7-Hydr­oxy-6-methoxy-3-[(2-oxo-2H-1-benzopyran-7-yl)oxy]-2H-1-benzopyran-2-one

The title compound, daphnoretin, C₁₉H₁₂O₇, was isolated from the leaves of Stellera chamaejasme L. Two independent mol­ecules are present in the asymmetric unit, with similar conformations. Each of the independent mol­ecules is composed of two chromene systems connected by an ether bridge. The dihedral angles between the mean planes of the two chromene systems are 86.9 (2) and 81.9 (3)°. Mol­ecules form chains via hydrogen bonds and adjacent chains are parallel to each other.

S1. Comment

Stellera chamaejasme, which is widespread in the northern area of China, has been used traditionally as a herbal remedy for scabies and tinea in China. It has been found to possess obvious antitumor and antiviral, especially anti-HIV, activities (Ikekawa & Ikekawa, 1996; Endo et al., 1998). S. chamaejasme is abundant in daphnoretin, which has been demonstrated to inhibit Ehrlich carcinoma growth significantly (Hall et al., 1982; Liou et al., 1982) and has anti-P-388 lymphocytic leukemia activity in vitro (Handa et al., 1983). It is also a protein kinase C (PKC) activator, which shows strong suppressive effects on the expression of the hepatitis B surface antigen (HBsAg) in human hepatoma Hep3B cells (Chen et al., 1996) and induces rabbit platelet aggregation through protein kinase C activation (Ko et al., 1993). Antimicrobial effects are the other important characteristics of daphnoretin. It has antibacterial activity (Cottiglia et al., 2001), and antifungal, antimitotic and anti-HIV-1 activities to some extent (Hu et al., 2000). In our investigation of the chemical constituents of the leaves of S. chamaejasme, daphnoretin was isolated by chromatographic technology and identified by X-ray diffraction. To the best of our knowledge, the crystal structure of daphnoretin has not been reported previously.

Single-crystal X-ray diffraction reveals that two independent molecules of (I), A and B, are present in the asymmetric unit, with similar conformations (Fig. 1). Each of the independent molecules is composed of two chromene systems, which are connected by an ether band. No significant difference is observed for all bond distances and angles between A and B but they are distinguished by some bond rotations (Table 1). Rotations about the O1n—C1n and C1n—C10n bonds (n = A and B) mainly contribute to the different orientations of the chromene systems in the independent molecules. The atoms in each chromene system are nearly coplanar. The dihedral angles between chromene planes of the rings are 81.9 (3) and 86.9 (2)° for A and B. The conformations are also different at the terminal methoxy groups; the C19n—O7n—C14n—C13n torsion angles are 18.7 (3) and −1.5 (3)° for A and B, respectively.

The bond distances and bond angles are in agreement with those of some analogous structures (Borowiak & Wolska, 1989; Rajnikant et al., 1993; Gupta et al., 1993; Singh et al., 1995)·The double bonds (C7n═O3n and C18n═O4n) and the multiple-character bands (C5n═C6n and C10n═ C11n) (n = A and B), which are generally responsible for the photoactivity of coumarins (Song & Gordon, 1970), are confirmed by their respective distances [1.208 (2) and 1.212 (2) Å, 1.207 (2) and 1.210 (2) Å, 1.340 (2) and 1.343 (2) Å, and 1.333 (2) and 1.333 (2) Å]. The C8n—O2n, C7n—O2n, C17n—O5n and C18n—O5n bonds [1.3808 (19) and 1.3817 (19) Å, 1.372 (2) and 1.378 (2) Å, 1.381 (2) and 1.384 (2) Å, and 1.370 (2) and 1.371 (2) Å] exhibit variation in their distances, a feature quite common in furano compounds and simple coumarins [e.g. 1.389 and 1.366 Å in sphondin (Rajnikant et al., 1993), and 1.390 and 1.368 Å in angenomalin (Gupta et al., 1993)]. These differences may be due to ring strain and electron delocalization. The C—C–O and C—C—C angles at the junctions of the pyrone and phenyl rings, viz. C9n—C8n—O2n [116.48 (17) and 116.59 (17)°], C3n—C4n—C5n [125.40 (19) and 125.14 (18)°], C16n—C17n—O5n [117.22 (16) and 117.11 (16)°] and C11n—C12 n—C13n [124.84 (17) and 124.54 (17)°], are slightly smaller than and greater than 120°, respectively. This phenomenon has also been observed in some other coumarin derivatives (Rajnikant et al., 1993; Stemple & Watson, 1972; Ueno, 1985). The widening of the C6n—C7n—O3n [126.5 (2) and 127.1 (2)°] and C10n—C18n—O4n [126.23 (18) and 126.08 (19)°] angles is another feature commonly observed in 5-pyrone systems, and the large value of this angle is attributed to the lone-pair interactions between atoms O3n and O4n (Chinnakali et al., 1999a,b; Singh et al., 1997).

In the packing of (I) (Fig. 2), each molecule forms a one-dimensional chain via O—H···O hydrogen-bonding interactions between the O atom of the hydroxy group of a phenyl ring and the ketone group of a pyrone ring (Table 2). Adjacent one-dimensional chains are parallel to each other.

S2. Experimental

The air-dried and crushed leaves of S. chamaejasme (2 kg) were extracted three times with 95% ethanol (36 l) for 30 min (for each extraction) by ultrasound-assisted leaching, and the extract after concentration was subsequently partitioned with petrol and acetone. The acetone extract (86 g) was subjected to repeated column chromatograph over silica gel, using petroleum ether–acetone mixtures of increasing polarity as eluants. The petroleum ether–acetone (7:3) fraction gave daphnoretin (52 mg). All purification steps were carried out at room temperature. Crystals grew in a mixed solution of ethanol and acetone (1:1). Daphnoretin was then recrystallized from CHCl₃–MeOH (1:1) to give colorless blocks.

S3. Refinement

Atoms H6OA and H6OB were refined isotropically, with the O—H distances restrained to 0.88</span>(2) and 0.87<span style=" font-weight:600;">(2) Å. [Are these the actual restraints or the final refined values? The value of the initial restraint should be given here.] All other H atoms were placed in geometrically idealized positions and refined as riding atoms, with C—H distances of 0.93 (chromene) and 0.96 Å (methyl), and with U_iso(H) values of 1.2 (chromene) or 1.5(methyl) times U_eq(C).

Computing details

Data collection: PROCESS-AUTO (Rigaku Corporation, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: program(s) (references)?.

Figures

	Fig. 1. A view of the two independent molecules of the title compound, (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted.
	Fig. 2. A packing diagram for (I), viewed along the a axis, showing the one-dimensional chains formed via O–H···O interactions (dashed lines). H atoms have been omitted.

7-Hydroxy-6-methoxy-2-oxo-2H-chromen-3-yl 2-oxo-2H-chromen-7-yl ether

Crystal data

C19H12O7	Z = 4
Mr = 352.29	F(000) = 728
Triclinic, P1	Dx = 1.503 Mg m^−3
a = 7.659 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.872 (5) Å	Cell parameters from 8396 reflections
c = 16.479 (5) Å	θ = 1.4–25.9°
α = 113.175 (5)°	µ = 0.12 mm^−1
β = 99.171 (6)°	T = 293 K
γ = 96.799 (5)°	Block, colorless
V = 1557.0 (10) Å^3	0.31 × 0.16 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	5966 independent reflections
Radiation source: fine-focus sealed tube	3894 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 10.0 pixels mm^-1	θmax = 26.0°, θmin = 1.4°
ω scans	h = −8→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −17→17
Tmin = 0.966, Tmax = 0.985	l = −20→19
8458 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) = 0.093	H-atom parameters constrained
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0306P)^2] where P = (Fo^2 + 2Fc^2)/3
5966 reflections	(Δ/σ)max = 0.001
477 parameters	Δρmax = 0.17 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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	0.4428 (2)	0.27260 (14)	0.00204 (13)	0.0388 (5)
C2A	0.4862 (2)	0.28008 (14)	0.08964 (12)	0.0415 (5)
H2A	0.4467	0.3303	0.1360	0.050*
C3A	0.5883 (2)	0.21244 (15)	0.10721 (12)	0.0427 (5)
H3A	0.6198	0.2185	0.1662	0.051*
C4A	0.6458 (2)	0.13477 (14)	0.03831 (12)	0.0375 (5)
C5A	0.7443 (2)	0.05791 (15)	0.04906 (13)	0.0452 (5)
H5A	0.7830	0.0612	0.1067	0.054*
C6A	0.7825 (2)	−0.01894 (15)	−0.02211 (14)	0.0460 (5)
H6A	0.8441	−0.0692	−0.0134	0.055*
C7A	0.7295 (3)	−0.02455 (16)	−0.11155 (15)	0.0473 (5)
C8A	0.5936 (2)	0.12851 (14)	−0.04881 (12)	0.0363 (4)
C9A	0.4956 (2)	0.19686 (14)	−0.06798 (12)	0.0414 (5)
H9A	0.4659	0.1921	−0.1266	0.050*
C10A	0.2349 (3)	0.39021 (15)	0.03182 (12)	0.0402 (5)
C11A	0.2546 (3)	0.49625 (15)	0.07293 (12)	0.0416 (5)
H11A	0.3566	0.5399	0.0729	0.050*
C12A	0.1196 (2)	0.54341 (14)	0.11712 (11)	0.0365 (4)
C13A	0.1265 (3)	0.65387 (14)	0.16137 (12)	0.0411 (5)
H13A	0.2248	0.7017	0.1633	0.049*
C14A	−0.0092 (3)	0.69260 (14)	0.20180 (12)	0.0390 (5)
C15A	−0.1591 (3)	0.62015 (15)	0.19821 (12)	0.0401 (5)
C16A	−0.1681 (3)	0.51251 (15)	0.15469 (12)	0.0426 (5)
H16A	−0.2671	0.4647	0.1521	0.051*
C17A	−0.0310 (2)	0.47467 (14)	0.11472 (11)	0.0368 (4)
C18A	0.0779 (3)	0.31726 (16)	0.02885 (12)	0.0418 (5)
C19A	0.1020 (3)	0.87447 (15)	0.23345 (14)	0.0645 (7)
H19A	0.0863	0.9452	0.2695	0.097*
H19B	0.0729	0.8607	0.1705	0.097*
H19C	0.2251	0.8690	0.2502	0.097*
C1B	0.5733 (2)	0.73632 (15)	0.52152 (13)	0.0397 (5)
C2B	0.4670 (3)	0.70613 (15)	0.43583 (13)	0.0477 (5)
H2B	0.4705	0.6422	0.3884	0.057*
C3B	0.3567 (3)	0.77144 (16)	0.42168 (13)	0.0474 (5)
H3B	0.2833	0.7505	0.3645	0.057*
C4B	0.3520 (2)	0.86928 (15)	0.49170 (12)	0.0380 (5)
C5B	0.2409 (2)	0.94177 (16)	0.48333 (14)	0.0466 (5)
H5B	0.1605	0.9236	0.4285	0.056*
C6B	0.2502 (3)	1.03592 (16)	0.55316 (14)	0.0477 (5)
H6B	0.1773	1.0822	0.5457	0.057*
C7B	0.3707 (3)	1.06612 (16)	0.63905 (14)	0.0439 (5)
C8B	0.4660 (2)	0.89720 (14)	0.57563 (12)	0.0353 (4)
C9B	0.5745 (2)	0.83201 (14)	0.59251 (12)	0.0381 (5)
H9B	0.6464	0.8517	0.6498	0.046*
C10B	0.7610 (2)	0.60870 (14)	0.47727 (12)	0.0387 (5)
C11B	0.7399 (2)	0.50301 (14)	0.44958 (12)	0.0400 (5)
H11B	0.6547	0.4673	0.4678	0.048*
C12B	0.8476 (2)	0.44413 (14)	0.39195 (11)	0.0366 (4)
C13B	0.8397 (2)	0.33368 (14)	0.36197 (12)	0.0397 (5)
H13B	0.7579	0.2938	0.3786	0.048*
C14B	0.9511 (3)	0.28363 (14)	0.30831 (12)	0.0389 (5)
C15B	1.0766 (3)	0.34384 (15)	0.28321 (12)	0.0399 (5)
C16B	1.0861 (3)	0.45151 (15)	0.31245 (12)	0.0421 (5)
H16B	1.1686	0.4916	0.2964	0.051*
C17B	0.9727 (2)	0.50083 (14)	0.36602 (11)	0.0373 (5)
C18B	0.8914 (3)	0.66903 (15)	0.45085 (13)	0.0425 (5)
C19B	0.8331 (3)	0.11117 (15)	0.29726 (13)	0.0601 (6)
H19D	0.8481	0.0384	0.2697	0.090*
H19E	0.7111	0.1152	0.2760	0.090*
H19F	0.8585	0.1356	0.3619	0.090*
O1A	0.35292 (18)	0.34319 (10)	−0.01971 (8)	0.0502 (4)
O1B	0.67541 (18)	0.66934 (10)	0.54187 (8)	0.0477 (4)
O2A	0.63689 (18)	0.05040 (10)	−0.12140 (8)	0.0480 (4)
O3A	0.7580 (2)	−0.08925 (12)	−0.18021 (10)	0.0708 (5)
O4A	0.04948 (18)	0.22080 (10)	−0.00833 (9)	0.0538 (4)
O5A	−0.04808 (17)	0.36499 (9)	0.07215 (8)	0.0451 (3)
O6A	−0.29514 (19)	0.65470 (12)	0.23758 (10)	0.0580 (4)
O7A	−0.01414 (18)	0.79814 (10)	0.24851 (9)	0.0555 (4)
O2B	0.47407 (16)	0.99413 (9)	0.64707 (8)	0.0431 (3)
O3B	0.39180 (19)	1.14857 (11)	0.70653 (10)	0.0604 (4)
O4B	0.92093 (18)	0.76494 (10)	0.47495 (9)	0.0573 (4)
O5B	0.98931 (17)	0.61015 (9)	0.39376 (8)	0.0462 (3)
O6B	1.1873 (2)	0.29731 (13)	0.23072 (10)	0.0575 (4)
O7B	0.95408 (18)	0.17695 (10)	0.27386 (9)	0.0520 (4)
H6OB	1.173 (3)	0.2285 (17)	0.2160 (14)	0.076 (8)*
H6OA	−0.288 (3)	0.7247 (17)	0.2602 (14)	0.078 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1A	0.0400 (11)	0.0369 (11)	0.0457 (12)	0.0147 (9)	0.0174 (9)	0.0188 (10)
C2A	0.0431 (12)	0.0373 (11)	0.0383 (11)	0.0086 (9)	0.0153 (9)	0.0077 (9)
C3A	0.0404 (12)	0.0479 (13)	0.0366 (11)	0.0083 (10)	0.0076 (9)	0.0150 (10)
C4A	0.0333 (11)	0.0369 (11)	0.0416 (11)	0.0063 (9)	0.0113 (9)	0.0149 (9)
C5A	0.0367 (12)	0.0515 (13)	0.0494 (13)	0.0093 (10)	0.0063 (9)	0.0243 (11)
C6A	0.0381 (12)	0.0424 (12)	0.0665 (14)	0.0146 (9)	0.0167 (10)	0.0285 (11)
C7A	0.0496 (13)	0.0404 (12)	0.0642 (15)	0.0206 (10)	0.0292 (11)	0.0250 (11)
C8A	0.0396 (11)	0.0331 (11)	0.0393 (11)	0.0131 (9)	0.0198 (9)	0.0128 (9)
C9A	0.0495 (13)	0.0436 (12)	0.0410 (12)	0.0200 (10)	0.0221 (9)	0.0206 (10)
C10A	0.0465 (12)	0.0407 (12)	0.0414 (11)	0.0212 (9)	0.0191 (9)	0.0185 (10)
C11A	0.0424 (12)	0.0402 (12)	0.0454 (12)	0.0122 (9)	0.0155 (9)	0.0180 (10)
C12A	0.0393 (11)	0.0343 (11)	0.0369 (11)	0.0103 (9)	0.0105 (8)	0.0145 (9)
C13A	0.0428 (12)	0.0315 (11)	0.0460 (12)	0.0047 (9)	0.0141 (9)	0.0123 (9)
C14A	0.0485 (12)	0.0277 (10)	0.0378 (11)	0.0107 (9)	0.0118 (9)	0.0090 (9)
C15A	0.0418 (12)	0.0388 (12)	0.0426 (12)	0.0153 (9)	0.0162 (9)	0.0156 (10)
C16A	0.0409 (12)	0.0349 (11)	0.0527 (12)	0.0077 (9)	0.0168 (9)	0.0167 (10)
C17A	0.0441 (12)	0.0278 (10)	0.0377 (11)	0.0105 (9)	0.0091 (9)	0.0119 (9)
C18A	0.0485 (13)	0.0374 (12)	0.0404 (12)	0.0177 (10)	0.0113 (9)	0.0144 (10)
C19A	0.0850 (18)	0.0335 (12)	0.0700 (15)	0.0047 (11)	0.0184 (13)	0.0183 (11)
C1B	0.0388 (11)	0.0383 (11)	0.0457 (12)	0.0135 (9)	0.0167 (9)	0.0171 (10)
C2B	0.0468 (13)	0.0394 (12)	0.0457 (13)	0.0118 (10)	0.0113 (10)	0.0053 (10)
C3B	0.0434 (12)	0.0499 (13)	0.0409 (12)	0.0094 (10)	0.0063 (9)	0.0123 (10)
C4B	0.0312 (11)	0.0422 (12)	0.0444 (12)	0.0096 (9)	0.0132 (9)	0.0198 (10)
C5B	0.0392 (12)	0.0548 (14)	0.0523 (13)	0.0113 (10)	0.0117 (10)	0.0283 (11)
C6B	0.0423 (12)	0.0485 (13)	0.0667 (15)	0.0208 (10)	0.0196 (11)	0.0330 (12)
C7B	0.0484 (13)	0.0374 (12)	0.0576 (14)	0.0193 (10)	0.0268 (11)	0.0234 (11)
C8B	0.0383 (11)	0.0303 (10)	0.0388 (11)	0.0103 (8)	0.0164 (9)	0.0121 (9)
C9B	0.0403 (11)	0.0381 (11)	0.0367 (11)	0.0143 (9)	0.0111 (9)	0.0139 (9)
C10B	0.0424 (12)	0.0359 (11)	0.0398 (11)	0.0168 (9)	0.0149 (9)	0.0135 (9)
C11B	0.0421 (12)	0.0364 (11)	0.0462 (12)	0.0123 (9)	0.0184 (9)	0.0178 (9)
C12B	0.0401 (11)	0.0346 (11)	0.0355 (11)	0.0125 (9)	0.0129 (9)	0.0121 (9)
C13B	0.0457 (12)	0.0331 (11)	0.0426 (11)	0.0100 (9)	0.0181 (9)	0.0147 (9)
C14B	0.0498 (12)	0.0308 (10)	0.0367 (11)	0.0127 (9)	0.0135 (9)	0.0119 (9)
C15B	0.0457 (12)	0.0422 (12)	0.0366 (11)	0.0166 (9)	0.0192 (9)	0.0155 (9)
C16B	0.0474 (12)	0.0404 (12)	0.0463 (12)	0.0117 (9)	0.0219 (9)	0.0211 (10)
C17B	0.0433 (12)	0.0308 (11)	0.0400 (11)	0.0116 (9)	0.0119 (9)	0.0153 (9)
C18B	0.0441 (12)	0.0358 (12)	0.0491 (12)	0.0150 (9)	0.0113 (10)	0.0174 (10)
C19B	0.0914 (18)	0.0354 (12)	0.0614 (14)	0.0152 (11)	0.0331 (13)	0.0216 (11)
O1A	0.0660 (10)	0.0501 (9)	0.0538 (9)	0.0333 (7)	0.0335 (7)	0.0282 (7)
O1B	0.0613 (9)	0.0429 (8)	0.0482 (8)	0.0294 (7)	0.0238 (7)	0.0192 (7)
O2A	0.0629 (9)	0.0454 (8)	0.0472 (8)	0.0286 (7)	0.0284 (7)	0.0203 (7)
O3A	0.1042 (13)	0.0601 (10)	0.0692 (11)	0.0515 (9)	0.0498 (10)	0.0277 (9)
O4A	0.0625 (10)	0.0322 (8)	0.0603 (9)	0.0172 (7)	0.0142 (7)	0.0107 (7)
O5A	0.0480 (8)	0.0291 (7)	0.0572 (9)	0.0118 (6)	0.0200 (7)	0.0128 (7)
O6A	0.0576 (10)	0.0388 (9)	0.0806 (11)	0.0196 (7)	0.0374 (8)	0.0170 (9)
O7A	0.0640 (10)	0.0294 (8)	0.0684 (10)	0.0110 (7)	0.0284 (8)	0.0104 (7)
O2B	0.0502 (8)	0.0351 (8)	0.0452 (8)	0.0186 (6)	0.0150 (6)	0.0136 (6)
O3B	0.0805 (11)	0.0434 (9)	0.0607 (10)	0.0322 (8)	0.0276 (8)	0.0154 (8)
O4B	0.0606 (10)	0.0321 (8)	0.0806 (11)	0.0145 (7)	0.0231 (8)	0.0208 (8)
O5B	0.0530 (9)	0.0332 (7)	0.0609 (9)	0.0155 (6)	0.0262 (7)	0.0216 (7)
O6B	0.0720 (11)	0.0480 (10)	0.0654 (10)	0.0272 (8)	0.0446 (8)	0.0220 (8)
O7B	0.0690 (10)	0.0330 (8)	0.0588 (9)	0.0171 (7)	0.0339 (7)	0.0148 (7)

Geometric parameters (Å, º)

C1A—C9A	1.376 (2)	C1B—C2B	1.386 (2)
C1A—O1A	1.385 (2)	C1B—O1B	1.386 (2)
C1A—C2A	1.388 (2)	C2B—C3B	1.369 (3)
C2A—C3A	1.375 (3)	C2B—H2B	0.9300
C2A—H2A	0.9300	C3B—C4B	1.402 (2)
C3A—C4A	1.397 (2)	C3B—H3B	0.9300
C3A—H3A	0.9300	C4B—C8B	1.392 (2)
C4A—C8A	1.393 (2)	C4B—C5B	1.424 (3)
C4A—C5A	1.426 (3)	C5B—C6B	1.343 (2)
C5A—C6A	1.340 (2)	C5B—H5B	0.9300
C5A—H5A	0.9300	C6B—C7B	1.434 (3)
C6A—C7A	1.433 (3)	C6B—H6B	0.9300
C6A—H6A	0.9300	C7B—O3B	1.212 (2)
C7A—O3A	1.208 (2)	C7B—O2B	1.378 (2)
C7A—O2A	1.372 (2)	C8B—C9B	1.374 (2)
C8A—C9A	1.375 (2)	C8B—O2B	1.3817 (19)
C8A—O2A	1.3808 (19)	C9B—H9B	0.9300
C9A—H9A	0.9300	C10B—C11B	1.333 (2)
C10A—C11A	1.333 (2)	C10B—O1B	1.385 (2)
C10A—O1A	1.383 (2)	C10B—C18B	1.454 (3)
C10A—C18A	1.458 (3)	C11B—C12B	1.431 (2)
C11A—C12A	1.433 (2)	C11B—H11B	0.9300
C11A—H11A	0.9300	C12B—C17B	1.391 (2)
C12A—C17A	1.391 (2)	C12B—C13B	1.403 (2)
C12A—C13A	1.404 (2)	C13B—C14B	1.375 (2)
C13A—C14A	1.372 (2)	C13B—H13B	0.9300
C13A—H13A	0.9300	C14B—O7B	1.365 (2)
C14A—O7A	1.369 (2)	C14B—C15B	1.414 (2)
C14A—C15A	1.411 (2)	C15B—O6B	1.345 (2)
C15A—O6A	1.351 (2)	C15B—C16B	1.366 (2)
C15A—C16A	1.366 (2)	C16B—C17B	1.382 (2)
C16A—C17A	1.375 (2)	C16B—H16B	0.9300
C16A—H16A	0.9300	C17B—O5B	1.384 (2)
C17A—O5A	1.381 (2)	C18B—O4B	1.210 (2)
C18A—O4A	1.207 (2)	C18B—O5B	1.371 (2)
C18A—O5A	1.370 (2)	C19B—O7B	1.425 (2)
C19A—O7A	1.424 (2)	C19B—H19D	0.9600
C19A—H19A	0.9600	C19B—H19E	0.9600
C19A—H19B	0.9600	C19B—H19F	0.9600
C19A—H19C	0.9600	O6A—H6OA	0.88 (2)
C1B—C9B	1.379 (2)	O6B—H6OB	0.87 (2)
C9A—C1A—O1A	115.92 (17)	C1B—C2B—H2B	120.4
C9A—C1A—C2A	121.26 (19)	C2B—C3B—C4B	121.30 (19)
O1A—C1A—C2A	122.73 (17)	C2B—C3B—H3B	119.3
C3A—C2A—C1A	119.31 (18)	C4B—C3B—H3B	119.3
C3A—C2A—H2A	120.3	C8B—C4B—C3B	116.94 (18)
C1A—C2A—H2A	120.3	C8B—C4B—C5B	117.92 (18)
C2A—C3A—C4A	121.35 (18)	C3B—C4B—C5B	125.14 (18)
C2A—C3A—H3A	119.3	C6B—C5B—C4B	121.19 (19)
C4A—C3A—H3A	119.3	C6B—C5B—H5B	119.4
C8A—C4A—C3A	116.95 (19)	C4B—C5B—H5B	119.4
C8A—C4A—C5A	117.55 (17)	C5B—C6B—C7B	121.0 (2)
C3A—C4A—C5A	125.40 (19)	C5B—C6B—H6B	119.5
C6A—C5A—C4A	121.42 (19)	C7B—C6B—H6B	119.5
C6A—C5A—H5A	119.3	O3B—C7B—O2B	115.58 (19)
C4A—C5A—H5A	119.3	O3B—C7B—C6B	127.1 (2)
C5A—C6A—C7A	120.8 (2)	O2B—C7B—C6B	117.28 (18)
C5A—C6A—H6A	119.6	C9B—C8B—O2B	116.59 (17)
C7A—C6A—H6A	119.6	C9B—C8B—C4B	123.04 (18)
O3A—C7A—O2A	115.9 (2)	O2B—C8B—C4B	120.37 (17)
O3A—C7A—C6A	126.5 (2)	C8B—C9B—C1B	117.71 (18)
O2A—C7A—C6A	117.59 (18)	C8B—C9B—H9B	121.1
C9A—C8A—O2A	116.48 (17)	C1B—C9B—H9B	121.1
C9A—C8A—C4A	122.96 (17)	C11B—C10B—O1B	121.54 (17)
O2A—C8A—C4A	120.55 (17)	C11B—C10B—C18B	122.41 (17)
C8A—C9A—C1A	118.11 (18)	O1B—C10B—C18B	115.59 (16)
C8A—C9A—H9A	120.9	C10B—C11B—C12B	120.43 (17)
C1A—C9A—H9A	120.9	C10B—C11B—H11B	119.8
C11A—C10A—O1A	121.24 (17)	C12B—C11B—H11B	119.8
C11A—C10A—C18A	122.59 (18)	C17B—C12B—C13B	117.68 (16)
O1A—C10A—C18A	115.76 (16)	C17B—C12B—C11B	117.75 (17)
C10A—C11A—C12A	120.39 (18)	C13B—C12B—C11B	124.54 (17)
C10A—C11A—H11A	119.8	C14B—C13B—C12B	120.84 (17)
C12A—C11A—H11A	119.8	C14B—C13B—H13B	119.6
C17A—C12A—C13A	117.57 (17)	C12B—C13B—H13B	119.6
C17A—C12A—C11A	117.58 (17)	O7B—C14B—C13B	126.28 (17)
C13A—C12A—C11A	124.84 (17)	O7B—C14B—C15B	113.80 (16)
C14A—C13A—C12A	121.22 (17)	C13B—C14B—C15B	119.92 (17)
C14A—C13A—H13A	119.4	O6B—C15B—C16B	118.91 (17)
C12A—C13A—H13A	119.4	O6B—C15B—C14B	121.39 (17)
O7A—C14A—C13A	126.10 (17)	C16B—C15B—C14B	119.70 (17)
O7A—C14A—C15A	114.46 (16)	C15B—C16B—C17B	119.85 (17)
C13A—C14A—C15A	119.43 (17)	C15B—C16B—H16B	120.1
O6A—C15A—C16A	118.67 (17)	C17B—C16B—H16B	120.1
O6A—C15A—C14A	121.44 (17)	C16B—C17B—O5B	117.11 (16)
C16A—C15A—C14A	119.89 (17)	C16B—C17B—C12B	122.01 (17)
C15A—C16A—C17A	120.14 (17)	O5B—C17B—C12B	120.87 (16)
C15A—C16A—H16A	119.9	O4B—C18B—O5B	118.08 (18)
C17A—C16A—H16A	119.9	O4B—C18B—C10B	126.08 (19)
C16A—C17A—O5A	117.22 (16)	O5B—C18B—C10B	115.84 (16)
C16A—C17A—C12A	121.76 (17)	O7B—C19B—H19D	109.5
O5A—C17A—C12A	121.02 (16)	O7B—C19B—H19E	109.5
O4A—C18A—O5A	118.28 (17)	H19D—C19B—H19E	109.5
O4A—C18A—C10A	126.23 (18)	O7B—C19B—H19F	109.5
O5A—C18A—C10A	115.49 (16)	H19D—C19B—H19F	109.5
O7A—C19A—H19A	109.5	H19E—C19B—H19F	109.5
O7A—C19A—H19B	109.5	C10A—O1A—C1A	118.73 (14)
H19A—C19A—H19B	109.5	C10B—O1B—C1B	118.17 (14)
O7A—C19A—H19C	109.5	C7A—O2A—C8A	122.09 (16)
H19A—C19A—H19C	109.5	C18A—O5A—C17A	122.91 (14)
H19B—C19A—H19C	109.5	C15A—O6A—H6OA	114.8 (14)
C9B—C1B—C2B	121.64 (19)	C14A—O7A—C19A	117.09 (15)
C9B—C1B—O1B	116.38 (17)	C7B—O2B—C8B	122.18 (15)
C2B—C1B—O1B	121.86 (17)	C18B—O5B—C17B	122.62 (15)
C3B—C2B—C1B	119.29 (19)	C15B—O6B—H6OB	112.7 (15)
C3B—C2B—H2B	120.4	C14B—O7B—C19B	117.10 (14)
C9A—C1A—C2A—C3A	1.8 (3)	O2B—C8B—C9B—C1B	−177.95 (14)
O1A—C1A—C2A—C3A	−174.76 (16)	C4B—C8B—C9B—C1B	2.2 (3)
C1A—C2A—C3A—C4A	−1.4 (3)	C2B—C1B—C9B—C8B	0.0 (3)
C2A—C3A—C4A—C8A	−0.6 (3)	O1B—C1B—C9B—C8B	−176.13 (15)
C2A—C3A—C4A—C5A	−176.83 (16)	O1B—C10B—C11B—C12B	−171.73 (17)
C8A—C4A—C5A—C6A	−1.3 (3)	C18B—C10B—C11B—C12B	0.2 (3)
C3A—C4A—C5A—C6A	174.96 (16)	C10B—C11B—C12B—C17B	−0.3 (3)
C4A—C5A—C6A—C7A	1.8 (3)	C10B—C11B—C12B—C13B	177.68 (17)
C5A—C6A—C7A—O3A	179.22 (19)	C17B—C12B—C13B—C14B	−0.5 (3)
C5A—C6A—C7A—O2A	−0.8 (3)	C11B—C12B—C13B—C14B	−178.45 (18)
C3A—C4A—C8A—C9A	2.3 (3)	C12B—C13B—C14B—O7B	−178.89 (16)
C5A—C4A—C8A—C9A	178.90 (17)	C12B—C13B—C14B—C15B	0.4 (3)
C3A—C4A—C8A—O2A	−176.66 (15)	O7B—C14B—C15B—O6B	−0.5 (3)
C5A—C4A—C8A—O2A	−0.1 (2)	C13B—C14B—C15B—O6B	−179.91 (18)
O2A—C8A—C9A—C1A	177.04 (15)	O7B—C14B—C15B—C16B	179.33 (17)
C4A—C8A—C9A—C1A	−2.0 (3)	C13B—C14B—C15B—C16B	0.0 (3)
O1A—C1A—C9A—C8A	176.66 (15)	O6B—C15B—C16B—C17B	179.61 (18)
C2A—C1A—C9A—C8A	−0.1 (3)	C14B—C15B—C16B—C17B	−0.3 (3)
O1A—C10A—C11A—C12A	172.67 (16)	C15B—C16B—C17B—O5B	179.77 (16)
C18A—C10A—C11A—C12A	0.4 (3)	C15B—C16B—C17B—C12B	0.2 (3)
C10A—C11A—C12A—C17A	−0.4 (3)	C13B—C12B—C17B—C16B	0.2 (3)
C10A—C11A—C12A—C13A	−179.26 (17)	C11B—C12B—C17B—C16B	178.29 (18)
C17A—C12A—C13A—C14A	0.9 (3)	C13B—C12B—C17B—O5B	−179.40 (16)
C11A—C12A—C13A—C14A	179.72 (18)	C11B—C12B—C17B—O5B	−1.3 (3)
C12A—C13A—C14A—O7A	178.25 (17)	C11B—C10B—C18B—O4B	−178.1 (2)
C12A—C13A—C14A—C15A	−0.5 (3)	O1B—C10B—C18B—O4B	−5.7 (3)
O7A—C14A—C15A—O6A	0.6 (3)	C11B—C10B—C18B—O5B	1.4 (3)
C13A—C14A—C15A—O6A	179.55 (18)	O1B—C10B—C18B—O5B	173.82 (15)
O7A—C14A—C15A—C16A	−178.95 (17)	C11A—C10A—O1A—C1A	123.6 (2)
C13A—C14A—C15A—C16A	0.0 (3)	C18A—C10A—O1A—C1A	−63.6 (2)
O6A—C15A—C16A—C17A	−179.33 (18)	C9A—C1A—O1A—C10A	153.95 (16)
C14A—C15A—C16A—C17A	0.3 (3)	C2A—C1A—O1A—C10A	−29.3 (3)
C15A—C16A—C17A—O5A	179.74 (16)	C11B—C10B—O1B—C1B	−127.07 (19)
C15A—C16A—C17A—C12A	0.1 (3)	C18B—C10B—O1B—C1B	60.5 (2)
C13A—C12A—C17A—C16A	−0.6 (3)	C9B—C1B—O1B—C10B	−144.91 (16)
C11A—C12A—C17A—C16A	−179.57 (18)	C2B—C1B—O1B—C10B	38.9 (2)
C13A—C12A—C17A—O5A	179.73 (16)	O3A—C7A—O2A—C8A	179.40 (16)
C11A—C12A—C17A—O5A	0.8 (3)	C6A—C7A—O2A—C8A	−0.5 (3)
C11A—C10A—C18A—O4A	178.6 (2)	C9A—C8A—O2A—C7A	−178.06 (16)
O1A—C10A—C18A—O4A	5.9 (3)	C4A—C8A—O2A—C7A	1.0 (2)
C11A—C10A—C18A—O5A	−0.7 (3)	O4A—C18A—O5A—C17A	−178.28 (15)
O1A—C10A—C18A—O5A	−173.38 (16)	C10A—C18A—O5A—C17A	1.1 (3)
C9B—C1B—C2B—C3B	−1.8 (3)	C16A—C17A—O5A—C18A	179.15 (17)
O1B—C1B—C2B—C3B	174.19 (17)	C12A—C17A—O5A—C18A	−1.2 (3)
C1B—C2B—C3B—C4B	1.4 (3)	C13A—C14A—O7A—C19A	18.7 (3)
C2B—C3B—C4B—C8B	0.7 (3)	C15A—C14A—O7A—C19A	−162.49 (17)
C2B—C3B—C4B—C5B	−179.57 (18)	O3B—C7B—O2B—C8B	−179.33 (14)
C8B—C4B—C5B—C6B	2.3 (3)	C6B—C7B—O2B—C8B	1.0 (2)
C3B—C4B—C5B—C6B	−177.40 (17)	C9B—C8B—O2B—C7B	−179.39 (16)
C4B—C5B—C6B—C7B	−0.8 (3)	C4B—C8B—O2B—C7B	0.5 (2)
C5B—C6B—C7B—O3B	179.56 (19)	O4B—C18B—O5B—C17B	176.54 (16)
C5B—C6B—C7B—O2B	−0.9 (3)	C10B—C18B—O5B—C17B	−3.1 (3)
C3B—C4B—C8B—C9B	−2.5 (3)	C16B—C17B—O5B—C18B	−176.48 (17)
C5B—C4B—C8B—C9B	177.71 (16)	C12B—C17B—O5B—C18B	3.1 (3)
C3B—C4B—C8B—O2B	177.60 (15)	C13B—C14B—O7B—C19B	−1.5 (3)
C5B—C4B—C8B—O2B	−2.2 (2)	C15B—C14B—O7B—C19B	179.13 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6A—H6OA···O3B^i	0.88 (2)	1.93 (2)	2.750 (2)	153 (2)
O6B—H6OB···O3A^ii	0.87 (2)	1.95 (2)	2.776 (2)	157 (2)

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