14B	0.2904	0.3711	0.1430	0.144*
H14C	0.3788	0.3987	0.0496	0.144*
C15A	1.0689 (6)	0.0062 (6)	0.2628 (3)	0.0641 (9)
H15A	1.1710	−0.1059	0.3016	0.096*
H15B	1.0619	0.1377	0.2719	0.096*
H15C	1.1169	−0.0110	0.2056	0.096*
O1A	0.8250 (4)	−0.3516 (3)	0.43921 (15)	0.0510 (5)
O2A	0.6240 (4)	0.1988 (3)	0.55499 (15)	0.0566 (6)
O3A	0.8205 (3)	−0.1130 (3)	0.51828 (14)	0.0474 (5)
C1B	0.5087 (6)	0.6373 (5)	0.7510 (2)	0.0550 (8)
H1BA	0.5265	0.5127	0.7301	0.066*
H1BB	0.6234	0.6810	0.7253	0.066*
C2B	0.5350 (7)	0.5847 (6)	0.8471 (2)	0.0673 (10)
H2BA	0.6805	0.4762	0.8614	0.081*
H2BB	0.4272	0.5315	0.8728	0.081*
C3B	0.5037 (7)	0.7788 (6)	0.8823 (2)	0.0665 (10)
H3BA	0.6188	0.8246	0.8594	0.080*
H3BB	0.5202	0.7411	0.9434	0.080*
C4B	0.2785 (6)	0.9624 (5)	0.8616 (2)	0.0529 (8)
C5B	0.2462 (5)	1.0063 (4)	0.76401 (19)	0.0414 (6)
H5BA	0.3637	1.0497	0.7396	0.050*
C6B	0.0321 (5)	1.1914 (4)	0.7315 (2)	0.0495 (7)
H6BA	−0.0897	1.1492	0.7441	0.059*
H6BB	0.0048	1.3059	0.7610	0.059*
C7B	0.0426 (5)	1.2675 (4)	0.6360 (2)	0.0470 (7)
H7BA	−0.1054	1.3408	0.6136	0.056*
H7BB	0.1135	1.3645	0.6253	0.056*
C8B	0.1685 (4)	1.0862 (4)	0.59250 (18)	0.0382 (6)
C9B	0.2757 (4)	0.8877 (4)	0.62997 (18)	0.0370 (6)
C10B	0.2828 (5)	0.8123 (4)	0.72441 (19)	0.0392 (6)
C11B	0.3888 (5)	0.7548 (4)	0.56421 (19)	0.0398 (6)
H11B	0.5488	0.6978	0.5706	0.048*
C12B	0.1989 (4)	1.0967 (4)	0.50102 (19)	0.0393 (6)
C13B	0.0953 (7)	0.9203 (7)	0.9151 (3)	0.0733 (11)
H13D	0.0999	0.7877	0.9085	0.110*
H13E	−0.0448	1.0293	0.8967	0.110*
H13F	0.1156	0.9175	0.9737	0.110*
C14B	0.2907 (9)	1.1561 (6)	0.8864 (3)	0.0855 (15)
H14D	0.1500	1.2725	0.8776	0.128*
H14E	0.4000	1.1908	0.8519	0.128*
H14F	0.3296	1.1250	0.9450	0.128*
C15B	0.1025 (6)	0.7270 (5)	0.7448 (2)	0.0556 (8)
H15D	0.1247	0.6249	0.7101	0.083*
H15E	−0.0396	0.8402	0.7335	0.083*
H15F	0.1101	0.6628	0.8035	0.083*
O1B	0.3228 (4)	0.5946 (3)	0.56564 (15)	0.0507 (5)
O2B	0.1319 (4)	1.2476 (3)	0.44398 (14)	0.0533 (6)
O3B	0.3231 (3)	0.9033 (3)	0.48363 (13)	0.0462 (5)
H1OB	0.415 (3)	0.481 (4)	0.549 (3)	0.103 (16)*
H1OA	0.909 (3)	−0.480 (2)	0.453 (3)	0.119 (19)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1A	0.084 (3)	0.0356 (16)	0.060 (2)	−0.0222 (17)	0.0026 (17)	−0.0166 (14)
C2A	0.106 (3)	0.0478 (19)	0.061 (2)	−0.031 (2)	0.000 (2)	−0.0251 (17)
C3A	0.088 (3)	0.075 (2)	0.062 (2)	−0.041 (2)	−0.008 (2)	−0.0210 (19)
C4A	0.068 (2)	0.0492 (18)	0.052 (2)	−0.0189 (16)	−0.0049 (16)	−0.0059 (15)
C5A	0.0492 (17)	0.0343 (14)	0.0517 (18)	−0.0172 (13)	0.0021 (13)	−0.0072 (12)
C6A	0.073 (2)	0.0278 (14)	0.058 (2)	−0.0152 (14)	0.0042 (16)	−0.0060 (13)
C7A	0.067 (2)	0.0256 (13)	0.064 (2)	−0.0145 (13)	0.0019 (16)	−0.0107 (13)
C8A	0.0440 (16)	0.0327 (13)	0.0516 (18)	−0.0173 (12)	0.0030 (13)	−0.0130 (12)
C9A	0.0511 (18)	0.0322 (14)	0.0523 (18)	−0.0127 (13)	0.0005 (14)	−0.0105 (12)
C10A	0.0471 (16)	0.0278 (12)	0.0491 (17)	−0.0122 (11)	0.0012 (13)	−0.0101 (11)
C11A	0.0411 (15)	0.0334 (14)	0.0493 (17)	−0.0081 (12)	−0.0009 (12)	−0.0130 (12)
C12A	0.0384 (15)	0.0335 (14)	0.0586 (18)	−0.0139 (12)	0.0001 (13)	−0.0155 (13)
C13A	0.106 (3)	0.065 (2)	0.058 (2)	−0.042 (2)	0.009 (2)	−0.0062 (18)
C14A	0.092 (3)	0.089 (3)	0.075 (3)	−0.008 (3)	−0.025 (3)	0.003 (2)
C15A	0.056 (2)	0.069 (2)	0.068 (2)	−0.0249 (18)	0.0052 (17)	−0.0150 (19)
O1A	0.0578 (13)	0.0268 (10)	0.0637 (14)	−0.0104 (9)	−0.0078 (11)	−0.0096 (9)
O2A	0.0631 (15)	0.0456 (12)	0.0584 (14)	−0.0129 (11)	0.0055 (11)	−0.0265 (11)
O3A	0.0487 (12)	0.0370 (11)	0.0505 (13)	−0.0082 (9)	−0.0031 (9)	−0.0143 (9)
C1B	0.057 (2)	0.0374 (16)	0.0527 (19)	−0.0016 (14)	−0.0043 (15)	−0.0061 (13)
C2B	0.071 (2)	0.0456 (18)	0.058 (2)	0.0031 (16)	−0.0132 (18)	−0.0038 (15)
C3B	0.080 (3)	0.060 (2)	0.051 (2)	−0.0184 (19)	−0.0173 (18)	−0.0046 (16)
C4B	0.070 (2)	0.0390 (16)	0.0461 (18)	−0.0177 (15)	−0.0071 (15)	−0.0073 (13)
C5B	0.0487 (16)	0.0317 (13)	0.0441 (16)	−0.0163 (12)	−0.0022 (13)	−0.0068 (11)
C6B	0.0554 (19)	0.0309 (14)	0.0562 (19)	−0.0087 (13)	−0.0012 (14)	−0.0145 (13)
C7B	0.0554 (18)	0.0255 (13)	0.0544 (18)	−0.0084 (12)	−0.0053 (14)	−0.0107 (12)
C8B	0.0396 (15)	0.0293 (13)	0.0476 (16)	−0.0150 (11)	−0.0016 (12)	−0.0079 (11)
C9B	0.0352 (14)	0.0289 (13)	0.0471 (16)	−0.0125 (11)	0.0015 (11)	−0.0090 (11)
C10B	0.0402 (15)	0.0259 (12)	0.0467 (16)	−0.0092 (11)	0.0011 (12)	−0.0064 (11)
C11B	0.0372 (14)	0.0290 (12)	0.0460 (16)	−0.0067 (11)	−0.0006 (12)	−0.0062 (11)
C12B	0.0363 (15)	0.0309 (13)	0.0484 (16)	−0.0108 (11)	−0.0003 (12)	−0.0088 (12)
C13B	0.091 (3)	0.067 (2)	0.052 (2)	−0.023 (2)	0.0132 (19)	−0.0156 (17)
C14B	0.136 (4)	0.058 (2)	0.066 (3)	−0.035 (3)	−0.034 (3)	−0.0147 (19)
C15B	0.071 (2)	0.0441 (17)	0.060 (2)	−0.0321 (16)	0.0083 (16)	−0.0122 (14)
O1B	0.0568 (13)	0.0280 (10)	0.0644 (14)	−0.0123 (9)	0.0048 (10)	−0.0157 (9)
O2B	0.0630 (15)	0.0343 (11)	0.0513 (13)	−0.0113 (10)	−0.0062 (10)	0.0004 (9)
O3B	0.0527 (12)	0.0326 (10)	0.0443 (12)	−0.0083 (9)	0.0008 (9)	−0.0079 (8)

Geometric parameters (Å, º)

C1A—C2A	1.521 (5)	C1B—C2B	1.526 (5)
C1A—C10A	1.540 (4)	C1B—C10B	1.535 (4)
C1A—H1AA	0.9700	C1B—H1BA	0.9700
C1A—H1AB	0.9700	C1B—H1BB	0.9700
C2A—C3A	1.511 (6)	C2B—C3B	1.527 (5)
C2A—H2AA	0.9700	C2B—H2BA	0.9700
C2A—H2AB	0.9700	C2B—H2BB	0.9700
C3A—C4A	1.540 (5)	C3B—C4B	1.539 (5)
C3A—H3AA	0.9700	C3B—H3BA	0.9700
C3A—H3AB	0.9700	C3B—H3BB	0.9700
C4A—C13A	1.536 (6)	C4B—C13B	1.527 (6)
C4A—C14A	1.542 (6)	C4B—C14B	1.547 (5)
C4A—C5A	1.551 (5)	C4B—C5B	1.556 (4)
C5A—C6A	1.540 (4)	C5B—C6B	1.534 (4)
C5A—C10A	1.558 (4)	C5B—C10B	1.557 (4)
C5A—H5AA	0.9800	C5B—H5BA	0.9800
C6A—C7A	1.515 (5)	C6B—C7B	1.531 (5)
C6A—H6AA	0.9700	C6B—H6BA	0.9700
C6A—H6AB	0.9700	C6B—H6BB	0.9700
C7A—C8A	1.469 (4)	C7B—C8B	1.489 (4)
C7A—H7AA	0.9700	C7B—H7BA	0.9700
C7A—H7AB	0.9700	C7B—H7BB	0.9700
C8A—C9A	1.342 (4)	C8B—C9B	1.333 (4)
C8A—C12A	1.452 (4)	C8B—C12B	1.459 (4)
C9A—C11A	1.504 (4)	C9B—C11B	1.499 (4)
C9A—C10A	1.506 (4)	C9B—C10B	1.506 (4)
C10A—C15A	1.538 (5)	C10B—C15B	1.544 (4)
C11A—O1A	1.379 (3)	C11B—O1B	1.380 (3)
C11A—O3A	1.462 (4)	C11B—O3B	1.471 (4)
C11A—H11A	0.9800	C11B—H11B	0.9800
C12A—O2A	1.221 (4)	C12B—O2B	1.217 (3)
C12A—O3A	1.356 (3)	C12B—O3B	1.352 (3)
C13A—H13A	0.9600	C13B—H13D	0.9600
C13A—H13B	0.9600	C13B—H13E	0.9600
C13A—H13C	0.9600	C13B—H13F	0.9600
C14A—H14A	0.9600	C14B—H14D	0.9600
C14A—H14B	0.9600	C14B—H14E	0.9600
C14A—H14C	0.9600	C14B—H14F	0.9600
C15A—H15A	0.9600	C15B—H15D	0.9600
C15A—H15B	0.9600	C15B—H15E	0.9600
C15A—H15C	0.9600	C15B—H15F	0.9600
O1A—H1OA	0.849 (14)	O1B—H1OB	0.865 (14)
C2A—C1A—C10A	111.7 (3)	C2B—C1B—C10B	111.9 (3)
C2A—C1A—H1AA	109.3	C2B—C1B—H1BA	109.2
C10A—C1A—H1AA	109.3	C10B—C1B—H1BA	109.2
C2A—C1A—H1AB	109.3	C2B—C1B—H1BB	109.2
C10A—C1A—H1AB	109.3	C10B—C1B—H1BB	109.2
H1AA—C1A—H1AB	107.9	H1BA—C1B—H1BB	107.9
C3A—C2A—C1A	110.5 (3)	C1B—C2B—C3B	110.6 (3)
C3A—C2A—H2AA	109.5	C1B—C2B—H2BA	109.5
C1A—C2A—H2AA	109.5	C3B—C2B—H2BA	109.5
C3A—C2A—H2AB	109.5	C1B—C2B—H2BB	109.5
C1A—C2A—H2AB	109.5	C3B—C2B—H2BB	109.5
H2AA—C2A—H2AB	108.1	H2BA—C2B—H2BB	108.1
C2A—C3A—C4A	114.2 (3)	C2B—C3B—C4B	113.6 (3)
C2A—C3A—H3AA	108.7	C2B—C3B—H3BA	108.8
C4A—C3A—H3AA	108.7	C4B—C3B—H3BA	108.8
C2A—C3A—H3AB	108.7	C2B—C3B—H3BB	108.8
C4A—C3A—H3AB	108.7	C4B—C3B—H3BB	108.8
H3AA—C3A—H3AB	107.6	H3BA—C3B—H3BB	107.7
C13A—C4A—C3A	110.0 (3)	C13B—C4B—C3B	111.1 (3)
C13A—C4A—C14A	108.1 (3)	C13B—C4B—C14B	107.4 (3)
C3A—C4A—C14A	107.2 (4)	C3B—C4B—C14B	106.8 (3)
C13A—C4A—C5A	114.3 (3)	C13B—C4B—C5B	115.0 (3)
C3A—C4A—C5A	108.0 (3)	C3B—C4B—C5B	107.9 (3)
C14A—C4A—C5A	109.1 (3)	C14B—C4B—C5B	108.3 (3)
C6A—C5A—C4A	114.8 (2)	C6B—C5B—C10B	110.5 (2)
C6A—C5A—C10A	110.4 (2)	C6B—C5B—C4B	115.0 (3)
C4A—C5A—C10A	116.6 (2)	C10B—C5B—C4B	115.5 (2)
C6A—C5A—H5AA	104.5	C6B—C5B—H5BA	104.8
C4A—C5A—H5AA	104.5	C10B—C5B—H5BA	104.8
C10A—C5A—H5AA	104.5	C4B—C5B—H5BA	104.8
C7A—C6A—C5A	111.8 (2)	C7B—C6B—C5B	111.8 (3)
C7A—C6A—H6AA	109.3	C7B—C6B—H6BA	109.3
C5A—C6A—H6AA	109.3	C5B—C6B—H6BA	109.3
C7A—C6A—H6AB	109.3	C7B—C6B—H6BB	109.3
C5A—C6A—H6AB	109.3	C5B—C6B—H6BB	109.3
H6AA—C6A—H6AB	107.9	H6BA—C6B—H6BB	107.9
C8A—C7A—C6A	111.4 (3)	C8B—C7B—C6B	110.1 (2)
C8A—C7A—H7AA	109.4	C8B—C7B—H7BA	109.6
C6A—C7A—H7AA	109.4	C6B—C7B—H7BA	109.6
C8A—C7A—H7AB	109.4	C8B—C7B—H7BB	109.6
C6A—C7A—H7AB	109.4	C6B—C7B—H7BB	109.6
H7AA—C7A—H7AB	108.0	H7BA—C7B—H7BB	108.1
C9A—C8A—C12A	108.0 (3)	C9B—C8B—C12B	108.1 (2)
C9A—C8A—C7A	126.1 (3)	C9B—C8B—C7B	126.2 (3)
C12A—C8A—C7A	125.8 (3)	C12B—C8B—C7B	125.6 (2)
C8A—C9A—C11A	109.4 (3)	C8B—C9B—C11B	109.7 (3)
C8A—C9A—C10A	123.5 (3)	C8B—C9B—C10B	124.3 (3)
C11A—C9A—C10A	126.8 (3)	C11B—C9B—C10B	125.9 (2)
C9A—C10A—C1A	112.3 (2)	C9B—C10B—C1B	110.8 (2)
C9A—C10A—C15A	104.7 (3)	C9B—C10B—C15B	105.9 (2)
C1A—C10A—C15A	109.1 (3)	C1B—C10B—C15B	110.0 (3)
C9A—C10A—C5A	106.1 (2)	C9B—C10B—C5B	105.3 (2)
C1A—C10A—C5A	108.9 (2)	C1B—C10B—C5B	109.3 (2)
C15A—C10A—C5A	115.7 (3)	C15B—C10B—C5B	115.5 (2)
O1A—C11A—O3A	108.8 (2)	O1B—C11B—O3B	109.5 (2)
O1A—C11A—C9A	114.2 (2)	O1B—C11B—C9B	113.4 (2)
O3A—C11A—C9A	103.8 (2)	O3B—C11B—C9B	103.6 (2)
O1A—C11A—H11A	110.0	O1B—C11B—H11B	110.1
O3A—C11A—H11A	110.0	O3B—C11B—H11B	110.1
C9A—C11A—H11A	110.0	C9B—C11B—H11B	110.1
O2A—C12A—O3A	119.7 (3)	O2B—C12B—O3B	120.5 (3)
O2A—C12A—C8A	130.1 (3)	O2B—C12B—C8B	129.6 (3)
O3A—C12A—C8A	110.1 (2)	O3B—C12B—C8B	109.9 (2)
C4A—C13A—H13A	109.5	C4B—C13B—H13D	109.5
C4A—C13A—H13B	109.5	C4B—C13B—H13E	109.5
H13A—C13A—H13B	109.5	H13D—C13B—H13E	109.5
C4A—C13A—H13C	109.5	C4B—C13B—H13F	109.5
H13A—C13A—H13C	109.5	H13D—C13B—H13F	109.5
H13B—C13A—H13C	109.5	H13E—C13B—H13F	109.5
C4A—C14A—H14A	109.5	C4B—C14B—H14D	109.5
C4A—C14A—H14B	109.5	C4B—C14B—H14E	109.5
H14A—C14A—H14B	109.5	H14D—C14B—H14E	109.5
C4A—C14A—H14C	109.5	C4B—C14B—H14F	109.5
H14A—C14A—H14C	109.5	H14D—C14B—H14F	109.5
H14B—C14A—H14C	109.5	H14E—C14B—H14F	109.5
C10A—C15A—H15A	109.5	C10B—C15B—H15D	109.5
C10A—C15A—H15B	109.5	C10B—C15B—H15E	109.5
H15A—C15A—H15B	109.5	H15D—C15B—H15E	109.5
C10A—C15A—H15C	109.5	C10B—C15B—H15F	109.5
H15A—C15A—H15C	109.5	H15D—C15B—H15F	109.5
H15B—C15A—H15C	109.5	H15E—C15B—H15F	109.5
C11A—O1A—H1OA	121.4 (14)	C11B—O1B—H1OB	118.5 (14)
C12A—O3A—C11A	108.7 (2)	C12B—O3B—C11B	108.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1B—H1OB···O2A	0.87 (1)	1.90 (3)	2.730 (3)	160 (4)
O1A—H1OA···O2B^i	0.85 (1)	1.92 (2)	2.729 (3)	160 (4)

Symmetry code: (i) x+1, y−2, z.