A new norkaurane-γ-lactone from Parinari sprucei

The title tetracyclic diterpenoid, 10,13,16,17-tetra­hydroxy-9-methyl-15-oxo-20-norkaurane-18,10-carbolactone hemihydrate, C₂₀H₂₈O₆·0.5H₂O, is a plant metabolite from Parinari sprucei, part of the Venezuelan Amazon flora. The asymmetric unit consists of two nearly identical mol­ecules of the diterpenoid and one mol­ecule of water. Some of the geometric parameters reflect steric strain in the mol­ecule. The extended structure is characterized by hydrogen bonds and weaker hydrogen-mediated interactions, which involve all of the hydroxy groups and propagate in sheets that coincide with the (002) family of planes. The water mol­ecule acts as a double hydrogen-bond donor and single acceptor and thus plays a critical role in the pattern of intermolecular interactions.

S1. Comment

Tetracyclic diterpenoids with hydrocarbon skeletons deriving from a rearranged norkaurane type are widespread among the plant metabolites (Bruno et al., 2002; Niu et al., 2002; Hanson, 2003, and previous reports). Many of these substances exhibit biological activities that are well known from ancient times and used by traditional healers in the treatment of various diseases. Such substances are usually employed in Chinese medicine and agricultural practices. Owing to their possible utilization in pharmacology and farming, this class of substances has been widely investigated, and several studies concerning both the development of new synthetic strategies (King et al., 1997; Zhang et al., 2001; Vieira et al., 2002) and structural and biological characterizations have been reported recently (Hedden & Phillips, 2000; Duan et al. 2001; Rundle et al., 2001; Yang et al., 2002). However, while there have been many spectroscopic studies on kauranoid derivatives, only a limited number of crystallographic analyses are present in the literature (e.g. Karle, 1972; Zabel et al., 1980; Reynolds et al. 1991; Hokelek et al., 2001; Sun et al., 2002).

The title compound, (I), was isolated from the leaves of Parinari sprucei, a tree of the Chrysobalanaceae family growing in the Amazon forest, as part of research on the medicinal and food plants native to Latin America (Braca et al., 1999, 2000). A few other species of the Parinari genus have been studied in depth, leading to the identification of nor- and ent-kaurene diterpenes (Lee et al., 1996; Garo et al., 1997) strictly correlated to (I). The crystallographic study of (I) reported here was carried out in order to obtain structural information that could help find a correlation between the stereochemistry of the functional groups and the biological effects of these substances (Puliti & Mattia, 1999, 2000; Puliti et al., 2001; Ciasullo et al., 2002).

The asymmetric unit of the crystal is formed by two diterpenoid units (10,13,16,17-tetrahydroxy-9-methyl-15-oxo-20-norkauran-18-oic acid- γ-lactone) and one water molecule. The two independent organic molecules display geometric and conformational similarity, and are related by a pseudo-twofold axis almost parallel to the c direction, coupled with a translation of 2.2 Å. Upon best-fit superposition, the r.m.s. deviation of corresponding atoms, excluding the disordered hydroxymethyl group on atom C16 (see below), is only 0.027 Å, the largest difference (0.069 Å) being associated with the carbonyl O6 atoms. Both of the molecules exhibit partial disorder limited to the exocyclic hydroxymethyl group on atom C16, which is disordered over ?two orientations in one molecule and three orientations in the other. A similar disorder, involving the axial hydroxymethyl substituent on atom C4, was found in psiadian, a related kaurane diterpene (Mossa et al., 1992). In (I), the lactone ring lies on the same side (α-oriented) as the axial C20 methyl group, which is shifted from atom C10 of the normal kaurane skeleton to the C9-atom position. These structural features are also present in tetrachyrin (Zabel et al., 1980) and in other tetracyclic friedo-kauranoids, analogues of rosane lactone, such as eupatalbin and eupatoralbin (Herz et al., 1979) as well as in kaurene lactones from Zimbabwean plants belonging to the Parinari genus (Garo et al., 1997). In addition to the tertiary hydroxy group on atom C13, which is equatorially oriented, a second tertiary hydroxy group is present on atom C16, where the hydroxymethyl substituent affected by positional disorder is also located.

Fig. 1 shows a perspective view of the two independent molecules of (I), together with the atom-labelling scheme. (The atom numbers for the second molecule are 20 greater than those in the first, while the latter reflects the chemical numbering scheme.) The enantiomer was chosen according to the absolute stereochemistry of a eupatalbin derivative, deduced by CD analysis (Herz et al., 1979), and that of a kaurene-γ-lactone Br derivative, determined using anomalous dispersion (Garo et al., 1997; note that the stereochemistry at atom C9 is reported incorrectly by these authors as R). On this basis, the configurations at the chiral centres of (I) are fixed as 4R,5R,8R,9S,10S,13S,16R.

On average, bond lengths and angles are in the expected ranges (Herz et al., 1979; Zabel et al., 1980; Garo et al., 1997; Hokelek et al., 1999, 2001; Sun et al., 2002). Some deviations from the normal values of bond lengths and angles can be attributed to intramolecular steric strain. In particular, the bond lengthening along the atomic sequence C10—C9—C8—C15—C16, as well as some deviations from the ideal Csp³ and Csp² angles, help alleviate the short intramolecular O1···C20, O3···C5 and O4···C11 contacts.

The A/B and B/C? ring junctions are trans. Rings A and C rings are in chair conformations, slightly distorted toward half-boats, while ring B adopts a twist-boat conformation. The γ-lactone group and ring D are both in envelope forms, with apices at C5 and C14, respectively. The displacements of these atoms from the best planes through the remaining ring atoms are 0.633 (2) Å for atom C5 and 0.683 (3) Å for atom C14 [0.624 (2) Å for atom C25 and 0.711 (2) Å for atom C34].

The packing pattern is governed chiefly by hydrogen-bond interactions, which extend along the a and b directions, at c = 0 and 1/2 (Fig. 2). Each water molecule is engaged in three hydrogen bonds, serving as a double donor toward the lactone carbonyl groups of the two independent diterpenoic units and as a single acceptor from the tertiary hydroxyl group (O2) attached to atom C13 of a screw-related molecule. Furthermore, weaker hydrogen-mediated contacts connect the organic moieties, yielding a complex array of interactions. The geometry of the hydrogen-bonding interactions and other contacts is given in Table 2. Excluding the disordered groups, the intermolecular van der Waals distances are greater than 3.40 Å for C···O and greater than 3.72 Å for C···C.

S2. Experimental

Compound (I) was isolated from the CHCl₃ extract of air-dried leaves of Parinari sprucei collected in the Amazon forest of Venezuela. Single crystals were obtained by slow evaporation from chloroform at room temperature.

S3. Refinement

All H atoms were located in difference Fourier maps and included, in the final refinements with expected geometry and U_iso(H) values of 1.5 U_eq(parent atom). H atoms attached to C and O atoms were constrained to lie 1.00 and 0.95 Å, respectively, from their parent atoms. Hydroxy H atoms were refined as members of rigid groups, allowing rotation about the adjacent C—O bonds. The H atoms of disordered hydroxymethyl groups were fixed in the last cycles of refinement. The water molecule was refined as a rigid group.

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: Structure Determination Package (Enraf–Nonius, 1985); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. A perspective view of the two independent molecules of (I), showing the atom labelling for non-H atoms. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing projected onto the ac plane; H atoms have been omitted for clarity. Dashed lines indicate hydrogen-bonds. [Symmetry codes: (i) 1 − x,y − 1/2,1/2 − z; (ii) 1/2 − x,1 − y,1/2 + z.]

10,13,16,17-tetrahydroxy-9-methyl-15-oxo-20-nor-kauran-18-oic acid-γ-lactone

Crystal data

2(C20H28O6)·H2O	F(000) = 1608
Mr = 746.86	Dx = 1.375 Mg m^−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 11.627 (3) Å	θ = 27.0–29.5°
b = 14.7157 (19) Å	µ = 0.84 mm^−1
c = 21.081 (3) Å	T = 291 K
V = 3607.0 (11) Å^3	Rectangular prism, colourless
Z = 4	0.48 × 0.17 × 0.09 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 74.8°, θmin = 3.7°
Graphite monochromator	h = 0→14
ω–2θ scans as suggested by peak–shape analysis	k = 0→18
4152 measured reflections	l = 0→26
4152 independent reflections	3 standard reflections every 200 min
3553 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0557P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
4152 reflections	Δρmax = 0.36 e Å^−3
512 parameters	Δρmin = −0.23 e Å^−3
32 restraints	Absolute structure: The absolute configuration was chosen according to that of the known bromine derivative of norkauren-γ-lactone (Garo et al., 1997) and is also supported by the refined Flack parameter (Flack, 1983).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (18)

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	Occ. (<1)
O1	0.09940 (14)	0.50010 (12)	0.38470 (7)	0.0383 (4)
O2	0.0439 (2)	0.50488 (14)	0.06255 (8)	0.0569 (5)
H1O	0.0816	0.4517	0.0477	0.085*
O3	−0.21416 (15)	0.50402 (16)	0.23607 (8)	0.0550 (5)
O4	−0.1140 (2)	0.36981 (15)	0.14609 (11)	0.0687 (6)
H2O	−0.1900	0.3530	0.1344	0.103*
O6	0.11379 (17)	0.54300 (17)	0.48547 (8)	0.0612 (6)
C1	−0.0464 (2)	0.39808 (16)	0.34619 (11)	0.0401 (5)
H1A	−0.1160	0.3914	0.3187	0.060*
H1B	0.0101	0.3502	0.3336	0.060*
C2	−0.0807 (3)	0.3843 (2)	0.41608 (12)	0.0512 (7)
H2A	−0.1364	0.3327	0.4186	0.077*
H2B	−0.0106	0.3665	0.4406	0.077*
C3	−0.1349 (2)	0.4680 (2)	0.44769 (12)	0.0491 (6)
H3A	−0.2171	0.4733	0.4342	0.074*
H3B	−0.1335	0.4601	0.4948	0.074*
C4	−0.0705 (2)	0.55520 (18)	0.42990 (11)	0.0408 (5)
C5	−0.07694 (19)	0.56657 (16)	0.35691 (10)	0.0354 (5)
H5	−0.1560	0.5501	0.3422	0.053*
C6	−0.0471 (3)	0.65943 (17)	0.33247 (11)	0.0491 (7)
H6A	0.0318	0.6765	0.3470	0.074*
H6B	−0.1026	0.7050	0.3498	0.074*
C7	−0.0517 (3)	0.66063 (16)	0.25919 (12)	0.0499 (7)
H7A	−0.1312	0.6780	0.2457	0.075*
H7B	0.0019	0.7088	0.2435	0.075*
C8	−0.0203 (2)	0.57105 (14)	0.22747 (10)	0.0327 (4)
C9	0.06334 (19)	0.50929 (15)	0.26801 (10)	0.0334 (4)
C10	0.00729 (18)	0.49281 (15)	0.33555 (9)	0.0301 (4)
C11	0.0828 (2)	0.41999 (17)	0.23172 (10)	0.0382 (5)
H11A	0.0130	0.3809	0.2368	0.057*
H11B	0.1490	0.3871	0.2514	0.057*
C12	0.1073 (2)	0.43221 (18)	0.16004 (11)	0.0434 (5)
H12A	0.1870	0.4564	0.1543	0.065*
H12B	0.1030	0.3717	0.1385	0.065*
C13	0.0224 (2)	0.49649 (17)	0.12925 (10)	0.0393 (5)
C14	0.0297 (2)	0.58705 (17)	0.16089 (10)	0.0418 (5)
H14A	−0.0164	0.6334	0.1373	0.063*
H14B	0.1113	0.6082	0.1635	0.063*
C15	−0.1250 (2)	0.51299 (17)	0.20750 (10)	0.0397 (5)
C16	−0.1020 (2)	0.46725 (19)	0.14227 (11)	0.0461 (6)
C17A	−0.1903 (3)	0.4982 (2)	0.09411 (14)	0.0683 (9)	0.80
H17A	−0.1734	0.4678	0.0527	0.102*	0.80
H17B	−0.2679	0.4773	0.1083	0.102*	0.80
O5A	−0.1944 (3)	0.5945 (2)	0.08404 (13)	0.0758 (9)	0.80
H3O	−0.1441	0.6104	0.0503	0.114*	0.80
C17B	−0.1903 (3)	0.4982 (2)	0.09411 (14)	0.0683 (9)	0.20
H17C	−0.1867	0.5659	0.0908	0.102*	0.20
H17D	−0.1690	0.4726	0.0517	0.102*	0.20
O5B	−0.3064 (4)	0.4722 (10)	0.1083 (5)	0.096 (4)	0.20
H4O	−0.3152	0.4661	0.1529	0.144*	0.20
C18	0.0553 (2)	0.53491 (18)	0.43808 (11)	0.0401 (5)
C19	−0.1091 (3)	0.6363 (2)	0.46970 (12)	0.0602 (8)
H19A	−0.1931	0.6472	0.4628	0.090*
H19B	−0.0648	0.6915	0.4567	0.090*
H19C	−0.0948	0.6233	0.5156	0.090*
C20	0.1810 (2)	0.5567 (2)	0.27536 (12)	0.0485 (6)
H20A	0.1707	0.6153	0.2987	0.073*
H20B	0.2142	0.5691	0.2325	0.073*
H20C	0.2343	0.5164	0.2997	0.073*
O21	0.38029 (14)	0.78946 (13)	0.30019 (7)	0.0406 (4)
O22	0.50877 (16)	0.82283 (13)	−0.01270 (7)	0.0450 (4)
H21O	0.5386	0.8783	−0.0289	0.068*
O23	0.72687 (14)	0.79774 (14)	0.17847 (8)	0.0461 (4)
O24	0.65908 (17)	0.93747 (12)	0.08694 (8)	0.0469 (4)
H22O	0.7386	0.9503	0.0920	0.070*
O26	0.33393 (18)	0.73224 (17)	0.39406 (9)	0.0613 (6)
C21	0.5385 (2)	0.89018 (15)	0.28138 (10)	0.0403 (5)
H21A	0.4879	0.9412	0.2671	0.060*
H21B	0.6149	0.8976	0.2603	0.060*
C22	0.5545 (2)	0.89586 (17)	0.35400 (11)	0.0442 (6)
H22A	0.6116	0.9447	0.3638	0.066*
H22B	0.4796	0.9135	0.3739	0.066*
C23	0.5961 (2)	0.80602 (18)	0.38393 (11)	0.0429 (5)
H23A	0.5824	0.8080	0.4308	0.064*
H23B	0.6807	0.7995	0.3768	0.064*
C24	0.5335 (2)	0.72267 (16)	0.35565 (10)	0.0372 (5)
C25	0.56073 (19)	0.72095 (14)	0.28466 (10)	0.0320 (4)
H25	0.6435	0.7368	0.2781	0.048*
C26	0.5345 (2)	0.63212 (15)	0.25121 (10)	0.0379 (5)
H26A	0.4514	0.6164	0.2570	0.057*
H26B	0.5817	0.5822	0.2701	0.057*
C27	0.5615 (2)	0.64083 (15)	0.18040 (11)	0.0403 (5)
H27A	0.6444	0.6254	0.1739	0.060*
H27B	0.5150	0.5946	0.1569	0.060*
C28	0.53877 (18)	0.73406 (13)	0.15075 (9)	0.0288 (4)
C29	0.44668 (18)	0.79237 (15)	0.18832 (10)	0.0303 (4)
C30	0.48493 (19)	0.79964 (14)	0.26067 (10)	0.0297 (4)
C31	0.4383 (2)	0.88640 (15)	0.15709 (10)	0.0340 (4)
H31A	0.3688	0.9183	0.1739	0.051*
H31B	0.5073	0.9229	0.1695	0.051*
C32	0.4310 (2)	0.88339 (16)	0.08470 (10)	0.0349 (5)
H32A	0.3527	0.8618	0.0721	0.052*
H32B	0.4410	0.9463	0.0676	0.052*
C33	0.5211 (2)	0.82140 (16)	0.05493 (9)	0.0333 (5)
C34	0.5030 (2)	0.72522 (15)	0.08015 (10)	0.0370 (5)
H34A	0.5529	0.6805	0.0573	0.055*
H34B	0.4208	0.7061	0.0761	0.055*
C35	0.64704 (18)	0.79140 (15)	0.14312 (9)	0.0315 (4)
C36	0.64355 (19)	0.84299 (15)	0.07892 (10)	0.0348 (5)
C37A	0.7377 (2)	0.8086 (2)	0.03447 (11)	0.0547 (7)	0.60
H37A	0.8127	0.8094	0.0577	0.082*	0.60
H37B	0.7206	0.7441	0.0230	0.082*	0.60
O25A	0.7492 (3)	0.8590 (3)	−0.02109 (14)	0.0641 (9)	0.60
H23O	0.7705	0.9195	−0.0108	0.096*	0.60
C37B	0.7377 (2)	0.8086 (2)	0.03447 (11)	0.0547 (7)	0.20
H37C	0.7158	0.8238	−0.0102	0.082*	0.20
H37D	0.8107	0.8416	0.0443	0.082*	0.20
O25B	0.7580 (7)	0.7156 (4)	0.0385 (4)	0.063 (2)	0.20
H24O	0.8281	0.7014	0.0176	0.095*	0.20
C37C	0.7377 (2)	0.8086 (2)	0.03447 (11)	0.0547 (7)	0.20
H37E	0.7123	0.7495	0.0156	0.082*	0.20
H37F	0.7470	0.8530	−0.0011	0.082*	0.20
O25C	0.8439 (4)	0.7960 (10)	0.0635 (4)	0.075 (3)	0.20
H25O	0.8426	0.7414	0.0876	0.112*	0.20
C38	0.4072 (2)	0.74509 (17)	0.35415 (11)	0.0422 (5)
C39	0.5592 (3)	0.6376 (2)	0.39278 (13)	0.0553 (7)
H39A	0.6439	0.6259	0.3922	0.083*
H39B	0.5180	0.5850	0.3732	0.083*
H39C	0.5328	0.6455	0.4376	0.083*
C40	0.3272 (2)	0.74649 (19)	0.18324 (12)	0.0455 (6)
H40A	0.3304	0.6848	0.2031	0.068*
H40B	0.3053	0.7405	0.1376	0.068*
H40C	0.2688	0.7845	0.2058	0.068*
O1W	0.32631 (19)	0.63066 (16)	0.51173 (9)	0.0617 (5)
H1W	0.2591	0.5946	0.5067	0.093*
H2W	0.3347	0.6696	0.4761	0.093*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0377 (8)	0.0545 (9)	0.0228 (7)	−0.0003 (8)	−0.0056 (6)	0.0017 (7)
O2	0.0857 (14)	0.0632 (11)	0.0217 (8)	0.0137 (11)	0.0090 (9)	0.0060 (8)
O3	0.0397 (9)	0.0895 (14)	0.0357 (9)	0.0008 (10)	0.0000 (7)	−0.0017 (10)
O4	0.0714 (14)	0.0631 (13)	0.0717 (15)	−0.0082 (11)	−0.0046 (12)	−0.0175 (12)
O6	0.0540 (11)	0.1030 (16)	0.0266 (8)	−0.0035 (12)	−0.0098 (8)	−0.0043 (10)
C1	0.0541 (13)	0.0426 (12)	0.0237 (10)	−0.0107 (11)	0.0045 (10)	0.0061 (9)
C2	0.0651 (16)	0.0594 (16)	0.0291 (12)	−0.0175 (14)	0.0069 (11)	0.0071 (11)
C3	0.0420 (12)	0.0732 (18)	0.0320 (11)	−0.0072 (13)	0.0071 (10)	0.0024 (12)
C4	0.0437 (12)	0.0553 (14)	0.0234 (10)	0.0016 (11)	−0.0012 (9)	−0.0016 (10)
C5	0.0361 (10)	0.0441 (12)	0.0260 (10)	0.0023 (9)	−0.0058 (9)	−0.0001 (9)
C6	0.0770 (19)	0.0403 (12)	0.0302 (11)	0.0116 (13)	−0.0036 (12)	−0.0033 (10)
C7	0.082 (2)	0.0344 (12)	0.0329 (12)	0.0078 (13)	−0.0059 (13)	0.0030 (9)
C8	0.0444 (11)	0.0310 (9)	0.0228 (9)	0.0048 (9)	−0.0018 (9)	0.0052 (8)
C9	0.0368 (11)	0.0386 (10)	0.0248 (9)	−0.0020 (10)	−0.0015 (8)	0.0079 (8)
C10	0.0320 (9)	0.0369 (10)	0.0213 (9)	−0.0014 (9)	−0.0040 (8)	0.0019 (8)
C11	0.0456 (12)	0.0459 (12)	0.0229 (10)	0.0102 (10)	0.0005 (9)	0.0071 (9)
C12	0.0495 (13)	0.0525 (14)	0.0283 (11)	0.0097 (12)	0.0059 (10)	0.0007 (10)
C13	0.0510 (13)	0.0464 (13)	0.0205 (10)	0.0072 (11)	0.0018 (9)	0.0026 (9)
C14	0.0575 (14)	0.0435 (12)	0.0246 (10)	0.0033 (11)	0.0000 (10)	0.0085 (9)
C15	0.0398 (11)	0.0513 (13)	0.0279 (10)	0.0101 (10)	−0.0083 (9)	0.0043 (10)
C16	0.0497 (13)	0.0584 (15)	0.0303 (11)	0.0061 (12)	−0.0058 (11)	−0.0085 (11)
C17A	0.072 (2)	0.092 (2)	0.0398 (14)	0.022 (2)	−0.0134 (15)	−0.0138 (16)
O5A	0.0789 (19)	0.098 (2)	0.0504 (15)	0.0344 (18)	0.0012 (15)	0.0119 (15)
C17B	0.072 (2)	0.092 (2)	0.0398 (14)	0.022 (2)	−0.0134 (15)	−0.0138 (16)
O5B	0.086 (7)	0.144 (9)	0.058 (6)	−0.004 (7)	−0.020 (6)	−0.017 (7)
C18	0.0413 (11)	0.0551 (14)	0.0239 (9)	−0.0079 (11)	−0.0019 (9)	−0.0003 (10)
C19	0.0649 (17)	0.083 (2)	0.0328 (12)	0.0065 (17)	0.0019 (12)	−0.0194 (13)
C20	0.0445 (13)	0.0670 (17)	0.0339 (12)	−0.0167 (12)	−0.0024 (10)	0.0117 (12)
O21	0.0369 (8)	0.0561 (10)	0.0288 (8)	0.0055 (7)	0.0057 (6)	0.0110 (7)
O22	0.0657 (11)	0.0540 (10)	0.0153 (7)	−0.0054 (9)	−0.0076 (7)	−0.0021 (6)
O23	0.0402 (8)	0.0675 (12)	0.0305 (8)	−0.0064 (8)	−0.0076 (7)	−0.0015 (8)
O24	0.0491 (10)	0.0468 (9)	0.0448 (10)	−0.0160 (8)	−0.0036 (8)	0.0054 (8)
O26	0.0547 (11)	0.0952 (16)	0.0341 (9)	−0.0054 (12)	0.0096 (9)	0.0209 (10)
C21	0.0604 (15)	0.0353 (11)	0.0253 (10)	0.0019 (11)	0.0025 (10)	−0.0023 (9)
C22	0.0619 (15)	0.0429 (13)	0.0279 (11)	−0.0022 (12)	0.0023 (11)	−0.0085 (10)
C23	0.0527 (13)	0.0523 (14)	0.0238 (10)	0.0021 (12)	−0.0029 (10)	−0.0036 (10)
C24	0.0459 (12)	0.0422 (12)	0.0235 (10)	0.0043 (10)	−0.0016 (9)	0.0058 (9)
C25	0.0388 (10)	0.0335 (10)	0.0237 (9)	0.0028 (9)	−0.0020 (8)	0.0010 (8)
C26	0.0549 (14)	0.0288 (10)	0.0300 (10)	0.0019 (10)	−0.0082 (10)	0.0024 (8)
C27	0.0592 (14)	0.0320 (11)	0.0296 (10)	0.0042 (11)	−0.0038 (10)	−0.0033 (8)
C28	0.0383 (10)	0.0277 (9)	0.0203 (8)	0.0032 (8)	−0.0019 (8)	−0.0025 (7)
C29	0.0338 (10)	0.0350 (10)	0.0222 (9)	−0.0002 (8)	−0.0016 (8)	0.0029 (8)
C30	0.0338 (10)	0.0313 (10)	0.0241 (10)	0.0028 (8)	0.0062 (8)	0.0029 (8)
C31	0.0398 (11)	0.0369 (10)	0.0254 (9)	0.0085 (9)	0.0003 (8)	0.0038 (8)
C32	0.0408 (11)	0.0376 (11)	0.0263 (10)	0.0022 (9)	−0.0002 (8)	0.0070 (9)
C33	0.0421 (11)	0.0404 (11)	0.0173 (9)	−0.0012 (10)	−0.0047 (8)	0.0001 (8)
C34	0.0492 (12)	0.0362 (11)	0.0254 (10)	−0.0038 (10)	−0.0078 (9)	−0.0023 (8)
C35	0.0361 (10)	0.0376 (10)	0.0207 (9)	0.0026 (9)	−0.0004 (8)	−0.0046 (8)
C36	0.0353 (11)	0.0460 (12)	0.0232 (10)	0.0004 (10)	0.0016 (8)	−0.0013 (9)
C37A	0.0444 (14)	0.087 (2)	0.0330 (12)	0.0081 (14)	0.0084 (11)	−0.0020 (13)
O25A	0.069 (2)	0.084 (2)	0.0393 (16)	0.016 (2)	0.0192 (16)	0.0141 (17)
C37B	0.0444 (14)	0.087 (2)	0.0330 (12)	0.0081 (14)	0.0084 (11)	−0.0020 (13)
O25B	0.045 (4)	0.092 (6)	0.053 (5)	−0.005 (5)	0.011 (4)	−0.004 (5)
C37C	0.0444 (14)	0.087 (2)	0.0330 (12)	0.0081 (14)	0.0084 (11)	−0.0020 (13)
O25C	0.053 (5)	0.108 (6)	0.062 (5)	0.018 (5)	0.005 (4)	−0.024 (5)
C38	0.0506 (13)	0.0502 (13)	0.0258 (10)	−0.0018 (11)	0.0049 (10)	0.0126 (10)
C39	0.078 (2)	0.0549 (15)	0.0335 (12)	0.0036 (15)	−0.0073 (13)	0.0151 (11)
C40	0.0394 (12)	0.0633 (16)	0.0339 (11)	−0.0112 (11)	−0.0042 (10)	0.0153 (12)
O1W	0.0621 (12)	0.0825 (15)	0.0406 (10)	−0.0093 (11)	−0.0053 (9)	0.0170 (10)

Geometric parameters (Å, º)

O1—C10	1.494 (2)	O23—C35	1.194 (3)
O1—C18	1.339 (3)	O24—C36	1.412 (3)
O2—C13	1.434 (3)	O24—H22O	0.9500
O2—H1O	0.9500	O26—C38	1.212 (3)
O3—C15	1.206 (3)	C21—C22	1.545 (3)
O4—C16	1.443 (3)	C21—C30	1.534 (3)
O4—H2O	0.9500	C21—H21A	1.0000
O6—C18	1.215 (3)	C21—H21B	1.0000
C1—C2	1.540 (3)	C22—C23	1.543 (3)
C1—C10	1.544 (3)	C22—H22A	1.0000
C1—H1A	1.0000	C22—H22B	1.0000
C1—H1B	1.0000	C23—C24	1.546 (3)
C2—C3	1.536 (4)	C23—H23A	1.0000
C2—H2A	1.0000	C23—H23B	1.0000
C2—H2B	1.0000	C24—C25	1.530 (3)
C3—C4	1.533 (4)	C24—C38	1.506 (4)
C3—H3A	1.0000	C24—C39	1.506 (3)
C3—H3B	1.0000	C25—C26	1.516 (3)
C4—C18	1.503 (3)	C25—C30	1.541 (3)
C4—C19	1.526 (4)	C25—H25	1.0000
C4—C5	1.550 (3)	C26—C27	1.531 (3)
C5—C6	1.501 (3)	C26—H26A	1.0000
C5—C10	1.530 (3)	C26—H26B	1.0000
C5—H5	1.0000	C27—C28	1.531 (3)
C6—C7	1.546 (3)	C27—H27A	1.0000
C6—H6A	1.0000	C27—H27B	1.0000
C6—H6B	1.0000	C28—C29	1.584 (3)
C7—C8	1.523 (3)	C28—C34	1.551 (3)
C7—H7A	1.0000	C28—C35	1.524 (3)
C7—H7B	1.0000	C29—C30	1.592 (3)
C8—C9	1.582 (3)	C29—C31	1.535 (3)
C8—C14	1.537 (3)	C29—C40	1.548 (3)
C8—C15	1.546 (3)	C31—C32	1.529 (3)
C9—C10	1.585 (3)	C31—H31A	1.0000
C9—C11	1.537 (3)	C31—H31B	1.0000
C9—C20	1.543 (3)	C32—C33	1.525 (3)
C11—C12	1.548 (3)	C32—H32A	1.0000
C11—H11A	1.0000	C32—H32B	1.0000
C11—H11B	1.0000	C33—C34	1.526 (3)
C12—C13	1.513 (3)	C33—C36	1.544 (3)
C12—H12A	1.0000	C34—H34A	1.0000
C12—H12B	1.0000	C34—H34B	1.0000
C13—C14	1.493 (3)	C35—C36	1.552 (3)
C13—C16	1.534 (4)	C36—C37A	1.527 (3)
C14—H14A	1.0000	C36—C37B	1.527 (3)
C14—H14B	1.0000	C36—C37C	1.527 (3)
C15—C16	1.554 (3)	C37A—O25A	1.393 (3)
C16—C17A	1.514 (4)	C37A—H37A	1.0000
C16—C17B	1.514 (4)	C37A—H37B	1.0000
C17A—O5A	1.434 (4)	C37B—O25B	1.391 (6)
C17A—H17A	1.0000	C37B—H37C	1.0000
C17A—H17B	1.0000	C37B—H37D	1.0000
C17B—O5B	1.435 (7)	C37C—O25C	1.392 (6)
C17B—H17C	1.0000	C37C—H37E	1.0000
C17B—H17D	1.0000	C37C—H37F	1.0000
O5A—H3O	0.9500	O25A—H23O	0.9500
O5B—H4O	0.9500	O25B—H24O	0.9500
C19—H19A	1.0000	O25C—H25O	0.9500
C19—H19B	1.0000	C39—H39A	1.0000
C19—H19C	1.0000	C39—H39B	1.0000
C20—H20A	1.0000	C39—H39C	1.0000
C20—H20B	1.0000	C40—H40A	1.0000
C20—H20C	1.0000	C40—H40B	1.0000
O21—C30	1.482 (2)	C40—H40C	1.0000
O21—C38	1.348 (3)	O1W—H1W	0.9500
O22—C33	1.433 (2)	O1W—H2W	0.9500
O22—H21O	0.9500
C10—O1—C18	109.61 (17)	C30—C21—H21A	109.2
C13—O2—H1O	109.5	C22—C21—H21A	109.2
C16—O4—H2O	109.5	C30—C21—H21B	109.2
C2—C1—C10	111.3 (2)	C22—C21—H21B	109.2
C2—C1—H1A	109.4	H21A—C21—H21B	107.9
C10—C1—H1A	109.4	C23—C22—C21	113.38 (19)
C2—C1—H1B	109.4	C23—C22—H22A	108.9
C10—C1—H1B	109.4	C21—C22—H22A	108.9
H1A—C1—H1B	108.0	C23—C22—H22B	108.9
C3—C2—C1	114.6 (2)	C21—C22—H22B	108.9
C3—C2—H2A	108.6	H22A—C22—H22B	107.7
C1—C2—H2A	108.6	C22—C23—C24	112.0 (2)
C3—C2—H2B	108.6	C22—C23—H23A	109.2
C1—C2—H2B	108.6	C24—C23—H23A	109.2
H2A—C2—H2B	107.6	C22—C23—H23B	109.2
C4—C3—C2	111.4 (2)	C24—C23—H23B	109.2
C4—C3—H3A	109.3	H23A—C23—H23B	107.9
C2—C3—H3A	109.3	C38—C24—C39	112.8 (2)
C4—C3—H3B	109.3	C25—C24—C38	100.68 (18)
C2—C3—H3B	109.3	C25—C24—C39	117.0 (2)
H3A—C3—H3B	108.0	C38—C24—C23	107.1 (2)
C18—C4—C19	112.2 (2)	C39—C24—C23	111.4 (2)
C18—C4—C3	106.3 (2)	C25—C24—C23	107.03 (19)
C19—C4—C3	112.2 (2)	C26—C25—C24	115.31 (19)
C5—C4—C18	100.49 (19)	C26—C25—C30	112.33 (18)
C5—C4—C19	116.6 (2)	C24—C25—C30	100.96 (17)
C3—C4—C5	108.1 (2)	C26—C25—H25	109.3
C6—C5—C10	113.4 (2)	C24—C25—H25	109.3
C6—C5—C4	115.34 (19)	C30—C25—H25	109.3
C10—C5—C4	100.65 (17)	C25—C26—C27	109.87 (19)
C6—C5—H5	109.0	C25—C26—H26A	109.7
C10—C5—H5	109.0	C27—C26—H26A	109.7
C4—C5—H5	109.0	C25—C26—H26B	109.7
C5—C6—C7	110.2 (2)	C27—C26—H26B	109.7
C5—C6—H6A	109.6	H26A—C26—H26B	108.2
C7—C6—H6A	109.6	C28—C27—C26	115.95 (19)
C5—C6—H6B	109.6	C28—C27—H27A	108.3
C7—C6—H6B	109.6	C26—C27—H27A	108.3
H6A—C6—H6B	108.1	C28—C27—H27B	108.3
C8—C7—C6	114.9 (2)	C26—C27—H27B	108.3
C8—C7—H7A	108.5	H27A—C27—H27B	107.4
C6—C7—H7A	108.5	C27—C28—C29	113.46 (18)
C8—C7—H7B	108.5	C27—C28—C35	113.36 (19)
C6—C7—H7B	108.5	C34—C28—C35	99.58 (16)
H7A—C7—H7B	107.5	C27—C28—C34	111.29 (17)
C7—C8—C9	114.06 (19)	C35—C28—C29	108.13 (16)
C7—C8—C14	111.04 (18)	C34—C28—C29	110.14 (17)
C7—C8—C15	114.2 (2)	C31—C29—C40	107.87 (18)
C14—C8—C15	97.68 (17)	C31—C29—C28	108.44 (17)
C14—C8—C9	110.42 (18)	C40—C29—C28	109.60 (19)
C15—C8—C9	108.30 (17)	C31—C29—C30	111.58 (17)
C11—C9—C20	107.8 (2)	C40—C29—C30	110.25 (17)
C11—C9—C8	108.22 (17)	C28—C29—C30	109.06 (16)
C20—C9—C8	109.85 (18)	O21—C30—C21	105.12 (17)
C11—C9—C10	112.13 (17)	O21—C30—C25	102.06 (16)
C20—C9—C10	110.09 (18)	C21—C30—C25	109.10 (18)
C8—C9—C10	108.70 (17)	O21—C30—C29	107.60 (17)
O1—C10—C5	101.77 (16)	C21—C30—C29	116.38 (17)
O1—C10—C1	104.72 (16)	C25—C30—C29	115.07 (17)
C5—C10—C1	109.81 (19)	C32—C31—C29	113.92 (18)
O1—C10—C9	108.50 (16)	C32—C31—H31A	108.8
C1—C10—C9	115.79 (18)	C29—C31—H31A	108.8
C5—C10—C9	114.78 (17)	C32—C31—H31B	108.8
C9—C11—C12	114.42 (19)	C29—C31—H31B	108.8
C9—C11—H11A	108.7	H31A—C31—H31B	107.7
C12—C11—H11A	108.7	C33—C32—C31	112.92 (18)
C9—C11—H11B	108.7	C33—C32—H32A	109.0
C12—C11—H11B	108.7	C31—C32—H32A	109.0
H11A—C11—H11B	107.6	C33—C32—H32B	109.0
C13—C12—C11	111.8 (2)	C31—C32—H32B	109.0
C13—C12—H12A	109.3	H32A—C32—H32B	107.8
C11—C12—H12A	109.3	O22—C33—C32	109.38 (18)
C13—C12—H12B	109.3	O22—C33—C34	110.26 (18)
C11—C12—H12B	109.3	C32—C33—C34	108.47 (18)
H12A—C12—H12B	107.9	O22—C33—C36	114.53 (18)
O2—C13—C14	110.6 (2)	C32—C33—C36	112.08 (18)
O2—C13—C12	111.1 (2)	C34—C33—C36	101.76 (18)
C14—C13—C12	109.2 (2)	C33—C34—C28	102.68 (16)
O2—C13—C16	111.4 (2)	C33—C34—H34A	111.2
C14—C13—C16	102.9 (2)	C28—C34—H34A	111.2
C12—C13—C16	111.3 (2)	C33—C34—H34B	111.2
C13—C14—C8	104.46 (18)	C28—C34—H34B	111.2
C13—C14—H14A	110.9	H34A—C34—H34B	109.1
C8—C14—H14A	110.9	O23—C35—C28	128.3 (2)
C13—C14—H14B	110.9	O23—C35—C36	121.8 (2)
C8—C14—H14B	110.9	C28—C35—C36	109.95 (17)
H14A—C14—H14B	108.9	O24—C36—C37A	107.95 (19)
O3—C15—C8	127.0 (2)	O24—C36—C33	111.09 (19)
O3—C15—C16	122.8 (2)	C37A—C36—C33	113.06 (18)
C8—C15—C16	110.2 (2)	O24—C36—C35	111.95 (18)
O4—C16—C17A	105.7 (2)	C37A—C36—C35	110.74 (16)
O4—C16—C13	112.3 (2)	C33—C36—C35	102.06 (17)
C17A—C16—C13	115.8 (2)	O25A—C37A—C36	114.1 (2)
O4—C16—C15	111.4 (2)	O25A—C37A—H37A	108.7
C17A—C16—C15	110.3 (2)	C36—C37A—H37A	108.7
C13—C16—C15	101.5 (2)	O25A—C37A—H37B	108.7
O5A—C17A—C16	114.8 (3)	C36—C37A—H37B	108.7
O5A—C17A—H17A	108.6	H37A—C37A—H37B	107.6
C16—C17A—H17A	108.6	O25B—C37B—C36	114.2 (2)
O5A—C17A—H17B	108.6	O25B—C37B—H37C	108.7
C16—C17A—H17B	108.6	C36—C37B—H37C	108.7
H17A—C17A—H17B	107.6	O25B—C37B—H37D	108.7
O5B—C17B—C16	114.8 (3)	C36—C37B—H37D	108.7
O5B—C17B—H17C	108.5	H37C—C37B—H37D	107.6
C16—C17B—H17C	108.5	O25C—C37C—C36	114.3 (2)
O5B—C17B—H17D	108.5	O25C—C37C—H37E	108.7
C16—C17B—H17D	108.5	C36—C37C—H37E	108.7
H17C—C17B—H17D	107.5	O25C—C37C—H37F	108.7
C17A—O5A—H3O	109.5	C36—C37C—H37F	108.7
C17B—O5B—H4O	109.5	H37E—C37C—H37F	107.6
O1—C18—O6	120.9 (2)	C37A—O25A—H23O	109.5
O6—C18—C4	128.3 (2)	C37B—O25B—H24O	109.5
O1—C18—C4	110.65 (19)	C37C—O25C—H25O	109.5
C4—C19—H19A	109.5	O26—C38—O21	119.9 (2)
C4—C19—H19B	109.5	O26—C38—C24	129.5 (2)
H19A—C19—H19B	109.5	O21—C38—C24	110.47 (19)
C4—C19—H19C	109.5	C24—C39—H39A	109.5
H19A—C19—H19C	109.5	C24—C39—H39B	109.5
H19B—C19—H19C	109.5	H39A—C39—H39B	109.5
C9—C20—H20A	109.5	C24—C39—H39C	109.5
C9—C20—H20B	109.5	H39A—C39—H39C	109.5
H20A—C20—H20B	109.5	H39B—C39—H39C	109.5
C9—C20—H20C	109.5	C29—C40—H40A	109.5
H20A—C20—H20C	109.5	C29—C40—H40B	109.5
H20B—C20—H20C	109.5	H40A—C40—H40B	109.5
C30—O21—C38	109.46 (17)	C29—C40—H40C	109.5
C33—O22—H21O	109.5	H40A—C40—H40C	109.5
C36—O24—H22O	109.5	H40B—C40—H40C	109.5
C30—C21—C22	112.22 (19)	H1W—O1W—H2W	109.5
C10—C1—C2—C3	40.4 (3)	C22—C23—C24—C38	−46.3 (2)
C1—C2—C3—C4	−42.7 (3)	C22—C23—C24—C39	−170.0 (2)
C2—C3—C4—C18	−46.8 (3)	C22—C23—C24—C25	60.9 (3)
C2—C3—C4—C19	−169.8 (2)	C38—C24—C25—C26	−83.8 (2)
C2—C3—C4—C5	60.4 (3)	C39—C24—C25—C26	38.8 (3)
C18—C4—C5—C6	−84.7 (3)	C23—C24—C25—C26	164.5 (2)
C19—C4—C5—C6	36.9 (3)	C38—C24—C25—C30	37.6 (2)
C3—C4—C5—C6	164.2 (2)	C39—C24—C25—C30	160.1 (2)
C18—C4—C5—C10	37.8 (2)	C23—C24—C25—C30	−74.2 (2)
C19—C4—C5—C10	159.3 (2)	C24—C25—C26—C27	178.0 (2)
C3—C4—C5—C10	−73.4 (2)	C30—C25—C26—C27	63.0 (3)
C10—C5—C6—C7	62.3 (3)	C25—C26—C27—C28	−34.5 (3)
C4—C5—C6—C7	177.6 (2)	C26—C27—C28—C35	100.2 (2)
C5—C6—C7—C8	−31.3 (4)	C26—C27—C28—C34	−148.6 (2)
C6—C7—C8—C14	−152.4 (3)	C26—C27—C28—C29	−23.7 (3)
C6—C7—C8—C15	98.4 (3)	C35—C28—C29—C31	49.1 (2)
C6—C7—C8—C9	−26.8 (3)	C27—C28—C29—C31	175.73 (18)
C7—C8—C9—C11	177.4 (2)	C34—C28—C29—C31	−58.8 (2)
C14—C8—C9—C11	−56.8 (2)	C35—C28—C29—C40	166.60 (16)
C15—C8—C9—C11	49.1 (2)	C27—C28—C29—C40	−66.7 (2)
C7—C8—C9—C20	−65.1 (3)	C34—C28—C29—C40	58.8 (2)
C14—C8—C9—C20	60.7 (2)	C35—C28—C29—C30	−72.6 (2)
C15—C8—C9—C20	166.58 (19)	C27—C28—C29—C30	54.0 (2)
C7—C8—C9—C10	55.4 (3)	C34—C28—C29—C30	179.53 (16)
C14—C8—C9—C10	−178.77 (18)	C38—O21—C30—C21	−90.0 (2)
C15—C8—C9—C10	−72.9 (2)	C38—O21—C30—C25	23.9 (2)
C18—O1—C10—C5	25.4 (2)	C38—O21—C30—C29	145.4 (2)
C18—O1—C10—C1	−88.9 (2)	C22—C21—C30—O21	51.9 (2)
C18—O1—C10—C9	146.85 (19)	C22—C21—C30—C25	−56.9 (3)
C6—C5—C10—O1	85.3 (2)	C22—C21—C30—C29	170.8 (2)
C4—C5—C10—O1	−38.5 (2)	C26—C25—C30—O21	85.5 (2)
C6—C5—C10—C1	−164.18 (19)	C24—C25—C30—O21	−37.9 (2)
C4—C5—C10—C1	72.0 (2)	C26—C25—C30—C21	−163.60 (19)
C6—C5—C10—C9	−31.7 (3)	C24—C25—C30—C21	73.0 (2)
C4—C5—C10—C9	−155.45 (18)	C26—C25—C30—C29	−30.7 (3)
C2—C1—C10—O1	51.5 (3)	C24—C25—C30—C29	−154.05 (18)
C2—C1—C10—C5	−57.1 (3)	C31—C29—C30—O21	101.00 (19)
C2—C1—C10—C9	170.9 (2)	C40—C29—C30—O21	−18.8 (2)
C11—C9—C10—O1	101.9 (2)	C28—C29—C30—O21	−139.23 (17)
C20—C9—C10—O1	−18.1 (2)	C31—C29—C30—C21	−16.6 (3)
C8—C9—C10—O1	−138.47 (18)	C40—C29—C30—C21	−136.4 (2)
C11—C9—C10—C5	−145.03 (19)	C28—C29—C30—C21	103.2 (2)
C20—C9—C10—C5	94.9 (2)	C31—C29—C30—C25	−146.01 (19)
C8—C9—C10—C5	−25.4 (2)	C40—C29—C30—C25	94.1 (2)
C11—C9—C10—C1	−15.4 (3)	C28—C29—C30—C25	−26.2 (2)
C20—C9—C10—C1	−135.4 (2)	C40—C29—C31—C32	−72.9 (2)
C8—C9—C10—C1	104.2 (2)	C28—C29—C31—C32	45.8 (2)
C20—C9—C11—C12	−73.6 (2)	C30—C29—C31—C32	165.90 (18)
C8—C9—C11—C12	45.1 (3)	C29—C31—C32—C33	−47.9 (3)
C10—C9—C11—C12	165.01 (19)	C31—C32—C33—O22	−179.67 (19)
C9—C11—C12—C13	−47.6 (3)	C31—C32—C33—C34	60.0 (2)
C11—C12—C13—O2	−178.2 (2)	C31—C32—C33—C36	−51.5 (3)
C11—C12—C13—C14	59.6 (3)	O22—C33—C34—C28	171.19 (18)
C11—C12—C13—C16	−53.4 (3)	C32—C33—C34—C28	−69.1 (2)
O2—C13—C14—C8	168.1 (2)	C36—C33—C34—C28	49.3 (2)
C12—C13—C14—C8	−69.3 (2)	C35—C28—C34—C33	−43.3 (2)
C16—C13—C14—C8	49.0 (2)	C27—C28—C34—C33	−163.1 (2)
C7—C8—C14—C13	−163.4 (2)	C29—C28—C34—C33	70.2 (2)
C15—C8—C14—C13	−43.7 (2)	C27—C28—C35—O23	−38.4 (3)
C9—C8—C14—C13	69.1 (2)	C34—C28—C35—O23	−156.7 (2)
C7—C8—C15—O3	−37.7 (3)	C29—C28—C35—O23	88.3 (3)
C14—C8—C15—O3	−154.9 (3)	C27—C28—C35—C36	140.27 (18)
C9—C8—C15—O3	90.5 (3)	C34—C28—C35—C36	22.0 (2)
C7—C8—C15—C16	140.8 (2)	C29—C28—C35—C36	−93.02 (19)
C14—C8—C15—C16	23.6 (2)	O22—C33—C36—O24	87.8 (2)
C9—C8—C15—C16	−91.0 (2)	C32—C33—C36—O24	−37.5 (2)
O2—C13—C16—O4	91.2 (3)	C34—C33—C36—O24	−153.22 (18)
C14—C13—C16—O4	−150.2 (2)	O22—C33—C36—C37A	−33.7 (3)
C12—C13—C16—O4	−33.4 (3)	C32—C33—C36—C37A	−159.06 (17)
O2—C13—C16—C17A	−30.3 (3)	C34—C33—C36—C37A	85.24 (19)
C14—C13—C16—C17A	88.2 (3)	O22—C33—C36—C35	−152.68 (18)
C12—C13—C16—C17A	−154.9 (2)	C32—C33—C36—C35	82.0 (2)
O2—C13—C16—C15	−149.7 (2)	C34—C33—C36—C35	−33.7 (2)
C14—C13—C16—C15	−31.2 (2)	O23—C35—C36—O24	−55.4 (3)
C12—C13—C16—C15	85.7 (2)	C28—C35—C36—O24	125.84 (19)
O3—C15—C16—O4	−57.8 (3)	O23—C35—C36—C37A	65.1 (3)
C8—C15—C16—O4	123.6 (2)	C28—C35—C36—C37A	−113.6 (2)
O3—C15—C16—C17A	59.3 (3)	O23—C35—C36—C33	−174.3 (2)
C8—C15—C16—C17A	−119.3 (2)	C28—C35—C36—C33	7.0 (2)
O3—C15—C16—C13	−177.5 (2)	O24—C36—C37A—O25A	−49.7 (3)
C8—C15—C16—C13	3.9 (2)	C33—C36—C37A—O25A	73.6 (3)
O4—C16—C17A—O5A	178.8 (3)	C35—C36—C37A—O25A	−172.6 (3)
C13—C16—C17A—O5A	−56.2 (4)	O24—C36—C37B—O25B	159.4 (5)
C15—C16—C17A—O5A	58.3 (3)	C33—C36—C37B—O25B	−77.3 (5)
O4—C16—C17B—O5B	56.7 (8)	C35—C36—C37B—O25B	36.6 (6)
C13—C16—C17B—O5B	−178.2 (7)	O24—C36—C37C—O25C	79.8 (7)
C15—C16—C17B—O5B	−63.8 (7)	C33—C36—C37C—O25C	−156.9 (7)
C10—O1—C18—O6	176.6 (2)	C35—C36—C37C—O25C	−43.1 (7)
C10—O1—C18—C4	−0.5 (3)	C30—O21—C38—O26	177.7 (2)
C19—C4—C18—O6	34.5 (4)	C30—O21—C38—C24	0.7 (3)
C3—C4—C18—O6	−88.5 (3)	C39—C24—C38—O26	32.9 (4)
C5—C4—C18—O6	159.0 (3)	C25—C24—C38—O26	158.3 (3)
C19—C4—C18—O1	−148.7 (2)	C23—C24—C38—O26	−90.0 (3)
C3—C4—C18—O1	88.3 (2)	C39—C24—C38—O21	−150.5 (2)
C5—C4—C18—O1	−24.2 (3)	C25—C24—C38—O21	−25.1 (3)
C30—C21—C22—C23	40.0 (3)	C23—C24—C38—O21	86.6 (2)
C21—C22—C23—C24	−42.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O···O1W^i	0.95	1.79	2.720 (3)	167
O4—H2O···O21^ii	0.95	2.77	3.503 (3)	135
O4—H2O···O26^ii	0.95	2.51	3.370 (3)	150
O5A—H3O···O2	0.95	2.69	3.102 (4)	107
O5A—H3O···O22^iii	0.95	2.18	3.053 (4)	152
O5B—H4O···O3	0.95	2.18	2.937 (10)	135
O5B—H4O···O21^ii	0.95	2.88	3.420 (12)	117
O22—H21O···O2^iv	0.95	1.86	2.775 (3)	161
O22—H21O···O25A	0.95	2.47	2.851 (4)	104
O24—H22O···O1^v	0.95	2.08	3.015 (2)	168
O24—H22O···O6^v	0.95	2.73	3.423 (3)	130
O25A—H23O···O6^v	0.95	2.32	3.230 (5)	160
O25B—H24O···O22^iv	0.95	2.13	3.020 (7)	155
O25C—H25O···O5A^vi	0.95	2.21	3.029 (15)	145
O25C—H25O···O23	0.95	2.48	2.780 (8)	98
O1W—H1W···O6	0.95	1.91	2.842 (3)	168
O1W—H2W···O26	0.95	1.96	2.898 (3)	169

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