Dispiro­[indene-2,5'-indeno[2,1-a]fluorene-6',2''-indene]-1,1'',3,3'',11',12'-hexa­one: a three-dimensional hydrogen-bonded framework

The title compound, C₃₆H₁₆O₆, (I), was obtained as a new and unexpected oxidation product of 1,2'-biindene-1',3,3'(2H)-trione. The mol­ecules of (I) exhibit approximate, but noncrystallographic, twofold rotation symmetry and the central ring of the fused penta­cyclic portion is distinctly puckered, with a conformation inter­mediate between half-chair and screw-boat. Six independent C-H...O hydrogen bonds link the mol­ecules into a three-dimensional framework structure of considerable complexity. Comparisons are drawn between the crystal structure of (I) and those of several simpler analogues, which show wide variation in their patterns of supra­molecular aggregation.

S1. Comment

Benzodiazepines are a class of psychoactive drugs which have found extensive use as minor tranquilisers with a broad range of applications (Pozharskii et al., 1997; Lueddens & Korpi, 2007). Pyrimidobenzodiazepines and their fused derivatives also display similar properties and they have extended the range of pharmaceutical applications (Długosz, 1995). In order to explore synthetic routes to new pyrimido[4,5-b][1,4]diazepine derivatives incorporating fused and/or spiro units linked to the diazepine moiety, we have utilized the chalcone reagent 1,2'-biindene-1',3,3'(2H)-trione, (III), prepared by autocondensation of 1,3-indandione, (II), in reactions with 4,5-diaminopyrimidines. Instead of the expected fused derivative, the reaction between 2,4,5-diaminopyrimidin-4(3H)-one and 1,2'-biindene-1',3,3'(2H)-trione produced 3-[(2,4-diamino-6-oxo-1,6-dihydropyrimidin-5-yl)amino]-1,2'-biindene-1',3'-dione in 90% yield, together with a small quantity of the unexpected dispiro[indene-2,5'-indeno[2,1-a]fluorene-6',2''-indene]-1,1'',3,3'',11',12'-hexaone, (I) (Fig. 1). Subsequently, we found that heating compound (III) in refluxing dilute aqueous hydrochloric acid gave compound (I) in modest, but still useful, yield. The formation of (I) from the indanetrione (III) must involve an oxidative process; the identity of the oxidant has not yet been investigated but plausible mechanisms for the conversion of (III) to (I) in aqueous or ethanolic solutions are not easy to envisage. Here, we report the molecular and supramolecular structure of (I) and briefly compare its supramolecular aggregation with that in some simpler analogues, (II)–(V) (see scheme).

The molecule of (I) exhibits approximate but noncrystallographic twofold rotation symmetry about the line joining the mid-points of the C11—C21 and C31—C41 bonds, as illustrated by the leading torsion angles (Table 1). Within the central ring, the C11—C17 and C21—C27 bonds are both clearly double bonds, while the C31—C41 bond is long, presumably as a consequence of the steric congestion around atoms C31 and C41. Unlike all the other rings in the molecule, the central ring is not planar, as exemplified by the C17—C31—C41—C27 torsion angle. The ring-puckering angles (Cremer & Pople, 1975) for the atom-sequence C11/C17/C31/C41/C27/C21 are θ = 119.3 (3)° and ϕ = 330.2 (4)°, with Q = 0.315 (2) Å, indicating a ring conformation intermediate between half-chair and screw-boat. The ring-puckering may be ascribed to the substitution at atoms C31 and C41. The remaining bond distances and inter-bond angles show no unusual features.

There are six independent C—H.·O hydrogen bonds in the crystal structure of (I), such that each molecule acts as both a sixfold donor and a sixfold acceptor of hydrogen bonds. The resulting aggregation is three-dimensional but it can readily be analysed in terms of four independent one-dimensional substructures. Three of these are very simple, involving only a single hydrogen bond in each substructure, while the fourth substructure is more complex, with three hydrogen bonds involved in its formation.

Atoms C35 and C43 in the molecule at (x, y, z) act as hydrogen-bond donors to, respectively, atom O47 at (-1/2 + x, 1/2 - y, -1/2 + z) and atom O12 at (1/2 + x, 1/2 - y, -1/2 + z), thereby forming a C(9) (Bernstein et al., 1995) chain parallel to the [101] direction and a C(10) chain parallel to the [101] direction, both built from molecules related by the n-glide plane at y = 1/4. In addition, atom C46 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O22 in the molecule at (3/2 - x, 1/2 + y, 3/2 - z), so forming a second C(9) chain, this time running parallel to the [010] direction and comprising molecules related by the 2₁ screw axis along (3/4, y, 3/4). These three chains, along [010], [101] and [101], respectively, would in fact suffice to generate a continuous three-dimensional framework.

The more complex motif involves three hydrogen bonds. Atoms C15 and C25 in the molecule at (x, y, z) act as hydrogen-bond donors to, respectively, atom O32 in the molecule at (-1 + x, y, z) and atom O47 in the molecule at (1 + x, y, z). The resulting pair of antiparallel chains generated by translation along [100] combine to form a C(8)C(8)[R²₂(18)] chain of rings. The final hydrogen bond links pairs of these chains into a complex tubular substructure. Atom C45 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O37 in the molecule at (1 - x, 1 - y, 1 - z), so forming a complex chain containing three types of ring. In addition to the R²₂(18) rings generated by translation, there are two types of ring generated by inversion, such that R²₂(18) rings centred at (n + 1/2, 1/2, 1/2), where n represents zero or an integer, alternate with R⁴₄(30) rings centred at (n, 1/2, 1/2), where n represents zero or an integer (Fig. 2).

It is of interest to compare briefly the supramolecular aggregation in the crystal structure of (I) with that of some close analogues, namely compound (II), and compounds (III)–(V), which are all notionally derived from (II) by condensation and/or oxidation. The original reports of compounds (II)–(V) were all concerned with proof of constitution, without discussion of any hydrogen bonding.

The crystal structure of compound (III) [Cambridge Structural Database (CSD; Allen, 2002) refcode BIINDO; Bravic, Bravic et al., 1976], which is a condensation product from the dione, (I), contains a single intermolecular C—H···O hydrogen bond which links molecules related by a 2₁ screw axis into simple C(4) chains.

Compound (IV) (CSD refcode WEVSUL; Khodorkovsky et al., 1994) is formally an oxidation product of (II) (Kaufmann, 1897), although most reported preparations involving oxidation of (II) are not readily reproducible (Khodorkovsky et al., 1994). The crystal structure of (IV) again contains a single intermolecular C—H···O hydrogen bond which links molecules related by a glide plane into C(6) chains.

By contrast, a single C—H···O hydrogen bond in compound (II) (CSD refcode INDDON; Bravic, Bechtel et al., 1976) links molecules related by a 4 axis into R⁴₃(20) tetramers (Fig. 3).

In compound (V) (CSD refcode KETROR; Ji et al., 2006), which was obtained as an unexpected oxidation product during the attempted nitration of (IV), the molecules lie across twofold rotation axes in space group C2/c, and a single C—H···O hydrogen bond links molecules related by translation along this axis into columns of R²₂(11) rings (Fig. 4).

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1995); Bravic, Bechtel, Gaultier & Hauw (1976); Bravic, Bravic, Gaultier & Hauw (1976); Cremer & Pople (1975); Długosz (1995); Ji et al. (2006); Kaufmann (1897); Khodorkovsky et al. (1994); Lueddens & Korpi (2007); Pozharskii et al. (1997).

S2. Experimental

A mixture of 2,5,6-triaminopyrimidin-4(3H)-one (1.1 mmol) and 1,2'-biindene-1',3,3'(2H)-trione (1.1 mmol) in dry ethanol (10 ml) was heated under reflux with magnetic stirring for 5 h, while the progress of the reaction was monitored by thin-layer chromatography. The reaction mixture was then cooled to ambient temperature, and the resulting precipitate was collected by filtration and washed with ethanol yielding 3-[(2,4-diamino-6-oxo-1,6-dihydropyrimidin-5-yl)amino]-1,2'-biindene-1',3'-dione as a violet solid (m.p. 561–563 K, yield 90%), from which crystals suitable for single-crystal X-ray diffraction have not yet been obtained. The resulting filtrate was evaporated to dryness and the solid residue was crystallized from a mixture of dimethylformamide and ethanol (1:10 v/v) to yield violet crystals of the title compound, (I) (m.p. 616 K), which proved to be suitable for single-crystal X-ray diffraction. When a solution of (III) in an excess of dilute (10%) aqueous hydrochloric acid was heated under reflux for 18 h, compound (I) was produced in 22% yield.

S3. Refinement

The space group P2₁/n was uniquely assigned from the systematic absences. All H atoms were located in a difference map and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C).

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 (Sheldrick, 2008) 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. A stereoview of part of the crystal structure of (I), showing the formation of a complex chain of rings along [100]. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
	Fig. 3. A stereoview of part of the crystal structure of (II), showing the formation of an R^44(20) [Should this be R^43(20) as in Comment?] [tetramer? (text missing)] around a 4 axis. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
	Fig. 4. A stereoview of part of the crystal structure of (V), showing the formation of a column of R^22(11) rings along a twofold rotation axis. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Dispiro[indene-2,5'-indeno[2,1-a]fluorene-6',2''-indene]- 1,1'',3,3'',11',12'-hexaone

Crystal data

C36H16O6	F(000) = 1120
Mr = 544.49	Dx = 1.456 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 55752 reflections
a = 8.2209 (11) Å	θ = 3.1–27.5°
b = 16.552 (3) Å	µ = 0.10 mm^−1
c = 18.423 (3) Å	T = 120 K
β = 97.775 (19)°	Needle, violet
V = 2483.8 (7) Å^3	0.51 × 0.28 × 0.10 mm
Z = 4

Data collection

Bruker Nonius KappaCCD diffractometer	5702 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	4483 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ϕ and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −21→21
Tmin = 0.958, Tmax = 0.990	l = −23→23
55752 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0281P)^2 + 1.8424P] where P = (Fo^2 + 2Fc^2)/3
5702 reflections	(Δ/σ)max < 0.001
379 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

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

	x	y	z	Uiso*/Ueq
O12	0.54398 (17)	0.08532 (9)	0.81835 (7)	0.0438 (3)
O22	0.90296 (17)	0.12060 (8)	0.82627 (7)	0.0410 (3)
O32	0.68268 (14)	0.06315 (7)	0.54259 (7)	0.0309 (3)
O37	0.34195 (15)	0.29388 (7)	0.53928 (6)	0.0309 (3)
O42	0.85081 (17)	0.21691 (8)	0.49159 (7)	0.0387 (3)
O47	0.58783 (14)	0.35327 (7)	0.66940 (6)	0.0297 (3)
C11	0.5942 (2)	0.14293 (9)	0.70187 (9)	0.0244 (3)
C12	0.5007 (2)	0.09946 (10)	0.75441 (9)	0.0291 (4)
C12A	0.3389 (2)	0.07959 (10)	0.71099 (10)	0.0290 (4)
C13	0.2107 (2)	0.03504 (11)	0.73099 (12)	0.0374 (4)
C14	0.0742 (2)	0.02286 (12)	0.67859 (13)	0.0420 (5)
C15	0.0683 (2)	0.05562 (11)	0.60996 (12)	0.0395 (5)
C16	0.1976 (2)	0.10180 (11)	0.58971 (11)	0.0336 (4)
C16A	0.3342 (2)	0.11299 (9)	0.64090 (10)	0.0259 (3)
C17	0.4939 (2)	0.15333 (9)	0.63809 (9)	0.0238 (3)
C21	0.7600 (2)	0.17309 (10)	0.71092 (9)	0.0243 (3)
C22	0.8975 (2)	0.16426 (11)	0.77355 (9)	0.0289 (4)
C22A	1.0285 (2)	0.21983 (10)	0.75535 (9)	0.0285 (4)
C23	1.1741 (2)	0.24119 (12)	0.79699 (11)	0.0366 (4)
C24	1.2740 (2)	0.29649 (12)	0.76746 (12)	0.0396 (5)
C25	1.2291 (2)	0.32759 (11)	0.69832 (11)	0.0364 (4)
C26	1.0810 (2)	0.30604 (11)	0.65629 (10)	0.0305 (4)
C26A	0.9800 (2)	0.25246 (10)	0.68586 (9)	0.0249 (3)
C27	0.81347 (19)	0.22107 (9)	0.65968 (9)	0.0228 (3)
C31	0.55217 (19)	0.19108 (9)	0.57235 (8)	0.0223 (3)
C32	0.5963 (2)	0.11947 (10)	0.52207 (9)	0.0245 (3)
C32A	0.4968 (2)	0.12966 (10)	0.44945 (9)	0.0262 (3)
C33	0.4966 (2)	0.08225 (11)	0.38748 (10)	0.0326 (4)
C34	0.3800 (3)	0.09873 (12)	0.32823 (10)	0.0370 (4)
C35	0.2664 (2)	0.16080 (12)	0.33046 (10)	0.0366 (4)
C36	0.2686 (2)	0.20951 (11)	0.39144 (9)	0.0321 (4)
C36A	0.3870 (2)	0.19318 (10)	0.45083 (9)	0.0264 (3)
C37	0.4136 (2)	0.23484 (10)	0.52183 (9)	0.0241 (3)
C41	0.70076 (19)	0.25015 (9)	0.59373 (8)	0.0217 (3)
C42	0.7876 (2)	0.26754 (10)	0.52546 (9)	0.0264 (3)
C42A	0.7765 (2)	0.35463 (10)	0.50979 (9)	0.0273 (4)
C43	0.8413 (2)	0.39652 (12)	0.45498 (10)	0.0361 (4)
C44	0.8213 (3)	0.47912 (12)	0.45293 (11)	0.0427 (5)
C45	0.7433 (2)	0.51889 (12)	0.50419 (12)	0.0441 (5)
C46	0.6799 (2)	0.47796 (11)	0.55979 (11)	0.0362 (4)
C46A	0.6960 (2)	0.39443 (10)	0.56108 (9)	0.0268 (4)
C47	0.6466 (2)	0.33715 (10)	0.61488 (8)	0.0240 (3)
H13	0.2153	0.0133	0.7790	0.045*
H14	−0.0155	−0.0084	0.6905	0.050*
H15	−0.0262	0.0467	0.5751	0.047*
H16	0.1913	0.1247	0.5421	0.040*
H23	1.2051	0.2188	0.8443	0.044*
H24	1.3744	0.3130	0.7952	0.048*
H25	1.3004	0.3645	0.6788	0.044*
H26	1.0508	0.3278	0.6086	0.037*
H33	0.5741	0.0399	0.3858	0.039*
H34	0.3770	0.0671	0.2850	0.044*
H35	0.1857	0.1698	0.2892	0.044*
H36	0.1923	0.2524	0.3927	0.039*
H43	0.8972	0.3693	0.4203	0.043*
H44	0.8622	0.5093	0.4154	0.051*
H45	0.7326	0.5760	0.5013	0.053*
H46	0.6278	0.5058	0.5954	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O12	0.0439 (8)	0.0595 (9)	0.0297 (7)	0.0003 (7)	0.0111 (6)	0.0146 (6)
O22	0.0423 (8)	0.0443 (8)	0.0344 (7)	0.0038 (6)	−0.0019 (6)	0.0164 (6)
O32	0.0297 (6)	0.0223 (6)	0.0399 (7)	0.0050 (5)	0.0017 (5)	0.0017 (5)
O37	0.0356 (7)	0.0251 (6)	0.0303 (6)	0.0082 (5)	−0.0013 (5)	−0.0006 (5)
O42	0.0528 (8)	0.0312 (7)	0.0365 (7)	−0.0053 (6)	0.0215 (6)	−0.0079 (6)
O47	0.0301 (6)	0.0349 (7)	0.0239 (6)	0.0049 (5)	0.0025 (5)	−0.0048 (5)
C11	0.0266 (8)	0.0218 (8)	0.0254 (8)	0.0031 (6)	0.0057 (6)	0.0044 (6)
C12	0.0308 (9)	0.0273 (9)	0.0312 (9)	0.0044 (7)	0.0111 (7)	0.0050 (7)
C12A	0.0285 (9)	0.0225 (8)	0.0381 (10)	0.0031 (7)	0.0122 (7)	0.0008 (7)
C13	0.0378 (10)	0.0276 (9)	0.0503 (12)	−0.0018 (8)	0.0186 (9)	0.0033 (8)
C14	0.0313 (10)	0.0300 (10)	0.0682 (14)	−0.0046 (8)	0.0197 (10)	−0.0036 (9)
C15	0.0253 (9)	0.0303 (10)	0.0627 (13)	−0.0008 (7)	0.0050 (9)	−0.0061 (9)
C16	0.0284 (9)	0.0277 (9)	0.0448 (11)	0.0025 (7)	0.0050 (8)	0.0005 (8)
C16A	0.0232 (8)	0.0194 (8)	0.0362 (9)	0.0028 (6)	0.0079 (7)	0.0000 (7)
C17	0.0241 (8)	0.0195 (7)	0.0282 (8)	0.0028 (6)	0.0051 (6)	0.0024 (6)
C21	0.0259 (8)	0.0225 (8)	0.0245 (8)	0.0048 (6)	0.0027 (6)	0.0026 (6)
C22	0.0294 (9)	0.0294 (9)	0.0274 (9)	0.0065 (7)	0.0014 (7)	0.0032 (7)
C22A	0.0264 (8)	0.0279 (9)	0.0304 (9)	0.0058 (7)	0.0012 (7)	−0.0005 (7)
C23	0.0302 (9)	0.0377 (10)	0.0392 (10)	0.0079 (8)	−0.0054 (8)	−0.0002 (8)
C24	0.0239 (9)	0.0374 (10)	0.0549 (12)	0.0008 (8)	−0.0043 (8)	−0.0067 (9)
C25	0.0266 (9)	0.0302 (10)	0.0529 (12)	−0.0020 (7)	0.0071 (8)	−0.0047 (8)
C26	0.0278 (9)	0.0280 (9)	0.0362 (9)	0.0002 (7)	0.0067 (7)	−0.0018 (7)
C26A	0.0229 (8)	0.0231 (8)	0.0288 (8)	0.0037 (6)	0.0033 (6)	−0.0033 (7)
C27	0.0228 (8)	0.0219 (8)	0.0240 (8)	0.0027 (6)	0.0037 (6)	−0.0007 (6)
C31	0.0244 (8)	0.0201 (7)	0.0217 (8)	0.0022 (6)	0.0003 (6)	0.0013 (6)
C32	0.0247 (8)	0.0209 (8)	0.0281 (8)	−0.0021 (6)	0.0039 (6)	0.0005 (6)
C32A	0.0299 (9)	0.0210 (8)	0.0276 (8)	−0.0031 (7)	0.0037 (7)	0.0007 (6)
C33	0.0440 (10)	0.0234 (9)	0.0311 (9)	−0.0032 (8)	0.0080 (8)	−0.0031 (7)
C34	0.0525 (12)	0.0334 (10)	0.0250 (9)	−0.0097 (9)	0.0051 (8)	−0.0051 (7)
C35	0.0419 (11)	0.0408 (11)	0.0252 (9)	−0.0064 (9)	−0.0026 (8)	0.0025 (8)
C36	0.0350 (10)	0.0331 (9)	0.0270 (9)	0.0015 (8)	−0.0004 (7)	0.0042 (7)
C36A	0.0309 (9)	0.0237 (8)	0.0242 (8)	−0.0012 (7)	0.0021 (7)	0.0023 (6)
C37	0.0257 (8)	0.0214 (8)	0.0246 (8)	0.0009 (6)	0.0013 (6)	0.0031 (6)
C41	0.0257 (8)	0.0193 (7)	0.0204 (7)	0.0005 (6)	0.0036 (6)	0.0012 (6)
C42	0.0310 (9)	0.0258 (8)	0.0225 (8)	−0.0053 (7)	0.0041 (7)	−0.0016 (6)
C42A	0.0341 (9)	0.0266 (8)	0.0198 (8)	−0.0070 (7)	−0.0020 (7)	0.0015 (6)
C43	0.0449 (11)	0.0363 (10)	0.0254 (9)	−0.0154 (8)	−0.0009 (8)	0.0045 (7)
C44	0.0487 (12)	0.0401 (11)	0.0360 (10)	−0.0146 (9)	−0.0060 (9)	0.0141 (9)
C45	0.0415 (11)	0.0238 (9)	0.0619 (14)	−0.0060 (8)	−0.0115 (10)	0.0155 (9)
C46	0.0355 (10)	0.0240 (9)	0.0455 (11)	0.0023 (7)	−0.0077 (8)	−0.0003 (8)
C46A	0.0278 (8)	0.0234 (8)	0.0267 (8)	−0.0020 (7)	−0.0060 (7)	0.0020 (7)
C47	0.0253 (8)	0.0246 (8)	0.0205 (8)	0.0025 (6)	−0.0031 (6)	−0.0015 (6)

Geometric parameters (Å, º)

O12—C12	1.207 (2)	C25—C26	1.399 (3)
O22—C22	1.207 (2)	C25—H25	0.9500
O32—C32	1.2014 (19)	C26—C26A	1.376 (2)
O37—C37	1.207 (2)	C26—H26	0.9500
O42—C42	1.204 (2)	C26A—C27	1.483 (2)
O47—C47	1.2021 (19)	C31—C37	1.550 (2)
C11—C21	1.440 (2)	C31—C32	1.577 (2)
C11—C17	1.352 (2)	C32—C32A	1.480 (2)
C17—C31	1.498 (2)	C32A—C33	1.385 (2)
C31—C41	1.573 (2)	C32A—C36A	1.388 (2)
C21—C27	1.352 (2)	C33—C34	1.379 (3)
C27—C41	1.504 (2)	C33—H33	0.9500
C11—C12	1.499 (2)	C34—C35	1.393 (3)
C12—C12A	1.493 (3)	C34—H34	0.9500
C12A—C13	1.376 (2)	C35—C36	1.381 (3)
C12A—C16A	1.400 (2)	C35—H35	0.9500
C13—C14	1.393 (3)	C36—C36A	1.389 (2)
C13—H13	0.9500	C36—H36	0.9500
C14—C15	1.370 (3)	C36A—C37	1.469 (2)
C14—H14	0.9500	C41—C42	1.555 (2)
C15—C16	1.400 (3)	C41—C47	1.572 (2)
C15—H15	0.9500	C42—C42A	1.470 (2)
C16—C16A	1.378 (2)	C42A—C43	1.389 (2)
C16—H16	0.9500	C42A—C46A	1.391 (2)
C16A—C17	1.480 (2)	C43—C44	1.377 (3)
C21—C22	1.509 (2)	C43—H43	0.9500
C22—C22A	1.489 (2)	C44—C45	1.379 (3)
C22A—C23	1.377 (2)	C44—H44	0.9500
C22A—C26A	1.397 (2)	C45—C46	1.387 (3)
C23—C24	1.389 (3)	C45—H45	0.9500
C23—H23	0.9500	C46—C46A	1.389 (2)
C24—C25	1.377 (3)	C46—H46	0.9500
C24—H24	0.9500	C46A—C47	1.468 (2)
C17—C11—C21	120.84 (15)	C17—C31—C32	106.60 (13)
C17—C11—C12	108.48 (14)	C37—C31—C32	101.98 (12)
C21—C11—C12	130.67 (15)	C41—C31—C32	112.45 (13)
O12—C12—C12A	127.16 (16)	O32—C32—C32A	127.14 (15)
O12—C12—C11	127.90 (17)	O32—C32—C31	124.86 (15)
C12A—C12—C11	104.90 (14)	C32A—C32—C31	107.59 (13)
C13—C12A—C16A	122.12 (17)	C33—C32A—C36A	121.07 (16)
C13—C12A—C12	129.28 (17)	C33—C32A—C32	128.24 (16)
C16A—C12A—C12	108.58 (14)	C36A—C32A—C32	110.55 (14)
C12A—C13—C14	117.78 (19)	C34—C33—C32A	117.59 (17)
C12A—C13—H13	121.1	C34—C33—H33	121.2
C14—C13—H13	121.1	C32A—C33—H33	121.2
C15—C14—C13	120.46 (18)	C33—C34—C35	121.31 (17)
C15—C14—H14	119.8	C33—C34—H34	119.3
C13—C14—H14	119.8	C35—C34—H34	119.3
C14—C15—C16	121.91 (19)	C36—C35—C34	121.30 (17)
C14—C15—H15	119.0	C36—C35—H35	119.3
C16—C15—H15	119.0	C34—C35—H35	119.3
C16A—C16—C15	117.94 (18)	C35—C36—C36A	117.26 (17)
C16A—C16—H16	121.0	C35—C36—H36	121.4
C15—C16—H16	121.0	C36A—C36—H36	121.4
C16—C16A—C12A	119.77 (16)	C32A—C36A—C36	121.40 (16)
C16—C16A—C17	132.95 (16)	C32A—C36A—C37	110.69 (14)
C12A—C16A—C17	107.24 (15)	C36—C36A—C37	127.89 (16)
C11—C17—C16A	110.58 (14)	O37—C37—C36A	126.76 (15)
C11—C17—C31	122.14 (14)	O37—C37—C31	124.33 (15)
C16A—C17—C31	126.77 (14)	C36A—C37—C31	108.91 (13)
C27—C21—C11	121.00 (14)	C27—C41—C42	114.37 (13)
C27—C21—C22	108.06 (14)	C27—C41—C47	104.90 (12)
C11—C21—C22	130.87 (15)	C42—C41—C47	101.96 (12)
O22—C22—C22A	127.00 (16)	C27—C41—C31	112.10 (13)
O22—C22—C21	128.03 (17)	C42—C41—C31	109.79 (12)
C22A—C22—C21	104.95 (14)	C47—C41—C31	113.29 (13)
C23—C22A—C26A	122.01 (17)	O42—C42—C42A	126.88 (16)
C23—C22A—C22	129.33 (17)	O42—C42—C41	124.61 (15)
C26A—C22A—C22	108.64 (15)	C42A—C42—C41	108.51 (14)
C22A—C23—C24	117.80 (18)	C43—C42A—C46A	121.46 (17)
C22A—C23—H23	121.1	C43—C42A—C42	127.77 (17)
C24—C23—H23	121.1	C46A—C42A—C42	110.70 (14)
C25—C24—C23	120.65 (17)	C44—C43—C42A	117.36 (19)
C25—C24—H24	119.7	C44—C43—H43	121.3
C23—C24—H24	119.7	C42A—C43—H43	121.3
C24—C25—C26	121.41 (18)	C43—C44—C45	121.34 (18)
C24—C25—H25	119.3	C43—C44—H44	119.3
C26—C25—H25	119.3	C45—C44—H44	119.3
C26A—C26—C25	118.16 (17)	C44—C45—C46	121.92 (18)
C26A—C26—H26	120.9	C44—C45—H45	119.0
C25—C26—H26	120.9	C46—C45—H45	119.0
C26—C26A—C22A	119.95 (16)	C45—C46—C46A	117.01 (19)
C26—C26A—C27	132.58 (16)	C45—C46—H46	121.5
C22A—C26A—C27	107.41 (14)	C46A—C46—H46	121.5
C21—C27—C26A	110.61 (14)	C46—C46A—C42A	120.88 (17)
C21—C27—C41	121.94 (14)	C46—C46A—C47	128.31 (17)
C26A—C27—C41	126.27 (14)	C42A—C46A—C47	110.69 (14)
C17—C31—C37	113.02 (13)	O47—C47—C46A	126.87 (15)
C17—C31—C41	112.28 (13)	O47—C47—C41	124.74 (15)
C37—C31—C41	110.06 (12)	C46A—C47—C41	108.11 (13)
C17—C11—C12—O12	−173.32 (18)	C17—C31—C32—C32A	122.72 (14)
C21—C11—C12—O12	5.5 (3)	C37—C31—C32—C32A	4.01 (16)
C17—C11—C12—C12A	4.85 (18)	C41—C31—C32—C32A	−113.83 (14)
C21—C11—C12—C12A	−176.36 (16)	O32—C32—C32A—C33	−8.5 (3)
O12—C12—C12A—C13	−6.8 (3)	C31—C32—C32A—C33	178.60 (16)
C11—C12—C12A—C13	175.03 (17)	O32—C32—C32A—C36A	167.24 (17)
O12—C12—C12A—C16A	174.69 (18)	C31—C32—C32A—C36A	−5.64 (18)
C11—C12—C12A—C16A	−3.51 (18)	C36A—C32A—C33—C34	−2.2 (3)
C16A—C12A—C13—C14	0.8 (3)	C32—C32A—C33—C34	173.18 (17)
C12—C12A—C13—C14	−177.60 (17)	C32A—C33—C34—C35	0.1 (3)
C12A—C13—C14—C15	−1.0 (3)	C33—C34—C35—C36	1.6 (3)
C13—C14—C15—C16	0.3 (3)	C34—C35—C36—C36A	−1.0 (3)
C14—C15—C16—C16A	0.8 (3)	C33—C32A—C36A—C36	2.8 (3)
C15—C16—C16A—C12A	−1.0 (2)	C32—C32A—C36A—C36	−173.36 (16)
C15—C16—C16A—C17	176.22 (17)	C33—C32A—C36A—C37	−178.99 (15)
C13—C12A—C16A—C16	0.3 (3)	C32—C32A—C36A—C37	4.90 (19)
C12—C12A—C16A—C16	178.94 (15)	C35—C36—C36A—C32A	−1.1 (3)
C13—C12A—C16A—C17	−177.62 (16)	C35—C36—C36A—C37	−179.01 (17)
C12—C12A—C16A—C17	1.04 (18)	C32A—C36A—C37—O37	177.37 (17)
C21—C11—C17—C16A	176.67 (14)	C36—C36A—C37—O37	−4.5 (3)
C12—C11—C17—C16A	−4.41 (18)	C32A—C36A—C37—C31	−2.11 (19)
C12—C11—C17—C31	−176.72 (14)	C36—C36A—C37—C31	176.00 (17)
C16—C16A—C17—C11	−175.34 (18)	C17—C31—C37—O37	65.2 (2)
C12A—C16A—C17—C11	2.17 (19)	C41—C31—C37—O37	−61.2 (2)
C16—C16A—C17—C31	−3.5 (3)	C32—C31—C37—O37	179.22 (16)
C12A—C16A—C17—C31	174.03 (15)	C17—C31—C37—C36A	−115.32 (15)
C17—C11—C21—C27	8.3 (2)	C41—C31—C37—C36A	118.26 (14)
C11—C21—C27—C41	4.4 (2)	C32—C31—C37—C36A	−1.28 (16)
C21—C27—C41—C31	−26.4 (2)	C26A—C27—C41—C42	41.4 (2)
C11—C17—C31—C32	97.2 (2)	C21—C27—C41—C47	96.96 (17)
C11—C17—C31—C37	−151.6 (2)	C26A—C27—C41—C47	−69.43 (19)
C17—C31—C41—C27	35.27 (18)	C21—C27—C41—C31	−26.4 (2)
C21—C11—C17—C31	4.4 (2)	C26A—C27—C41—C31	167.24 (14)
C11—C17—C31—C41	−26.4 (2)	C37—C31—C41—C27	162.10 (13)
C21—C27—C41—C47	97.0 (2)	C32—C31—C41—C27	−84.96 (15)
C21—C27—C41—C42	−152.19 (15)	C17—C31—C41—C42	163.54 (13)
C12—C11—C21—C27	−170.36 (16)	C37—C31—C41—C42	−69.63 (16)
C17—C11—C21—C22	−175.11 (16)	C32—C31—C41—C42	43.32 (17)
C12—C11—C21—C22	6.2 (3)	C17—C31—C41—C47	−83.21 (16)
C27—C21—C22—O22	−172.64 (18)	C37—C31—C41—C47	43.62 (17)
C11—C21—C22—O22	10.4 (3)	C32—C31—C41—C47	156.56 (12)
C27—C21—C22—C22A	5.86 (18)	C27—C41—C42—O42	66.4 (2)
C11—C21—C22—C22A	−171.07 (16)	C47—C41—C42—O42	179.00 (16)
O22—C22—C22A—C23	−8.4 (3)	C31—C41—C42—O42	−60.6 (2)
C21—C22—C22A—C23	173.10 (18)	C27—C41—C42—C42A	−114.36 (15)
O22—C22—C22A—C26A	173.50 (18)	C47—C41—C42—C42A	−1.76 (16)
C21—C22—C22A—C26A	−5.01 (18)	C31—C41—C42—C42A	118.62 (14)
C26A—C22A—C23—C24	−0.5 (3)	O42—C42—C42A—C43	−2.6 (3)
C22—C22A—C23—C24	−178.40 (17)	C41—C42—C42A—C43	178.14 (16)
C22A—C23—C24—C25	−1.0 (3)	O42—C42—C42A—C46A	−179.50 (17)
C23—C24—C25—C26	1.3 (3)	C41—C42—C42A—C46A	1.28 (19)
C24—C25—C26—C26A	0.0 (3)	C46A—C42A—C43—C44	−0.6 (3)
C25—C26—C26A—C22A	−1.4 (2)	C42—C42A—C43—C44	−177.18 (17)
C25—C26—C26A—C27	175.41 (17)	C42A—C43—C44—C45	1.4 (3)
C23—C22A—C26A—C26	1.8 (3)	C43—C44—C45—C46	−0.6 (3)
C22—C22A—C26A—C26	−179.95 (15)	C44—C45—C46—C46A	−1.0 (3)
C23—C22A—C26A—C27	−175.81 (16)	C45—C46—C46A—C42A	1.8 (3)
C22—C22A—C26A—C27	2.46 (18)	C45—C46—C46A—C47	177.30 (16)
C11—C21—C27—C26A	172.72 (14)	C43—C42A—C46A—C46	−1.0 (3)
C22—C21—C27—C26A	−4.57 (18)	C42—C42A—C46A—C46	176.12 (15)
C22—C21—C27—C41	−172.87 (14)	C43—C42A—C46A—C47	−177.24 (15)
C26—C26A—C27—C21	−175.76 (18)	C42—C42A—C46A—C47	−0.15 (19)
C22A—C26A—C27—C21	1.39 (19)	C46—C46A—C47—O47	−2.8 (3)
C26—C26A—C27—C41	−8.1 (3)	C42A—C46A—C47—O47	173.10 (16)
C22A—C26A—C27—C41	169.07 (15)	C46—C46A—C47—C41	−176.94 (17)
C16A—C17—C31—C37	37.4 (2)	C42A—C46A—C47—C41	−1.03 (18)
C11—C17—C31—C41	−26.4 (2)	C27—C41—C47—O47	−53.1 (2)
C16A—C17—C31—C41	162.61 (14)	C42—C41—C47—O47	−172.61 (15)
C16A—C17—C31—C32	−73.84 (19)	C31—C41—C47—O47	69.5 (2)
C17—C31—C32—O32	−50.4 (2)	C27—C41—C47—C46A	121.19 (14)
C37—C31—C32—O32	−169.07 (16)	C42—C41—C47—C46A	1.67 (16)
C41—C31—C32—O32	73.1 (2)	C31—C41—C47—C46A	−116.24 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O32^i	0.95	2.40	3.247 (2)	148
C25—H25···O47^ii	0.95	2.40	3.096 (2)	130
C35—H35···O47^iii	0.95	2.28	3.136 (2)	150
C43—H43···O12^iv	0.95	2.48	3.215 (2)	134
C45—H45···O37^v	0.95	2.33	3.253 (2)	163
C46—H46···O22^vi	0.95	2.42	3.291 (2)	152

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