Chains of edge-fused hydrogen-bonded R₃³(22) rings in 5,3'-dihydr­oxy-3,6,7,4',5'-penta­methoxy­flavone

The title compound [systematic name: 5-hydroxy-2-(3-hydroxy-4,5-dimethoxy­phenyl)-3,6,7-trimethoxy-4H-chromen-4-one], C₂₀H₂₀O₉, was isolated from the seeds of Cleom viscosa Linn. Two independent mol­ecules (A and B) are present in the asymmetric unit with almost similar conformations. The dihedral angles between the fused chromene ring system and the benzene ring bonded to it in mol­ecules A and B are 4.2 (1) and 12.7 (1)°, respectively. The hydroxy O atoms are involved in intra­molecular hydrogen bonding. The mol­ecules are linked by C-H...O and O-H...O inter­actions into chains of edge-fused R₃³(22) rings. Aromatic [pi]-[pi] and weak C-H...[pi](arene) inter­actions are also observed.

S1. Comment

Cleome viscosa Linn (Capparaceae) is a bushy and sticky aromatic herb with secretory glandular trichomes (Adams, 1972). This widely distributed herb may have derived from the glandular trichomes [Meaning of sentence not clear - please rephrase]. The ethanolic extracts of the leaves, flowers and stem of this plant have been tested for anti-microbial (Sudhakar et al., 2006), insecticidal and nemeticidal (Williams et al., 2003) activities. The seeds of this plant are said to be anthelmintic and useful in fever, diarrhoea and infantile cunvulsions (Asolkar et al., 1992). As the whole plant, it is useful in treating liver diseases, chronic painful joints and mental disorders (Chatterjee & Pakrashi, 1991). Furthermore, C. Viscosa Linn. has also been studied for its psychopharmacological effects in rat and mouse models (Parimala et al., 2004). In view of the above important properties, the extract of the seeds of this plant has been studied and a number of compounds have been isolated (Mahender, 2006). The title compound, (I), is one of these, and we report its structure here.

In compound (I), two independent molecules, A and B, are present in the asymmetric unit with similar conformations (Fig. 1). The bond lengths and angles show normal values and are comparable with those observed in 5,3'-dihydroxy-3,7,4',5'-tetramethoxyflavone (Etti et al., 2005) and calycopterin (Vijayalakshmi et al., 1986). The geometric parameters in the main skeletons of molecules A and B show no significant differences, but they are distinguished by some bond rotations (Table 1). The dihedral angles between the chromene ring system (C1n–C9n/O1n, n = A or B) and the benzene ring (C13n–C18n) are 4.2 (1) and 12.7 (1)° for molecules A and B, respectively. We understand from the literature (Krishnaiah et al., 2005) that there is a correlation (directly proportional) between the dihedral angle between the benzene ring and the chromene ring system and the C—C bond length joining them. However, this may not necessarily be true, because in (I) the bond length (C8n—C13n) is approximately the same in the two molecules [1.475 (2) Å in A and 1.472 (2) Å in B], despite them having different dihedral angles. Furthermore, Wallet and co-workers (Wallet et al., 1988, 1990; Cody, 1988) reported that there is no relationship between the dihedral angle and the bond distance. The double bonds (C1n—O2n) and the multiple-character bonds (C8n—C9n), which are generally responsible for the photoactivity of coumarins (Song & Gordon, 1970), are confirmed by their respective distances (Table 1). Similarly, the C7n—O1n and C8n—O1n bonds (Table 1) exhibit variation in their distances, a feature quite common in furano compounds and simple coumarins (Rajnikanth et al., 1993; Gupta et al., 1993).

In contrast, some relatively large conformational differences are found in the methoxy substituents. With respect to the chromene ring system, the methoxy substituents at C4n, C5n and C9n make angles of 70.7 (1), 6.3 (1) and 72.9 (1)°, respectively, in molecule A, and 89.5 (2), 3.4 (1), and 80.5 (2)°, respectively, in molecule B. With respect to the benzene ring, the methoxy groups at positions C15n and C16n make angles of 4.7 (1) and 74.5 (1)°, respectively, in A, and 14.8 (1) and 89.8 (1)°, respectively, in B.

Within the asymmetric unit, hydroxy atom O9B attached to the benzene ring acts as hydrogen-bond donor, via atom H9B, to ketone atom O2A attached to the chromene ring system (Fig. 2). In both molecules, the hydroxy atom O3n is involved in an intramolecular hydrogen bond with the adjacent ketone O atom, forming a six-membered pseudo-ring (O2n/C1n/C2n/C3n/O3n/H3n) with an S(6) pattern (Bernstein et al., 1995). Similarly, in molecule A, hydroxy atom O9A is involved in an intramolecular hydrogen bond with methoxy atom O8A, which completes a five-membered pseudo-ring (O8A/C16A/C17A/O9A/H9A) with an S(5) pattern. Similar interactions have been reported in the literature (Smith et al., 2001). Interestingly, the latter interaction is absent in molecule B.

Molecules A in (I) are linked into chains by the co-operative action of a C—H···O hydrogen bond of moderate strength (Table 2). Methyl atom C10A at (x, y, z) acts as hydrogen-bond donor to the methoxy atom O7A at (1 + x, y − 1, z), so forming a C(13) chain (Bernstein et al., 1995) running along the [110] direction (Fig. 2). Each molecule B is linked to two molecules A through O—H···O and C—H···O interactions. The combination of these A and B molecules then generates edge-fused R³₃(22) rings. Interestingly, only molecules A are involved in aromatic π–π stacking interactions along the a axis. The pyrone rings in the fused chromene ring system are stacked with a centre-to-centre distance of 3.556 Å. In addition, the pyrone ring and the C13A–C18A benzene ring (centroid-to-centroid distance 3.742 Å), and the six-membered C2A–C7A ring in the chromene ring system and the C13A–C18A benzene ring (centroid-to-centroid distance 3.764 Å) are also involved in similar interactions. The structure is further stabilized by weak C—H···π interations (Table 2).

S2. Experimental

The dried and ground seeds of Cleome viscosa Linn. (4 kg) were soaked in CHCl₃:MeOH (1:1) (8 l) for two weeks. The crude extract was suspended in hexane–ethyl acetate (9:1) and then fractionated by silica-gel chromatography using increasing proportions of hexane:ethyl acetate as eluant, to obtain compound (I) (Mahender, 2006). Crystals were grown from an MeOH–water (1:1) solution by slow evaporation.

S3. Refinement

All H atoms were placed in geometrically idealized positions and allowed to ride on their parent atoms, with C—H distances in the range 0.93–0.98 Å and O—H = 0.82 Å, and with U_iso(H) = 1.5U_eq(C,O) for methyl or hydroxy H atoms or 1.2U_eq(C) for all others. [Please check added text]

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

Figures

	Fig. 1. The asymmetric unit of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
	Fig. 2. Part of the crystal structure of (I), highlighting the formation of a chain of R^33(22) rings along [110]. Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. [Symmetry codes: (i) 1 + x, y − 1, z; (ii) x − 1, 1 + y, z.]

5-hydroxy-2-(3-hydroxy-4,5-dimethoxyphenyl)-3,6,7-trimethoxy-4H-chromene-4-one

Crystal data

C20H20O9	Z = 4
Mr = 404.36	F(000) = 848
Triclinic, P1	Dx = 1.445 Mg m^−3
a = 7.5629 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 15.2199 (9) Å	Cell parameters from 5057 reflections
c = 17.6543 (11) Å	θ = 2.2–27.2°
α = 69.621 (1)°	µ = 0.12 mm^−1
β = 83.145 (1)°	T = 273 K
γ = 77.760 (1)°	Prism, colourless
V = 1859.3 (2) Å^3	0.22 × 0.18 × 0.16 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	6127 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
Graphite monochromator	θmax = 28.0°, θmin = 2.2°
ω scans	h = −9→9
16152 measured reflections	k = −20→19
8323 independent reflections	l = −22→22

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0608P)^2 + 0.4046P] where P = (Fo^2 + 2Fc^2)/3
8323 reflections	(Δ/σ)max < 0.001
537 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.22 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.

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
C1A	0.3907 (2)	−0.01377 (12)	0.37569 (10)	0.0392 (4)
C2A	0.4328 (2)	−0.10321 (11)	0.43907 (10)	0.0370 (4)
C3A	0.5430 (2)	−0.18467 (12)	0.42496 (11)	0.0412 (4)
C4A	0.5896 (2)	−0.26713 (12)	0.48888 (11)	0.0420 (4)
C5A	0.5293 (2)	−0.27050 (12)	0.56833 (11)	0.0420 (4)
C6A	0.4179 (2)	−0.19286 (12)	0.58362 (11)	0.0414 (4)
H6A	0.3760	−0.1955	0.6359	0.050*
C7A	0.3715 (2)	−0.11139 (11)	0.51821 (10)	0.0357 (4)
C8A	0.2118 (2)	0.04939 (11)	0.47697 (10)	0.0342 (3)
C9A	0.2712 (2)	0.06171 (11)	0.39850 (10)	0.0373 (4)
C10A	0.6183 (3)	−0.42100 (14)	0.48411 (14)	0.0634 (6)
H10A	0.5143	−0.3988	0.4516	0.095*
H10B	0.5808	−0.4483	0.5399	0.095*
H10C	0.7016	−0.4684	0.4670	0.095*
C11A	0.5470 (4)	−0.36044 (15)	0.70907 (13)	0.0675 (6)
H11A	0.4183	−0.3552	0.7195	0.101*
H11B	0.5862	−0.3100	0.7196	0.101*
H11C	0.6068	−0.4209	0.7437	0.101*
C12A	0.1033 (3)	0.15391 (16)	0.28324 (13)	0.0649 (6)
H12A	−0.0139	0.1508	0.3107	0.097*
H12B	0.1396	0.1016	0.2629	0.097*
H12C	0.0979	0.2129	0.2390	0.097*
C13A	0.0961 (2)	0.11803 (11)	0.51211 (10)	0.0359 (4)
C14A	0.0352 (2)	0.21234 (12)	0.46458 (10)	0.0405 (4)
H14A	0.0632	0.2322	0.4092	0.049*
C15A	−0.0671 (2)	0.27660 (12)	0.49982 (11)	0.0420 (4)
C16A	−0.1089 (2)	0.24704 (12)	0.58228 (11)	0.0422 (4)
C17A	−0.0539 (2)	0.15281 (13)	0.62867 (11)	0.0453 (4)
C18A	0.0496 (2)	0.08846 (12)	0.59467 (11)	0.0418 (4)
H18A	0.0882	0.0256	0.6268	0.050*
C19A	−0.0781 (4)	0.40433 (15)	0.37563 (13)	0.0735 (7)
H19A	−0.1246	0.3716	0.3469	0.110*
H19B	0.0518	0.3937	0.3693	0.110*
H19C	−0.1253	0.4714	0.3543	0.110*
C20A	−0.1020 (3)	0.37206 (16)	0.63045 (14)	0.0653 (6)
H20A	−0.0674	0.4130	0.5781	0.098*
H20B	0.0047	0.3360	0.6589	0.098*
H20C	−0.1737	0.4100	0.6605	0.098*
O1A	0.26342 (15)	−0.03581 (7)	0.53572 (7)	0.0388 (3)
O2A	0.45445 (19)	−0.00009 (9)	0.30425 (8)	0.0524 (3)
O3A	0.6038 (2)	−0.18191 (9)	0.34934 (8)	0.0575 (4)
H3A	0.5772	−0.1274	0.3180	0.086*
O4A	0.70446 (17)	−0.34325 (9)	0.47488 (9)	0.0550 (3)
O5A	0.59107 (19)	−0.35347 (9)	0.62640 (8)	0.0555 (3)
O6A	0.23295 (17)	0.14845 (8)	0.33891 (7)	0.0448 (3)
O7A	−0.13092 (19)	0.36948 (9)	0.45837 (8)	0.0583 (4)
O8A	−0.20616 (17)	0.30792 (10)	0.62120 (8)	0.0552 (3)
O9A	−0.1010 (2)	0.12297 (11)	0.70954 (8)	0.0723 (5)
H9A	−0.1795	0.1640	0.7200	0.108*
C1B	1.2373 (2)	−0.17055 (14)	0.08625 (11)	0.0479 (4)
C2B	1.1070 (2)	−0.23139 (13)	0.12285 (11)	0.0439 (4)
C3B	1.1454 (3)	−0.33054 (14)	0.13385 (12)	0.0494 (5)
C4B	1.0189 (3)	−0.38680 (13)	0.17088 (12)	0.0501 (5)
C5B	0.8476 (3)	−0.34519 (13)	0.19619 (11)	0.0469 (4)
C6B	0.8065 (2)	−0.24875 (12)	0.18592 (11)	0.0446 (4)
H6B	0.6937	−0.2216	0.2030	0.053*
C7B	0.9368 (2)	−0.19385 (12)	0.14982 (10)	0.0406 (4)
C8B	1.0128 (2)	−0.03991 (12)	0.11122 (10)	0.0385 (4)
C9B	1.1810 (2)	−0.07229 (13)	0.08330 (10)	0.0433 (4)
C10B	1.0251 (5)	−0.51783 (19)	0.12832 (19)	0.1049 (11)
H10D	0.8970	−0.5032	0.1213	0.157*
H10E	1.0657	−0.5856	0.1446	0.157*
H10F	1.0872	−0.4879	0.0782	0.157*
C11B	0.5600 (3)	−0.36933 (17)	0.26295 (16)	0.0727 (6)
H11D	0.5788	−0.3390	0.3000	0.109*
H11E	0.4962	−0.4207	0.2908	0.109*
H11F	0.4901	−0.3237	0.2194	0.109*
C12B	1.4323 (3)	−0.01767 (19)	0.10558 (15)	0.0740 (7)
H12D	1.3704	−0.0091	0.1539	0.111*
H12E	1.5029	0.0314	0.0806	0.111*
H12F	1.5107	−0.0789	0.1190	0.111*
C13B	0.9394 (2)	0.05572 (12)	0.11613 (10)	0.0385 (4)
C14B	1.0266 (2)	0.13294 (12)	0.07688 (10)	0.0425 (4)
H14B	1.1311	0.1254	0.0444	0.051*
C15B	0.9582 (2)	0.22054 (12)	0.08606 (10)	0.0430 (4)
C16B	0.7992 (3)	0.23370 (12)	0.13260 (11)	0.0443 (4)
C17B	0.7108 (2)	0.15706 (13)	0.17119 (11)	0.0447 (4)
C18B	0.7814 (2)	0.06876 (12)	0.16352 (11)	0.0423 (4)
H18B	0.7228	0.0176	0.1902	0.051*
C19B	1.2221 (3)	0.28292 (16)	0.02194 (14)	0.0640 (6)
H19D	1.2950	0.2358	0.0636	0.096*
H19E	1.2675	0.3415	0.0047	0.096*
H19F	1.2268	0.2610	−0.0232	0.096*
C20B	0.6144 (4)	0.38522 (17)	0.09036 (17)	0.0889 (8)
H20D	0.6683	0.3976	0.0365	0.133*
H20E	0.5832	0.4436	0.1025	0.133*
H20F	0.5070	0.3594	0.0942	0.133*
O1B	0.89050 (15)	−0.09924 (8)	0.14122 (7)	0.0429 (3)
O2B	1.39150 (19)	−0.20068 (11)	0.06065 (10)	0.0674 (4)
O3B	1.3092 (2)	−0.36996 (11)	0.10888 (11)	0.0681 (4)
H3B	1.3709	−0.3286	0.0880	0.102*
O4B	1.0624 (2)	−0.48396 (9)	0.18801 (9)	0.0685 (4)
O5B	0.7314 (2)	−0.40605 (9)	0.23112 (9)	0.0605 (4)
O6B	1.30210 (17)	−0.01232 (9)	0.05055 (8)	0.0523 (3)
O7B	1.03974 (19)	0.29848 (9)	0.05259 (9)	0.0595 (4)
O8B	0.73797 (19)	0.31948 (9)	0.14574 (8)	0.0558 (3)
O9B	0.5573 (2)	0.17353 (9)	0.21665 (10)	0.0639 (4)
H9B	0.5228	0.1231	0.2412	0.096*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1A	0.0410 (9)	0.0395 (9)	0.0429 (9)	−0.0121 (7)	0.0007 (7)	−0.0188 (7)
C2A	0.0349 (8)	0.0355 (8)	0.0451 (9)	−0.0082 (7)	−0.0001 (7)	−0.0187 (7)
C3A	0.0383 (9)	0.0422 (9)	0.0496 (10)	−0.0099 (7)	0.0053 (8)	−0.0244 (8)
C4A	0.0338 (9)	0.0367 (9)	0.0594 (11)	−0.0034 (7)	0.0023 (8)	−0.0242 (8)
C5A	0.0389 (9)	0.0352 (9)	0.0522 (10)	−0.0028 (7)	−0.0040 (8)	−0.0167 (8)
C6A	0.0412 (9)	0.0389 (9)	0.0445 (10)	−0.0042 (7)	0.0001 (7)	−0.0168 (8)
C7A	0.0326 (8)	0.0324 (8)	0.0467 (9)	−0.0052 (6)	−0.0018 (7)	−0.0196 (7)
C8A	0.0332 (8)	0.0298 (8)	0.0412 (9)	−0.0063 (6)	−0.0037 (7)	−0.0129 (7)
C9A	0.0393 (9)	0.0332 (8)	0.0419 (9)	−0.0091 (7)	−0.0037 (7)	−0.0136 (7)
C10A	0.0753 (14)	0.0407 (11)	0.0781 (15)	−0.0007 (10)	−0.0066 (12)	−0.0295 (10)
C11A	0.0898 (17)	0.0480 (12)	0.0523 (12)	0.0098 (11)	−0.0113 (11)	−0.0119 (10)
C12A	0.0757 (15)	0.0619 (13)	0.0525 (12)	−0.0036 (11)	−0.0205 (11)	−0.0130 (10)
C13A	0.0325 (8)	0.0344 (8)	0.0442 (9)	−0.0065 (6)	−0.0035 (7)	−0.0167 (7)
C14A	0.0429 (9)	0.0373 (9)	0.0394 (9)	−0.0014 (7)	−0.0019 (7)	−0.0141 (7)
C15A	0.0372 (9)	0.0346 (9)	0.0512 (10)	0.0012 (7)	−0.0053 (8)	−0.0142 (8)
C16A	0.0347 (9)	0.0446 (10)	0.0489 (10)	0.0004 (7)	−0.0010 (7)	−0.0222 (8)
C17A	0.0452 (10)	0.0486 (10)	0.0400 (9)	−0.0040 (8)	0.0003 (8)	−0.0156 (8)
C18A	0.0423 (9)	0.0362 (9)	0.0441 (10)	−0.0028 (7)	−0.0031 (7)	−0.0121 (7)
C19A	0.0945 (18)	0.0463 (12)	0.0569 (13)	0.0149 (11)	−0.0022 (12)	−0.0055 (10)
C20A	0.0657 (13)	0.0707 (14)	0.0724 (14)	−0.0006 (11)	−0.0070 (11)	−0.0455 (12)
O1A	0.0436 (6)	0.0313 (6)	0.0401 (6)	−0.0007 (5)	−0.0004 (5)	−0.0143 (5)
O2A	0.0677 (9)	0.0452 (7)	0.0433 (7)	−0.0097 (6)	0.0106 (6)	−0.0181 (6)
O3A	0.0725 (9)	0.0485 (8)	0.0528 (8)	−0.0072 (7)	0.0146 (7)	−0.0265 (6)
O4A	0.0473 (7)	0.0415 (7)	0.0790 (10)	−0.0012 (6)	0.0079 (7)	−0.0311 (7)
O5A	0.0640 (8)	0.0402 (7)	0.0552 (8)	0.0092 (6)	−0.0062 (7)	−0.0172 (6)
O6A	0.0549 (7)	0.0366 (6)	0.0403 (7)	−0.0071 (5)	−0.0025 (6)	−0.0103 (5)
O7A	0.0684 (9)	0.0394 (7)	0.0520 (8)	0.0129 (6)	0.0010 (7)	−0.0111 (6)
O8A	0.0495 (8)	0.0567 (8)	0.0619 (8)	0.0027 (6)	0.0050 (6)	−0.0328 (7)
O9A	0.0931 (12)	0.0646 (10)	0.0421 (8)	0.0085 (8)	0.0109 (7)	−0.0144 (7)
C1B	0.0440 (10)	0.0542 (11)	0.0460 (10)	0.0036 (8)	−0.0019 (8)	−0.0249 (9)
C2B	0.0462 (10)	0.0439 (10)	0.0424 (9)	0.0012 (8)	−0.0043 (8)	−0.0202 (8)
C3B	0.0518 (11)	0.0491 (11)	0.0487 (11)	0.0082 (9)	−0.0085 (9)	−0.0264 (9)
C4B	0.0628 (12)	0.0373 (9)	0.0493 (11)	0.0040 (9)	−0.0119 (9)	−0.0180 (8)
C5B	0.0572 (11)	0.0393 (10)	0.0430 (10)	−0.0039 (8)	−0.0095 (8)	−0.0130 (8)
C6B	0.0457 (10)	0.0397 (9)	0.0475 (10)	−0.0007 (8)	−0.0037 (8)	−0.0174 (8)
C7B	0.0447 (10)	0.0382 (9)	0.0396 (9)	0.0003 (7)	−0.0076 (7)	−0.0166 (7)
C8B	0.0403 (9)	0.0411 (9)	0.0349 (8)	−0.0054 (7)	−0.0037 (7)	−0.0140 (7)
C9B	0.0429 (10)	0.0491 (10)	0.0381 (9)	−0.0058 (8)	−0.0002 (7)	−0.0169 (8)
C10B	0.156 (3)	0.0605 (16)	0.118 (2)	−0.0132 (17)	−0.025 (2)	−0.0515 (17)
C11B	0.0671 (14)	0.0593 (13)	0.0865 (17)	−0.0164 (11)	0.0094 (13)	−0.0192 (12)
C12B	0.0529 (13)	0.0959 (18)	0.0783 (16)	−0.0225 (12)	−0.0087 (11)	−0.0284 (14)
C13B	0.0401 (9)	0.0400 (9)	0.0362 (9)	−0.0043 (7)	−0.0050 (7)	−0.0146 (7)
C14B	0.0422 (9)	0.0450 (10)	0.0401 (9)	−0.0082 (8)	0.0019 (7)	−0.0149 (8)
C15B	0.0486 (10)	0.0428 (10)	0.0400 (9)	−0.0146 (8)	−0.0016 (8)	−0.0131 (8)
C16B	0.0544 (11)	0.0384 (9)	0.0435 (10)	−0.0090 (8)	−0.0009 (8)	−0.0183 (8)
C17B	0.0467 (10)	0.0441 (10)	0.0454 (10)	−0.0096 (8)	0.0050 (8)	−0.0191 (8)
C18B	0.0452 (10)	0.0369 (9)	0.0465 (10)	−0.0106 (7)	0.0023 (8)	−0.0157 (8)
C19B	0.0570 (13)	0.0665 (14)	0.0689 (14)	−0.0267 (11)	0.0078 (11)	−0.0174 (11)
C20B	0.110 (2)	0.0575 (15)	0.093 (2)	0.0150 (14)	−0.0179 (17)	−0.0302 (14)
O1B	0.0398 (6)	0.0352 (6)	0.0550 (7)	−0.0026 (5)	−0.0004 (5)	−0.0195 (5)
O2B	0.0511 (8)	0.0674 (9)	0.0849 (11)	−0.0007 (7)	0.0151 (8)	−0.0386 (8)
O3B	0.0590 (9)	0.0609 (9)	0.0884 (12)	0.0080 (7)	0.0042 (8)	−0.0433 (9)
O4B	0.0890 (11)	0.0370 (7)	0.0753 (10)	0.0071 (7)	−0.0116 (8)	−0.0220 (7)
O5B	0.0690 (9)	0.0391 (7)	0.0685 (9)	−0.0093 (7)	0.0008 (7)	−0.0134 (7)
O6B	0.0442 (7)	0.0590 (8)	0.0539 (8)	−0.0104 (6)	0.0052 (6)	−0.0209 (6)
O7B	0.0616 (9)	0.0469 (8)	0.0714 (9)	−0.0218 (7)	0.0139 (7)	−0.0199 (7)
O8B	0.0689 (9)	0.0417 (7)	0.0624 (9)	−0.0125 (6)	0.0067 (7)	−0.0260 (6)
O9B	0.0668 (9)	0.0449 (8)	0.0794 (10)	−0.0148 (7)	0.0323 (8)	−0.0289 (7)

Geometric parameters (Å, º)

C1A—O2A	1.257 (2)	C1B—O2B	1.252 (2)
C1A—C2A	1.431 (2)	C1B—C2B	1.436 (3)
C1A—C9A	1.447 (2)	C1B—C9B	1.450 (3)
C2A—C7A	1.390 (2)	C2B—C7B	1.393 (2)
C2A—C3A	1.422 (2)	C2B—C3B	1.422 (3)
C3A—O3A	1.348 (2)	C3B—O3B	1.352 (2)
C3A—C4A	1.376 (2)	C3B—C4B	1.373 (3)
C4A—O4A	1.371 (2)	C4B—O4B	1.376 (2)
C4A—C5A	1.409 (3)	C4B—C5B	1.410 (3)
C5A—O5A	1.351 (2)	C5B—O5B	1.352 (2)
C5A—C6A	1.388 (2)	C5B—C6B	1.385 (2)
C6A—C7A	1.382 (2)	C6B—C7B	1.380 (3)
C6A—H6A	0.9300	C6B—H6B	0.9300
C7A—O1A	1.370 (2)	C7B—O1B	1.366 (2)
C8A—O1A	1.362 (2)	C8B—O1B	1.362 (2)
C8A—C9A	1.365 (2)	C8B—C9B	1.363 (2)
C8A—C13A	1.475 (2)	C8B—C13B	1.472 (2)
C9A—O6A	1.370 (2)	C9B—O6B	1.366 (2)
C10A—O4A	1.421 (2)	C10B—O4B	1.402 (3)
C10A—H10A	0.9600	C10B—H10D	0.9600
C10A—H10B	0.9600	C10B—H10E	0.9600
C10A—H10C	0.9600	C10B—H10F	0.9600
C11A—O5A	1.429 (2)	C11B—O5B	1.430 (3)
C11A—H11A	0.9600	C11B—H11D	0.9600
C11A—H11B	0.9600	C11B—H11E	0.9600
C11A—H11C	0.9600	C11B—H11F	0.9600
C12A—O6A	1.440 (2)	C12B—O6B	1.435 (3)
C12A—H12A	0.9600	C12B—H12D	0.9600
C12A—H12B	0.9600	C12B—H12E	0.9600
C12A—H12C	0.9600	C12B—H12F	0.9600
C13A—C18A	1.392 (2)	C13B—C18B	1.394 (2)
C13A—C14A	1.396 (2)	C13B—C14B	1.396 (2)
C14A—C15A	1.389 (2)	C14B—C15B	1.382 (2)
C14A—H14A	0.9300	C14B—H14B	0.9300
C15A—O7A	1.357 (2)	C15B—O7B	1.368 (2)
C15A—C16A	1.384 (3)	C15B—C16B	1.392 (3)
C16A—O8A	1.380 (2)	C16B—O8B	1.379 (2)
C16A—C17A	1.382 (2)	C16B—C17B	1.393 (2)
C17A—O9A	1.366 (2)	C17B—O9B	1.360 (2)
C17A—C18A	1.380 (2)	C17B—C18B	1.384 (2)
C18A—H18A	0.9300	C18B—H18B	0.9300
C19A—O7A	1.409 (2)	C19B—O7B	1.423 (2)
C19A—H19A	0.9600	C19B—H19D	0.9600
C19A—H19B	0.9600	C19B—H19E	0.9600
C19A—H19C	0.9600	C19B—H19F	0.9600
C20A—O8A	1.438 (2)	C20B—O8B	1.404 (3)
C20A—H20A	0.9600	C20B—H20D	0.9600
C20A—H20B	0.9600	C20B—H20E	0.9600
C20A—H20C	0.9600	C20B—H20F	0.9600
O3A—H3A	0.8200	O3B—H3B	0.8200
O9A—H9A	0.8200	O9B—H9B	0.8200
O2A—C1A—C2A	122.64 (15)	O2B—C1B—C2B	122.42 (17)
O2A—C1A—C9A	121.22 (15)	O2B—C1B—C9B	121.91 (18)
C2A—C1A—C9A	116.13 (15)	C2B—C1B—C9B	115.64 (15)
C7A—C2A—C3A	117.75 (15)	C7B—C2B—C3B	117.70 (17)
C7A—C2A—C1A	119.89 (14)	C7B—C2B—C1B	119.98 (16)
C3A—C2A—C1A	122.31 (15)	C3B—C2B—C1B	122.32 (16)
O3A—C3A—C4A	119.39 (15)	O3B—C3B—C4B	119.76 (17)
O3A—C3A—C2A	120.63 (16)	O3B—C3B—C2B	119.64 (19)
C4A—C3A—C2A	119.98 (16)	C4B—C3B—C2B	120.60 (17)
O4A—C4A—C3A	119.28 (16)	C3B—C4B—O4B	120.32 (18)
O4A—C4A—C5A	120.60 (16)	C3B—C4B—C5B	119.54 (16)
C3A—C4A—C5A	119.97 (15)	O4B—C4B—C5B	120.00 (19)
O5A—C5A—C6A	124.10 (16)	O5B—C5B—C6B	123.76 (17)
O5A—C5A—C4A	114.66 (14)	O5B—C5B—C4B	115.23 (16)
C6A—C5A—C4A	121.23 (16)	C6B—C5B—C4B	121.00 (18)
C7A—C6A—C5A	117.53 (16)	C7B—C6B—C5B	118.47 (17)
C7A—C6A—H6A	121.2	C7B—C6B—H6B	120.8
C5A—C6A—H6A	121.2	C5B—C6B—H6B	120.8
O1A—C7A—C6A	115.89 (14)	O1B—C7B—C6B	116.42 (15)
O1A—C7A—C2A	120.61 (14)	O1B—C7B—C2B	120.92 (16)
C6A—C7A—C2A	123.47 (15)	C6B—C7B—C2B	122.67 (16)
O1A—C8A—C9A	119.96 (14)	O1B—C8B—C9B	120.43 (15)
O1A—C8A—C13A	110.64 (13)	O1B—C8B—C13B	111.59 (14)
C9A—C8A—C13A	129.39 (15)	C9B—C8B—C13B	127.96 (16)
C8A—C9A—O6A	121.44 (14)	C8B—C9B—O6B	120.73 (16)
C8A—C9A—C1A	121.50 (15)	C8B—C9B—C1B	121.62 (17)
O6A—C9A—C1A	116.84 (15)	O6B—C9B—C1B	117.65 (16)
O4A—C10A—H10A	109.5	O4B—C10B—H10D	109.5
O4A—C10A—H10B	109.5	O4B—C10B—H10E	109.5
H10A—C10A—H10B	109.5	H10D—C10B—H10E	109.5
O4A—C10A—H10C	109.5	O4B—C10B—H10F	109.5
H10A—C10A—H10C	109.5	H10D—C10B—H10F	109.5
H10B—C10A—H10C	109.5	H10E—C10B—H10F	109.5
O5A—C11A—H11A	109.5	O5B—C11B—H11D	109.5
O5A—C11A—H11B	109.5	O5B—C11B—H11E	109.5
H11A—C11A—H11B	109.5	H11D—C11B—H11E	109.5
O5A—C11A—H11C	109.5	O5B—C11B—H11F	109.5
H11A—C11A—H11C	109.5	H11D—C11B—H11F	109.5
H11B—C11A—H11C	109.5	H11E—C11B—H11F	109.5
O6A—C12A—H12A	109.5	O6B—C12B—H12D	109.5
O6A—C12A—H12B	109.5	O6B—C12B—H12E	109.5
H12A—C12A—H12B	109.5	H12D—C12B—H12E	109.5
O6A—C12A—H12C	109.5	O6B—C12B—H12F	109.5
H12A—C12A—H12C	109.5	H12D—C12B—H12F	109.5
H12B—C12A—H12C	109.5	H12E—C12B—H12F	109.5
C18A—C13A—C14A	119.43 (15)	C18B—C13B—C14B	119.05 (15)
C18A—C13A—C8A	119.20 (15)	C18B—C13B—C8B	118.99 (15)
C14A—C13A—C8A	121.36 (15)	C14B—C13B—C8B	121.93 (15)
C15A—C14A—C13A	120.20 (16)	C15B—C14B—C13B	120.23 (16)
C15A—C14A—H14A	119.9	C15B—C14B—H14B	119.9
C13A—C14A—H14A	119.9	C13B—C14B—H14B	119.9
O7A—C15A—C16A	115.95 (15)	O7B—C15B—C14B	123.80 (16)
O7A—C15A—C14A	124.13 (16)	O7B—C15B—C16B	115.59 (15)
C16A—C15A—C14A	119.92 (15)	C14B—C15B—C16B	120.60 (16)
O8A—C16A—C17A	117.58 (16)	O8B—C16B—C15B	120.26 (16)
O8A—C16A—C15A	122.71 (16)	O8B—C16B—C17B	120.22 (16)
C17A—C16A—C15A	119.71 (15)	C15B—C16B—C17B	119.31 (16)
O9A—C17A—C18A	119.39 (16)	O9B—C17B—C18B	122.96 (16)
O9A—C17A—C16A	119.64 (16)	O9B—C17B—C16B	116.90 (15)
C18A—C17A—C16A	120.96 (17)	C18B—C17B—C16B	120.14 (16)
C17A—C18A—C13A	119.72 (16)	C17B—C18B—C13B	120.63 (16)
C17A—C18A—H18A	120.1	C17B—C18B—H18B	119.7
C13A—C18A—H18A	120.1	C13B—C18B—H18B	119.7
O7A—C19A—H19A	109.5	O7B—C19B—H19D	109.5
O7A—C19A—H19B	109.5	O7B—C19B—H19E	109.5
H19A—C19A—H19B	109.5	H19D—C19B—H19E	109.5
O7A—C19A—H19C	109.5	O7B—C19B—H19F	109.5
H19A—C19A—H19C	109.5	H19D—C19B—H19F	109.5
H19B—C19A—H19C	109.5	H19E—C19B—H19F	109.5
O8A—C20A—H20A	109.5	O8B—C20B—H20D	109.5
O8A—C20A—H20B	109.5	O8B—C20B—H20E	109.5
H20A—C20A—H20B	109.5	H20D—C20B—H20E	109.5
O8A—C20A—H20C	109.5	O8B—C20B—H20F	109.5
H20A—C20A—H20C	109.5	H20D—C20B—H20F	109.5
H20B—C20A—H20C	109.5	H20E—C20B—H20F	109.5
C8A—O1A—C7A	121.74 (13)	C8B—O1B—C7B	121.21 (13)
C3A—O3A—H3A	109.5	C3B—O3B—H3B	109.5
C4A—O4A—C10A	113.57 (14)	C4B—O4B—C10B	115.82 (18)
C5A—O5A—C11A	118.25 (14)	C5B—O5B—C11B	117.83 (15)
C9A—O6A—C12A	114.65 (14)	C9B—O6B—C12B	114.20 (16)
C15A—O7A—C19A	117.61 (15)	C15B—O7B—C19B	117.34 (15)
C16A—O8A—C20A	113.04 (14)	C16B—O8B—C20B	115.04 (16)
C17A—O9A—H9A	109.5	C17B—O9B—H9B	109.5
O2A—C1A—C2A—C7A	174.12 (15)	O2B—C1B—C2B—C7B	−179.59 (17)
C9A—C1A—C2A—C7A	−5.0 (2)	C9B—C1B—C2B—C7B	2.5 (3)
O2A—C1A—C2A—C3A	−3.2 (3)	O2B—C1B—C2B—C3B	1.1 (3)
C9A—C1A—C2A—C3A	177.65 (15)	C9B—C1B—C2B—C3B	−176.82 (16)
C7A—C2A—C3A—O3A	178.67 (15)	C7B—C2B—C3B—O3B	−179.71 (17)
C1A—C2A—C3A—O3A	−3.9 (3)	C1B—C2B—C3B—O3B	−0.4 (3)
C7A—C2A—C3A—C4A	−1.8 (2)	C7B—C2B—C3B—C4B	−0.9 (3)
C1A—C2A—C3A—C4A	175.60 (16)	C1B—C2B—C3B—C4B	178.41 (17)
O3A—C3A—C4A—O4A	3.3 (2)	O3B—C3B—C4B—O4B	4.8 (3)
C2A—C3A—C4A—O4A	−176.21 (15)	C2B—C3B—C4B—O4B	−174.04 (16)
O3A—C3A—C4A—C5A	179.00 (16)	O3B—C3B—C4B—C5B	−179.45 (17)
C2A—C3A—C4A—C5A	−0.5 (3)	C2B—C3B—C4B—C5B	1.7 (3)
O4A—C4A—C5A—O5A	−1.1 (2)	C3B—C4B—C5B—O5B	179.22 (17)
C3A—C4A—C5A—O5A	−176.78 (15)	O4B—C4B—C5B—O5B	−5.0 (3)
O4A—C4A—C5A—C6A	177.83 (15)	C3B—C4B—C5B—C6B	−1.5 (3)
C3A—C4A—C5A—C6A	2.2 (3)	O4B—C4B—C5B—C6B	174.30 (17)
O5A—C5A—C6A—C7A	177.47 (16)	O5B—C5B—C6B—C7B	179.61 (16)
C4A—C5A—C6A—C7A	−1.4 (3)	C4B—C5B—C6B—C7B	0.4 (3)
C5A—C6A—C7A—O1A	−179.14 (14)	C5B—C6B—C7B—O1B	−179.77 (15)
C5A—C6A—C7A—C2A	−1.1 (2)	C5B—C6B—C7B—C2B	0.5 (3)
C3A—C2A—C7A—O1A	−179.35 (14)	C3B—C2B—C7B—O1B	−179.97 (15)
C1A—C2A—C7A—O1A	3.2 (2)	C1B—C2B—C7B—O1B	0.7 (3)
C3A—C2A—C7A—C6A	2.7 (2)	C3B—C2B—C7B—C6B	−0.2 (3)
C1A—C2A—C7A—C6A	−174.79 (15)	C1B—C2B—C7B—C6B	−179.56 (17)
O1A—C8A—C9A—O6A	−175.10 (13)	O1B—C8B—C9B—O6B	177.72 (15)
C13A—C8A—C9A—O6A	3.3 (3)	C13B—C8B—C9B—O6B	−4.1 (3)
O1A—C8A—C9A—C1A	−0.7 (2)	O1B—C8B—C9B—C1B	−1.5 (3)
C13A—C8A—C9A—C1A	177.69 (15)	C13B—C8B—C9B—C1B	176.64 (16)
O2A—C1A—C9A—C8A	−175.29 (16)	O2B—C1B—C9B—C8B	179.95 (18)
C2A—C1A—C9A—C8A	3.8 (2)	C2B—C1B—C9B—C8B	−2.1 (3)
O2A—C1A—C9A—O6A	−0.6 (2)	O2B—C1B—C9B—O6B	0.7 (3)
C2A—C1A—C9A—O6A	178.49 (14)	C2B—C1B—C9B—O6B	178.63 (15)
O1A—C8A—C13A—C18A	−2.8 (2)	O1B—C8B—C13B—C18B	13.3 (2)
C9A—C8A—C13A—C18A	178.72 (16)	C9B—C8B—C13B—C18B	−164.99 (17)
O1A—C8A—C13A—C14A	175.99 (14)	O1B—C8B—C13B—C14B	−168.81 (15)
C9A—C8A—C13A—C14A	−2.5 (3)	C9B—C8B—C13B—C14B	12.9 (3)
C18A—C13A—C14A—C15A	1.6 (3)	C18B—C13B—C14B—C15B	1.0 (3)
C8A—C13A—C14A—C15A	−177.20 (15)	C8B—C13B—C14B—C15B	−176.89 (16)
C13A—C14A—C15A—O7A	179.68 (16)	C13B—C14B—C15B—O7B	177.03 (16)
C13A—C14A—C15A—C16A	−0.1 (3)	C13B—C14B—C15B—C16B	−1.8 (3)
O7A—C15A—C16A—O8A	−1.4 (3)	O7B—C15B—C16B—O8B	−3.1 (2)
C14A—C15A—C16A—O8A	178.36 (16)	C14B—C15B—C16B—O8B	175.83 (16)
O7A—C15A—C16A—C17A	178.02 (16)	O7B—C15B—C16B—C17B	−177.78 (16)
C14A—C15A—C16A—C17A	−2.2 (3)	C14B—C15B—C16B—C17B	1.1 (3)
O8A—C16A—C17A—O9A	1.8 (3)	O8B—C16B—C17B—O9B	4.5 (3)
C15A—C16A—C17A—O9A	−177.61 (17)	C15B—C16B—C17B—O9B	179.23 (17)
O8A—C16A—C17A—C18A	−177.52 (16)	O8B—C16B—C17B—C18B	−174.38 (17)
C15A—C16A—C17A—C18A	3.0 (3)	C15B—C16B—C17B—C18B	0.3 (3)
O9A—C17A—C18A—C13A	179.12 (17)	O9B—C17B—C18B—C13B	−179.96 (17)
C16A—C17A—C18A—C13A	−1.5 (3)	C16B—C17B—C18B—C13B	−1.1 (3)
C14A—C13A—C18A—C17A	−0.8 (2)	C14B—C13B—C18B—C17B	0.5 (3)
C8A—C13A—C18A—C17A	178.01 (15)	C8B—C13B—C18B—C17B	178.41 (16)
C9A—C8A—O1A—C7A	−1.4 (2)	C9B—C8B—O1B—C7B	5.0 (2)
C13A—C8A—O1A—C7A	179.90 (13)	C13B—C8B—O1B—C7B	−173.49 (14)
C6A—C7A—O1A—C8A	178.30 (14)	C6B—C7B—O1B—C8B	175.69 (15)
C2A—C7A—O1A—C8A	0.2 (2)	C2B—C7B—O1B—C8B	−4.6 (2)
C3A—C4A—O4A—C10A	−109.62 (19)	C3B—C4B—O4B—C10B	−91.9 (3)
C5A—C4A—O4A—C10A	74.7 (2)	C5B—C4B—O4B—C10B	92.3 (3)
C6A—C5A—O5A—C11A	−3.3 (3)	C6B—C5B—O5B—C11B	−3.4 (3)
C4A—C5A—O5A—C11A	175.60 (17)	C4B—C5B—O5B—C11B	175.89 (18)
C8A—C9A—O6A—C12A	−108.49 (18)	C8B—C9B—O6B—C12B	98.1 (2)
C1A—C9A—O6A—C12A	76.84 (19)	C1B—C9B—O6B—C12B	−82.6 (2)
C16A—C15A—O7A—C19A	174.64 (19)	C14B—C15B—O7B—C19B	−14.0 (3)
C14A—C15A—O7A—C19A	−5.1 (3)	C16B—C15B—O7B—C19B	164.84 (17)
C17A—C16A—O8A—C20A	106.1 (2)	C15B—C16B—O8B—C20B	92.9 (2)
C15A—C16A—O8A—C20A	−74.5 (2)	C17B—C16B—O8B—C20B	−92.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3A—H3A···O2A	0.82	1.91	2.6311 (18)	147
O3B—H3B···O2B	0.82	1.87	2.603 (2)	148
O9A—H9A···O8A	0.82	2.26	2.698 (2)	114
O9B—H9B···O2A	0.82	1.96	2.7783 (18)	176
C10A—H10C···O7A^i	0.96	2.57	3.495 (2)	162
C14A—H14A···O6A	0.93	2.20	2.863 (2)	128
C14B—H14B···O6B	0.93	2.19	2.824 (2)	125
C19A—H19C···O5B^ii	0.96	2.50	3.302 (3)	141
C19B—H19F···Cg1^iii	0.96	2.88	3.668	141

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