9-Benzoyl-3,3,6,6-tetra­methyl-1,2,3,4,5,6,7,8-octa­hydroxanthene-1,8-dione: mol­ecular conformation and supra­molecular aggregation in xanthenediones

In the title compound, C₂₄H₂₆O₄, (I), the central ring of the fused tricyclic ring system adopts a shallow boat conformation, while the two outer rings adopt envelope conformations. The mol­ecules are linked into C(9) chains by a single C—H...O hydrogen bond. The significance of this study lies in its comparison of the conformation and supra­molecular aggregation of (I) with those of related compounds in the published literature.

S1. Comment

We have recently reported the preparation of new fused heterocyclic compounds containing the pyrimidine fragment, such as pyrimidino[4,5-b]quinolines, using multicomponent reactions between 4,4-dimethyl-1,3-cyclohexanedione (dimedone), 6-aminopyrimidine derivatives and aryl aldehydes (Quiroga et al., 2006). We have attempted to modify the procedure by replacing the aldehyde component with a glyoxal derivative, and here we report the structure of the title product, (I), synthesized as an intermediate for subsequent reactions with 6-aminopyrimidine derivatives. Compound (I) was formed by a condensation reaction between phenylglyoxal and dimedone, which was induced by microwave irradiation under solvent-free reaction conditions. Here we not only report the molecular and supramolecular structure of (I), but compare its conformation with those of simple analogues taken from the recent literature or retrieved from the Cambridge Structural Database (CSD, Version 5.29, January 2008; Allen, 2002).

The central ring in the molecule of (I) (Fig. 1) adopts a shallow boat conformation, while the two outer rings adopt envelope conformations. For the atom sequences C1a/C2–C5/C5a and C10a/C10–C7/C6a, respectively, the ring-puckering angles (Cremer & Pople, 1975) are θ = 56.6 (2)° and ϕ = 127.7 (3)°, and θ = 127.3 (3)° and ϕ = 312.1 (3)°, with the fold of the envelopes across the lines C2···C4 and C8···C10. For the idealized envelope conformation, the ring-puckering angles are θ = 54.7° (or 125.3°) and ϕ = 60k°, where k represents an integer. The relationship between the puckering angles for the two outer rings indicates that the fused ring system has approximate but non-crystallographic mirror symmetry. However, because of the orientation of the pendent benzoyl group, as indicated by the relevant torsion angles (Table 1), the molecule has no internal symmetry, and hence it is chiral. However, the centrosymmetric space group accommodates equal numbers of the two conformational enantiomers. The C5—O5 and C7—O7 bonds (Table 1) are slightly longer than normal for cyclohexanones (mean value 1.211 Å; upper quartile value 1.216 Å; Allen et al., 1987), while the C67—O6 bond is slightly shorter than typical for benzoyl groups (mean value 1.221 Å; lower quartile value 1.212 Å). Otherwise the bond distances in (I) show no unexpected features.

A single C—H···O hydrogen bond (Table 2) links molecules of (I), which are related by the b-glide plane at x = 3/4, into C(9) (Bernstein et al., 1995) chains running parallel to the [010] direction (Fig. 2). Four chains of this type run through each unit cell but there are no direction-specific interactions between the chains.

The structures of several other tetramethylxanthene-1,8-diones, compounds (II)–(VI) (see scheme) have been reported in recent years and it is of interest to compare briefly both the molecular conformations and the supramolecular aggregation in these compounds with those in (I) as, in many cases, these properties were either not mentioned in the original reports, or they were only partly analysed.

In compounds (II) and (V) (Jeyakanthan et al., 1999), so-called sofa conformations were deduced for the two outer rings, apparently by using only the ring-puckering amplitudes; the ring-puckering angles, which are the primary diagnostic of conformation, were not mentioned. For compound (IV) (Bigdeli et al., 2007), the outer rings were reported to be in a trans conformation, without any indication of reference points or of ring shape. Compound (III) (Tu et al., 2001) is isomorphous with (IV), although this was not noted in the subsequent report on (IV) (Bigdeli et al., 2007); no analysis of ring conformation was made for (III). The outer rings in (VI) were reported (Selvanayagam et al., 2005) as having half-boat conformations but, as with (II) and (V), no ring-puckering angles were cited, only the puckering amplitudes. Re-analysis of all of these structures, using the published atom coordinates followed by inspection of the ring-puckering angles, shows that, in every case, the outer two rings adopt envelope conformations, folded just as in (I) reported here. In addition to (II)–(VI), several analogues, compounds (VII)–(X) (see scheme), which do not carry the four methyl substituents, have been retrieved from the CSD. Again, the ring-puckering angles show that the outer rings adopt envelope conformations, folded as in (I)–(VI), despite the absence of the methyl groups.

With the exception of (VIII), PAMXOM, where the molecules lie across a mirror plane in space group Cmc2₁, the senses of the folding in the two outer rings are independent. Thus, the flap atoms of the envelopes could be on the same side of the mean plane describing the rest of the tricyclic system, or on opposite sides. Where they are on the same side they could be directed towards the pendent substituent or away from it, apart from (II), where no such substituent is present. Where the flap atoms are on the same side of the tricyclic system, this has approximate mirror (C_s) symmetry; where the flap atoms are on opposite sides of the tricyclic system, this has approximate twofold rotation (C₂) symmetry.

The overall molecular conformations are most readily assessed via the molecular profiles. For (I), the profile (Fig. 3a) shows two flap atoms, both on the same face of the tricyclic system as the pendent benzoyl group. Similarly for (II), both flap atoms are on the same side despite the absence of a pendent aryl substituent (Fig. 3b). This type of conformation is also found for (V) (Fig. 3c) and (VI), and for (VII)–(IX). On the other hand, the isomorphous pair (III) and (IV) have the flap atoms on opposite faces of the tricyclic system (Fig. 3d), as does (X).

Finally, we compare very briefly the hydrogen-bonded aggregation in (I)–(VI) with the simple C(9) chains found in (I). The report on (II) and (V) (Jeyakanthan et al., 1999) makes no mention of any intermolecular interactions. In fact, two independent C—H···O hydrogen bonds, both with a ketonic O atom as the acceptor, link the molecules of (II) into a C(6)C(6)[R²₂(14)] chain of rings (Fig. 4a). In (V), there are again two C—H···O hydrogen bonds, one each with ketonic and nitro O atoms as the acceptors, and these link the molecules into a C(6)C(8)[R²₂(12)] chain of rings (Fig. 4b). Again, for (IV), the original report (Bigdeli et al., 2007) makes no mention of intermolecular interactions, but in fact a single C—H···O hydrogen bond links the molecules into a simple C(7) chain. A similar chain can be expected in the isomorphous compound (III) (Tu et al., 2001), but no H-atom coordinates are available for this structure. Two hydrogen bonds were reported for (VI) (Selvanayagam et al., 2005) and the authors mention R²₂(8) dimers further linked by a C—H···O hydrogen bond, but without further specification of the structural consequences. In fact, the molecules are linked into a chain of alternating edge-fused R²₂(8) and R⁴₄(28) rings (Fig. 4c).

Related literature

For related literature, see: Allen (2002); Allen et al. (1987); Bernstein et al. (1995); Bigdeli et al. (2007); Cremer & Pople (1975); Jeyakanthan et al. (1999); Quiroga et al. (2006); Selvanayagam et al. (2005); Tu et al. (2001).

S2. Experimental

A mixture of 4,4-dimethyl-1,3-cyclohexanedione (dimedone, 2.0 mmol) and phenylglyoxal hydrate (1.0 mmol) was placed in an open Pyrex glass flask and irradiated in a domestic microwave oven for 6 min at 600 W. The product mixture was extracted with ethanol and, after removal of the solvent, the product, (I), was recrystallized from ethanol to give crystals suitable for single-crystal X-ray diffraction (yield 45%, m.p. 478–479 K). MS (EI 70 eV) m/z: 379 (2), 378 (M+, 1), 373 (100), 217 (23), 131 (13), 77 (19).

S3. Refinement

The space group Pbca was uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.93 (aromatic), 0.96 (CH₃), 0.97 (CH₂) or 0.98 Å (aliphatic CH), and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups and 1.2 for all other H atoms.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a C(9) chain along [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash symbol (#) are at the symmetry positions (3/2 - x, -1/2 + y, z) and (3/2 - x, 1/2 + y, z), respectively.
	Fig. 3. Molecular profiles of selected tetramethylxanthenediones. (a) (I), (b) (II), (c) (V), (d) (IV). For (II), (IV) and (V), the original atom coordinates (Jeyakanthan et al., 1999; Bigdeli et al., 2007) were used. In all cases, H atoms have been omitted for the sake of clarity.
	Fig. 4. Stereoviews of parts of the crystal structures of selected tetramethylxanthenediones, showing the formation of chains of rings. (a) (II), (b) (V), (c) (VI). The original atom coordinates (Jeyakanthan et al., 1999; Selvanayagam et al., 2005) were used. In all cases, H atoms not involved in the motifs shown have been omitted for the sake of clarity.

9-Benzoyl-3,3,6,6-tetramethyl-1,2,3,4,5,6,7,8-octahydroxanthene-1,8-dione

Crystal data

C24H26O4	F(000) = 1616
Mr = 378.45	Dx = 1.212 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4252 reflections
a = 11.6394 (15) Å	θ = 3.2–27.5°
b = 11.5736 (15) Å	µ = 0.08 mm^−1
c = 30.782 (4) Å	T = 293 K
V = 4146.6 (9) Å^3	Rod, colourless
Z = 8	0.80 × 0.20 × 0.18 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	4239 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2266 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
Tmin = 0.964, Tmax = 0.986	l = −27→38
17519 measured 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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0719P)^2] where P = (Fo^2 + 2Fc^2)/3
4239 reflections	(Δ/σ)max < 0.001
253 parameters	Δρmax = 0.13 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

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

	x	y	z	Uiso*/Ueq
O1	0.19430 (10)	0.60890 (10)	0.13050 (4)	0.0483 (4)
O5	0.51744 (13)	0.65873 (12)	0.22134 (5)	0.0718 (5)
O6	0.45688 (13)	0.52924 (13)	0.09348 (6)	0.0825 (5)
O7	0.46564 (13)	0.87097 (12)	0.07470 (5)	0.0765 (5)
C1a	0.25964 (15)	0.58829 (15)	0.16719 (6)	0.0421 (5)
C2	0.19758 (17)	0.51427 (16)	0.19894 (6)	0.0523 (5)
C3	0.27971 (18)	0.45715 (16)	0.23122 (7)	0.0575 (6)
C4	0.35933 (19)	0.55077 (17)	0.24930 (7)	0.0620 (6)
C5	0.42196 (18)	0.61711 (15)	0.21478 (6)	0.0492 (5)
C5a	0.36481 (15)	0.63299 (13)	0.17290 (6)	0.0402 (5)
C6	0.42590 (14)	0.69460 (15)	0.13638 (6)	0.0412 (5)
C6a	0.33699 (14)	0.73877 (14)	0.10471 (6)	0.0405 (5)
C7	0.36825 (17)	0.83189 (16)	0.07461 (7)	0.0485 (5)
C8	0.27560 (17)	0.87732 (15)	0.04515 (7)	0.0530 (5)
C9	0.18988 (15)	0.78682 (15)	0.02994 (6)	0.0475 (5)
C10	0.14132 (15)	0.72612 (16)	0.07039 (6)	0.0485 (5)
C10a	0.23198 (15)	0.69348 (15)	0.10199 (6)	0.0405 (5)
C31	0.2100 (2)	0.4034 (2)	0.26837 (9)	0.0917 (9)
C32	0.3522 (2)	0.36500 (16)	0.20841 (9)	0.0796 (8)
C61	0.63104 (15)	0.60765 (16)	0.11757 (6)	0.0448 (5)
C62	0.69161 (19)	0.51449 (18)	0.10119 (7)	0.0656 (6)
C63	0.8090 (2)	0.5108 (2)	0.10312 (9)	0.0799 (8)
C64	0.86900 (19)	0.6000 (2)	0.12154 (8)	0.0768 (7)
C65	0.81123 (18)	0.6938 (2)	0.13737 (8)	0.0749 (7)
C66	0.69176 (17)	0.69744 (19)	0.13530 (7)	0.0610 (6)
C67	0.50405 (16)	0.60561 (16)	0.11357 (6)	0.0473 (5)
C91	0.09082 (17)	0.84488 (18)	0.00523 (7)	0.0695 (6)
C92	0.24792 (18)	0.69955 (18)	−0.00006 (7)	0.0662 (6)
H2A	0.1555	0.4549	0.1834	0.063*
H2B	0.1424	0.5610	0.2147	0.063*
H4A	0.3142	0.6043	0.2665	0.074*
H4B	0.4152	0.5149	0.2684	0.074*
H6	0.4718	0.7588	0.1478	0.049*
H8A	0.3115	0.9119	0.0198	0.064*
H8B	0.2342	0.9379	0.0603	0.064*
H10A	0.0867	0.7771	0.0845	0.058*
H10B	0.1004	0.6571	0.0614	0.058*
H31A	0.2614	0.3686	0.2890	0.137*
H31B	0.1593	0.3456	0.2569	0.137*
H31C	0.1658	0.4625	0.2825	0.137*
H32A	0.4042	0.3308	0.2289	0.119*
H32B	0.3951	0.4000	0.1853	0.119*
H32C	0.3026	0.3064	0.1967	0.119*
H62	0.6518	0.4533	0.0886	0.079*
H63	0.8481	0.4475	0.0919	0.096*
H64	0.9487	0.5968	0.1233	0.092*
H65	0.8517	0.7551	0.1495	0.090*
H66	0.6528	0.7615	0.1461	0.073*
H91A	0.0373	0.7871	−0.0043	0.104*
H91B	0.1208	0.8852	−0.0195	0.104*
H91C	0.0525	0.8986	0.0241	0.104*
H92A	0.1928	0.6427	−0.0091	0.099*
H92B	0.3097	0.6623	0.0151	0.099*
H92C	0.2778	0.7388	−0.0251	0.099*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0369 (7)	0.0599 (8)	0.0481 (8)	−0.0083 (6)	−0.0057 (7)	0.0093 (7)
O5	0.0634 (10)	0.0925 (11)	0.0595 (10)	−0.0169 (8)	−0.0232 (8)	0.0017 (8)
O6	0.0536 (9)	0.0846 (11)	0.1094 (14)	−0.0022 (8)	−0.0014 (10)	−0.0516 (10)
O7	0.0558 (9)	0.0842 (10)	0.0896 (13)	−0.0298 (8)	−0.0110 (9)	0.0233 (9)
C1a	0.0383 (11)	0.0468 (11)	0.0411 (11)	0.0041 (9)	−0.0021 (10)	−0.0002 (9)
C2	0.0502 (12)	0.0574 (12)	0.0494 (12)	−0.0051 (10)	0.0007 (11)	0.0068 (10)
C3	0.0643 (14)	0.0541 (13)	0.0540 (13)	−0.0041 (11)	−0.0069 (12)	0.0123 (10)
C4	0.0767 (15)	0.0655 (13)	0.0438 (12)	−0.0064 (11)	−0.0114 (12)	0.0020 (10)
C5	0.0515 (13)	0.0496 (12)	0.0465 (12)	0.0001 (10)	−0.0088 (11)	−0.0071 (10)
C5a	0.0378 (11)	0.0422 (11)	0.0407 (11)	0.0030 (8)	−0.0055 (9)	−0.0049 (8)
C6	0.0329 (10)	0.0455 (10)	0.0451 (11)	−0.0024 (8)	−0.0022 (9)	−0.0056 (9)
C6a	0.0330 (10)	0.0466 (11)	0.0420 (11)	−0.0007 (8)	−0.0003 (9)	−0.0002 (9)
C7	0.0436 (12)	0.0484 (11)	0.0535 (12)	−0.0058 (10)	−0.0007 (11)	−0.0027 (10)
C8	0.0559 (13)	0.0503 (12)	0.0528 (13)	−0.0016 (9)	−0.0035 (11)	0.0084 (9)
C9	0.0456 (11)	0.0554 (12)	0.0414 (11)	0.0018 (9)	−0.0019 (10)	0.0021 (9)
C10	0.0355 (10)	0.0625 (12)	0.0474 (12)	0.0026 (9)	−0.0039 (10)	0.0038 (10)
C10a	0.0369 (11)	0.0446 (11)	0.0401 (11)	−0.0007 (8)	0.0019 (9)	0.0020 (9)
C31	0.099 (2)	0.0996 (18)	0.0764 (18)	−0.0185 (16)	−0.0118 (17)	0.0369 (15)
C32	0.0854 (17)	0.0492 (13)	0.104 (2)	0.0058 (12)	−0.0204 (16)	0.0029 (13)
C61	0.0367 (11)	0.0567 (12)	0.0411 (11)	0.0046 (10)	0.0036 (9)	0.0026 (10)
C62	0.0556 (15)	0.0673 (15)	0.0740 (16)	0.0151 (11)	0.0059 (13)	−0.0069 (12)
C63	0.0532 (16)	0.0868 (19)	0.100 (2)	0.0257 (14)	0.0112 (15)	−0.0005 (15)
C64	0.0351 (12)	0.119 (2)	0.0764 (18)	0.0158 (14)	0.0092 (13)	0.0158 (16)
C65	0.0417 (13)	0.1037 (18)	0.0793 (18)	−0.0119 (13)	0.0024 (13)	−0.0071 (14)
C66	0.0415 (12)	0.0729 (14)	0.0687 (15)	0.0012 (11)	0.0025 (11)	−0.0124 (12)
C67	0.0407 (11)	0.0538 (12)	0.0475 (12)	0.0001 (9)	−0.0012 (10)	−0.0051 (10)
C91	0.0655 (15)	0.0841 (14)	0.0589 (14)	0.0084 (12)	−0.0159 (13)	0.0082 (12)
C92	0.0689 (15)	0.0742 (15)	0.0556 (14)	−0.0013 (11)	0.0047 (13)	−0.0095 (11)

Geometric parameters (Å, º)

O1—C1a	1.382 (2)	C62—C63	1.368 (3)
O1—C10a	1.386 (2)	C62—H62	0.93
C1a—C5a	1.341 (2)	C63—C64	1.369 (3)
C1a—C2	1.487 (2)	C63—H63	0.93
C2—C3	1.529 (3)	C64—C65	1.367 (3)
C2—H2A	0.97	C64—H64	0.93
C2—H2B	0.97	C65—C66	1.393 (3)
C3—C32	1.530 (3)	C65—H65	0.93
C3—C4	1.530 (3)	C66—H66	0.93
C3—C31	1.534 (3)	C6a—C10a	1.332 (2)
C31—H31A	0.96	C6a—C7	1.467 (3)
C31—H31B	0.96	C7—O7	1.220 (2)
C31—H31C	0.96	C7—C8	1.504 (3)
C32—H32A	0.96	C8—C9	1.520 (2)
C32—H32B	0.96	C8—H8A	0.97
C32—H32C	0.96	C8—H8B	0.97
C4—C5	1.500 (3)	C9—C92	1.526 (3)
C4—H4A	0.97	C9—C91	1.536 (2)
C4—H4B	0.97	C9—C10	1.537 (3)
C5—O5	1.228 (2)	C91—H91A	0.96
C5—C5a	1.462 (3)	C91—H91B	0.96
C5a—C6	1.509 (2)	C91—H91C	0.96
C6—C6a	1.511 (2)	C92—H92A	0.96
C6—C67	1.543 (2)	C92—H92B	0.96
C6—H6	0.98	C92—H92C	0.96
C67—O6	1.211 (2)	C10—C10a	1.484 (2)
C67—C61	1.483 (3)	C10—H10A	0.97
C61—C66	1.370 (3)	C10—H10B	0.97
C61—C62	1.383 (3)
C1a—O1—C10a	117.72 (13)	C63—C62—H62	119.4
C5a—C1a—O1	122.89 (16)	C61—C62—H62	119.4
C5a—C1a—C2	125.43 (17)	C62—C63—C64	120.3 (2)
O1—C1a—C2	111.66 (15)	C62—C63—H63	119.9
C1a—C2—C3	111.88 (16)	C64—C63—H63	119.9
C1a—C2—H2A	109.2	C65—C64—C63	119.7 (2)
C3—C2—H2A	109.2	C65—C64—H64	120.2
C1a—C2—H2B	109.2	C63—C64—H64	120.2
C3—C2—H2B	109.2	C64—C65—C66	119.9 (2)
H2A—C2—H2B	107.9	C64—C65—H65	120.0
C2—C3—C32	110.34 (18)	C66—C65—H65	120.0
C2—C3—C4	107.98 (15)	C61—C66—C65	120.7 (2)
C32—C3—C4	109.06 (18)	C61—C66—H66	119.7
C2—C3—C31	109.22 (17)	C65—C66—H66	119.7
C32—C3—C31	110.56 (17)	C10a—C6a—C7	118.48 (17)
C4—C3—C31	109.64 (18)	C10a—C6a—C6	122.38 (16)
C3—C31—H31A	109.5	C7—C6a—C6	119.09 (15)
C3—C31—H31B	109.5	O7—C7—C6a	120.07 (18)
H31A—C31—H31B	109.5	O7—C7—C8	122.54 (18)
C3—C31—H31C	109.5	C6a—C7—C8	117.37 (16)
H31A—C31—H31C	109.5	C7—C8—C9	114.54 (15)
H31B—C31—H31C	109.5	C7—C8—H8A	108.6
C3—C32—H32A	109.5	C9—C8—H8A	108.6
C3—C32—H32B	109.5	C7—C8—H8B	108.6
H32A—C32—H32B	109.5	C9—C8—H8B	108.6
C3—C32—H32C	109.5	H8A—C8—H8B	107.6
H32A—C32—H32C	109.5	C8—C9—C92	110.59 (16)
H32B—C32—H32C	109.5	C8—C9—C91	110.10 (15)
C5—C4—C3	113.53 (17)	C92—C9—C91	108.79 (16)
C5—C4—H4A	108.9	C8—C9—C10	107.87 (16)
C3—C4—H4A	108.9	C92—C9—C10	110.51 (15)
C5—C4—H4B	108.9	C91—C9—C10	108.96 (15)
C3—C4—H4B	108.9	C9—C91—H91A	109.5
H4A—C4—H4B	107.7	C9—C91—H91B	109.5
O5—C5—C5a	120.48 (18)	H91A—C91—H91B	109.5
O5—C5—C4	121.62 (19)	C9—C91—H91C	109.5
C5a—C5—C4	117.89 (17)	H91A—C91—H91C	109.5
C1a—C5a—C5	118.85 (17)	H91B—C91—H91C	109.5
C1a—C5a—C6	120.99 (16)	C9—C92—H92A	109.5
C5—C5a—C6	120.11 (15)	C9—C92—H92B	109.5
C5a—C6—C6a	108.53 (14)	H92A—C92—H92B	109.5
C5a—C6—C67	107.53 (14)	C9—C92—H92C	109.5
C6a—C6—C67	109.62 (15)	H92A—C92—H92C	109.5
C5a—C6—H6	110.4	H92B—C92—H92C	109.5
C6a—C6—H6	110.4	C10a—C10—C9	112.69 (15)
C67—C6—H6	110.4	C10a—C10—H10A	109.1
O6—C67—C61	120.39 (17)	C9—C10—H10A	109.1
O6—C67—C6	116.90 (16)	C10a—C10—H10B	109.1
C61—C67—C6	122.62 (16)	C9—C10—H10B	109.1
C66—C61—C62	118.26 (19)	H10A—C10—H10B	107.8
C66—C61—C67	123.99 (17)	C6a—C10a—O1	121.90 (16)
C62—C61—C67	117.72 (18)	C6a—C10a—C10	126.38 (17)
C63—C62—C61	121.2 (2)	O1—C10a—C10	111.70 (14)
C10a—O1—C1a—C5a	−10.4 (2)	C66—C61—C62—C63	1.0 (3)
C10a—O1—C1a—C2	168.16 (15)	C67—C61—C62—C63	179.1 (2)
C5a—C1a—C2—C3	−21.1 (3)	C61—C62—C63—C64	0.1 (4)
O1—C1a—C2—C3	160.30 (15)	C62—C63—C64—C65	−1.1 (4)
C1a—C2—C3—C32	−70.0 (2)	C63—C64—C65—C66	1.0 (4)
C1a—C2—C3—C4	49.1 (2)	C62—C61—C66—C65	−1.1 (3)
C1a—C2—C3—C31	168.26 (17)	C67—C61—C66—C65	−179.1 (2)
C2—C3—C4—C5	−54.9 (2)	C64—C65—C66—C61	0.1 (4)
C32—C3—C4—C5	65.0 (2)	C5a—C6—C6a—C10a	−22.2 (2)
C31—C3—C4—C5	−173.83 (18)	C67—C6—C6a—C10a	95.0 (2)
C3—C4—C5—O5	−150.00 (19)	C5a—C6—C6a—C7	160.25 (16)
C3—C4—C5—C5a	31.1 (2)	C67—C6—C6a—C7	−82.57 (19)
O1—C1a—C5a—C5	173.15 (15)	C10a—C6a—C7—O7	−176.11 (18)
C2—C1a—C5a—C5	−5.2 (3)	C6—C6a—C7—O7	1.6 (3)
O1—C1a—C5a—C6	−9.3 (3)	C10a—C6a—C7—C8	5.3 (3)
C2—C1a—C5a—C6	172.30 (16)	C6—C6a—C7—C8	−177.04 (16)
O5—C5—C5a—C1a	−178.69 (17)	O7—C7—C8—C9	146.86 (19)
C4—C5—C5a—C1a	0.2 (3)	C6a—C7—C8—C9	−34.5 (2)
O5—C5—C5a—C6	3.7 (3)	C7—C8—C9—C92	−67.2 (2)
C4—C5—C5a—C6	−177.38 (15)	C7—C8—C9—C91	172.54 (17)
C1a—C5a—C6—C6a	23.9 (2)	C7—C8—C9—C10	53.8 (2)
C5—C5a—C6—C6a	−158.59 (15)	C8—C9—C10—C10a	−45.9 (2)
C1a—C5a—C6—C67	−94.62 (19)	C92—C9—C10—C10a	75.1 (2)
C5—C5a—C6—C67	82.89 (19)	C91—C9—C10—C10a	−165.38 (15)
C5a—C6—C67—O6	68.3 (2)	C7—C6a—C10a—O1	−177.08 (15)
C6a—C6—C67—O6	−49.5 (2)	C6—C6a—C10a—O1	5.3 (3)
C5a—C6—C67—C61	−108.35 (19)	C7—C6a—C10a—C10	1.4 (3)
C6a—C6—C67—C61	133.84 (18)	C6—C6a—C10a—C10	−176.23 (17)
O6—C67—C61—C66	172.1 (2)	C1a—O1—C10a—C6a	12.5 (2)
C6—C67—C61—C66	−11.3 (3)	C1a—O1—C10a—C10	−166.18 (15)
O6—C67—C61—C62	−5.9 (3)	C9—C10—C10a—C6a	20.6 (3)
C6—C67—C61—C62	170.66 (17)	C9—C10—C10a—O1	−160.77 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C63—H63···O7^i	0.93	2.40	3.204 (3)	145

Symmetry code: (i) −x+3/2, y−1/2, z.