Methyl 5,7-dihydr-oxy-2,2,9-trimethyl-6,11-dioxo-6,11-dihydro-2H-anthra[2,3-b]pyran-8-carboxyl-ate.

The title compound, C(22)H(18)O(7), also known as laurentiquinone B, is a new anthraquinone which was isolated from Vismia laurentii, a Cameroonian medicinal plant. The asymmetric unit contains two independent mol-ecules. Each of them contains four fused rings, three of which are coplanar and typical of anthracene, while the heterocyclic rings adopt envelope conformations. Intra-molecular O-H⋯O hydrogen bonds result in the formation of two planar rings, which are also almost coplanar with the adjacent rings. In the crystal structure, inter-molecular O-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules and a π-π contact is also present [centroid-centroid distance = 3.967 (3) Å].

Related literature

For the biosynthesis of anthraquinones, see: Birch et al. (1965 ▶); Shibata & Ikekawa (1963 ▶). For the bioactivity of anthraquinones, see: ; Adwankar & Chitnis (1982 ▶); Sittie et al. (1999 ▶); Rath et al. (1995 ▶); Ismail et al. (1997 ▶); Nagem & de Oliveira (1997 ▶); Nguemeving et al. (2006 ▶). For the pharmacology of Vismia laurentii, see: Kerharo (1974 ▶); Macfoy & Sama (1983 ▶). For other classes of natural products isolated from Vismia species, see: Simmonds et al. (1985 ▶); Nagem & de Oliveira (1997 ▶); Seo et al. (2000 ▶); Nguemeving et al. (2006 ▶). For related structures, see: Noungoue et al. (2008 ▶).

Experimental

Crystal data

C22H18O7

M = 394.36

Triclinic,

a = 6.9234 (4) Å

b = 16.0765 (9) Å

c = 17.5304 (9) Å

α = 108.746 (2)°

β = 98.725 (3)°

γ = 94.147 (2)°

V = 1810.97 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 173 (2) K

0.30 × 0.20 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: none

17235 measured reflections

8260 independent reflections

4538 reflections with I > 2σ(I)

R int = 0.062

Refinement

R[F 2 > 2σ(F 2)] = 0.072

wR(F 2) = 0.171

S = 1.02

8260 reflections

547 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.25 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680803794X/hk2545sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680803794X/hk2545Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C22H18O7	Z = 4
Mr = 394.36	F000 = 824
Triclinic, P1	Dx = 1.446 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 6.9234 (4) Å	Cell parameters from 8986 reflections
b = 16.0765 (9) Å	θ = 1.0–27.5º
c = 17.5304 (9) Å	µ = 0.11 mm−1
α = 108.746 (2)º	T = 173 (2) K
β = 98.725 (3)º	Plate, orange
γ = 94.147 (2)º	0.30 × 0.20 × 0.15 mm
V = 1810.97 (17) Å3

Nonius KappaCCD diffractometer	4538 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.062
Monochromator: graphite	θmax = 27.6º
T = 173(2) K	θmin = 1.3º
φ and ω scans	h = −8→6
Absorption correction: none	k = −20→20
17235 measured reflections	l = −22→22
8260 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.072	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.171	w = 1/[σ2(Fo2) + (0.0685P)2 + 0.3328P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
8260 reflections	Δρmax = 0.28 e Å−3
547 parameters	Δρmin = −0.24 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
O1	0.9256 (3)	0.20606 (10)	0.34068 (10)	0.0353 (4)
O2	0.7679 (3)	0.44308 (11)	0.55456 (9)	0.0297 (4)
H2O	0.742 (4)	0.498 (2)	0.5634 (18)	0.069 (10)*
O3	0.6830 (2)	0.58232 (10)	0.52267 (9)	0.0284 (4)
O4	0.5973 (3)	0.72378 (11)	0.49464 (9)	0.0311 (4)
H4O	0.614 (5)	0.682 (2)	0.5196 (19)	0.082 (11)*
O5	0.6860 (3)	0.89104 (11)	0.42063 (12)	0.0494 (5)
O6	0.3755 (3)	0.82417 (10)	0.38316 (10)	0.0371 (4)
O7	0.8008 (3)	0.43662 (10)	0.21238 (9)	0.0335 (4)
O8	0.3921 (3)	0.20125 (10)	0.08818 (10)	0.0375 (5)
O9	0.2613 (3)	0.45070 (11)	0.29753 (9)	0.0310 (4)
H9O	0.231 (5)	0.507 (2)	0.3026 (19)	0.078 (11)*
O10	0.1911 (2)	0.58838 (10)	0.26044 (9)	0.0298 (4)
O11	0.1139 (3)	0.72764 (11)	0.22628 (10)	0.0327 (4)
H11O	0.128 (5)	0.689 (2)	0.252 (2)	0.092 (13)*
O12	0.1994 (3)	0.88730 (12)	0.15164 (14)	0.0650 (7)
O13	−0.1093 (3)	0.81995 (10)	0.10974 (10)	0.0352 (4)
O14	0.2996 (2)	0.42633 (10)	−0.04866 (9)	0.0311 (4)
C1	0.9107 (4)	0.14397 (15)	0.38645 (15)	0.0335 (6)
C2	0.9295 (4)	0.19223 (15)	0.47656 (14)	0.0312 (6)
H2	0.9744	0.1633	0.5141	0.037*
C3	0.8851 (3)	0.27426 (15)	0.50542 (14)	0.0284 (6)
H3	0.8830	0.3005	0.5621	0.034*
C4	0.8398 (3)	0.32371 (14)	0.44995 (13)	0.0238 (5)
C5	0.7869 (3)	0.40951 (14)	0.47550 (13)	0.0231 (5)
C6	0.7611 (3)	0.45848 (14)	0.42189 (13)	0.0232 (5)
C7	0.7075 (3)	0.54731 (14)	0.44998 (13)	0.0227 (5)
C8	0.6849 (3)	0.59752 (14)	0.39322 (13)	0.0234 (5)
C9	0.6330 (3)	0.68391 (14)	0.41885 (13)	0.0252 (5)
C10	0.6215 (3)	0.73234 (14)	0.36560 (14)	0.0256 (5)
C11	0.6576 (3)	0.69623 (15)	0.28607 (14)	0.0255 (5)
C12	0.7058 (3)	0.61005 (15)	0.26013 (14)	0.0256 (5)
H12	0.7294	0.5847	0.2060	0.031*
C13	0.7199 (3)	0.56095 (14)	0.31249 (13)	0.0236 (5)
C14	0.7733 (3)	0.46976 (14)	0.28247 (13)	0.0245 (5)
C15	0.7928 (3)	0.41905 (14)	0.34075 (13)	0.0235 (5)
C16	0.8462 (3)	0.33469 (14)	0.31475 (13)	0.0255 (5)
H16	0.8686	0.3091	0.2604	0.031*
C17	0.8669 (3)	0.28760 (14)	0.36917 (14)	0.0267 (5)
C18	0.7102 (4)	0.08818 (18)	0.35335 (17)	0.0492 (8)
H18A	0.6065	0.1265	0.3641	0.074*
H18B	0.6984	0.0439	0.3805	0.074*
H18C	0.6965	0.0582	0.2941	0.074*
C19	1.0782 (4)	0.08948 (17)	0.36805 (17)	0.0479 (7)
H19A	1.0675	0.0631	0.3086	0.072*
H19B	1.0711	0.0424	0.3921	0.072*
H19C	1.2043	0.1277	0.3916	0.072*
C20	0.5689 (4)	0.82504 (16)	0.39418 (14)	0.0310 (6)
C21	0.3033 (4)	0.90901 (17)	0.39716 (18)	0.0502 (8)
H21A	0.3422	0.9449	0.4553	0.075*
H21B	0.1592	0.8999	0.3818	0.075*
H21C	0.3594	0.9397	0.3639	0.075*
C22	0.6469 (4)	0.75002 (16)	0.22934 (15)	0.0346 (6)
H22A	0.5282	0.7797	0.2322	0.052*
H22B	0.6419	0.7107	0.1730	0.052*
H22C	0.7637	0.7945	0.2460	0.052*
C23	0.3687 (4)	0.14102 (15)	0.13466 (15)	0.0362 (6)
C24	0.3587 (4)	0.18934 (17)	0.22190 (16)	0.0390 (7)
H24	0.3704	0.1574	0.2591	0.047*
C25	0.3347 (4)	0.27396 (16)	0.25069 (15)	0.0354 (6)
H25	0.3259	0.3010	0.3066	0.042*
C26	0.3219 (3)	0.32519 (15)	0.19542 (13)	0.0250 (5)
C27	0.2816 (3)	0.41312 (15)	0.21919 (13)	0.0239 (5)
C28	0.2650 (3)	0.46045 (14)	0.16364 (13)	0.0219 (5)
C29	0.2162 (3)	0.54995 (14)	0.18846 (13)	0.0238 (5)
C30	0.1976 (3)	0.59654 (14)	0.12902 (13)	0.0236 (5)
C31	0.1486 (3)	0.68315 (15)	0.15087 (13)	0.0258 (5)
C32	0.1365 (3)	0.72859 (14)	0.09460 (14)	0.0257 (5)
C33	0.1732 (3)	0.68879 (15)	0.01611 (14)	0.0254 (5)
C34	0.2184 (3)	0.60181 (15)	−0.00646 (13)	0.0255 (5)
H34	0.2415	0.5737	−0.0603	0.031*
C35	0.2301 (3)	0.55620 (14)	0.04830 (13)	0.0229 (5)
C36	0.2777 (3)	0.46361 (14)	0.02161 (13)	0.0234 (5)
C37	0.2963 (3)	0.41710 (14)	0.08309 (13)	0.0223 (5)
C38	0.3410 (3)	0.33106 (14)	0.05955 (14)	0.0249 (5)
H38	0.3651	0.3032	0.0058	0.030*
C39	0.3502 (3)	0.28573 (14)	0.11525 (14)	0.0254 (5)
C40	0.1808 (5)	0.0794 (2)	0.0916 (2)	0.0791 (12)
H40A	0.0681	0.1130	0.0972	0.119*
H40B	0.1666	0.0331	0.1162	0.119*
H40C	0.1857	0.0522	0.0333	0.119*
C41	0.5481 (5)	0.0925 (2)	0.12807 (19)	0.0678 (10)
H41A	0.5594	0.0673	0.0703	0.102*
H41B	0.5347	0.0448	0.1512	0.102*
H41C	0.6665	0.1340	0.1585	0.102*
C42	0.0842 (4)	0.82113 (16)	0.12240 (14)	0.0315 (6)
C43	−0.1864 (4)	0.90363 (17)	0.13526 (18)	0.0479 (8)
H43A	−0.1394	0.9338	0.1942	0.072*
H43B	−0.3308	0.8932	0.1239	0.072*
H43C	−0.1415	0.9407	0.1050	0.072*
C44	0.1659 (4)	0.73895 (16)	−0.04345 (15)	0.0332 (6)
H44A	0.0585	0.7756	−0.0370	0.050*
H44B	0.1433	0.6969	−0.0996	0.050*
H44C	0.2913	0.7769	−0.0325	0.050*

	U11	U22	U33	U12	U13	U23
O1	0.0528 (12)	0.0233 (9)	0.0364 (10)	0.0154 (8)	0.0186 (9)	0.0120 (8)
O2	0.0440 (11)	0.0264 (10)	0.0218 (9)	0.0105 (8)	0.0097 (8)	0.0092 (7)
O3	0.0379 (10)	0.0267 (9)	0.0224 (8)	0.0108 (7)	0.0100 (8)	0.0071 (7)
O4	0.0419 (11)	0.0255 (9)	0.0272 (9)	0.0099 (8)	0.0115 (8)	0.0071 (8)
O5	0.0432 (12)	0.0245 (10)	0.0737 (14)	0.0003 (9)	−0.0003 (10)	0.0132 (9)
O6	0.0349 (11)	0.0276 (9)	0.0510 (11)	0.0134 (8)	0.0081 (9)	0.0140 (8)
O7	0.0500 (12)	0.0301 (9)	0.0241 (9)	0.0116 (8)	0.0146 (8)	0.0091 (7)
O8	0.0563 (12)	0.0222 (9)	0.0423 (10)	0.0125 (8)	0.0219 (9)	0.0147 (8)
O9	0.0422 (11)	0.0325 (10)	0.0221 (9)	0.0114 (8)	0.0089 (8)	0.0116 (8)
O10	0.0404 (11)	0.0280 (9)	0.0232 (8)	0.0100 (8)	0.0106 (8)	0.0084 (7)
O11	0.0472 (12)	0.0268 (9)	0.0256 (9)	0.0156 (8)	0.0108 (8)	0.0067 (8)
O12	0.0509 (14)	0.0246 (11)	0.1069 (18)	−0.0017 (10)	0.0025 (13)	0.0118 (11)
O13	0.0359 (11)	0.0254 (9)	0.0455 (10)	0.0130 (8)	0.0104 (9)	0.0103 (8)
O14	0.0425 (11)	0.0295 (9)	0.0234 (9)	0.0103 (8)	0.0106 (8)	0.0084 (7)
C1	0.0412 (16)	0.0256 (13)	0.0380 (14)	0.0107 (11)	0.0058 (12)	0.0159 (11)
C2	0.0339 (15)	0.0311 (14)	0.0340 (14)	0.0103 (11)	0.0055 (12)	0.0174 (11)
C3	0.0268 (14)	0.0310 (14)	0.0315 (13)	0.0065 (11)	0.0060 (11)	0.0150 (11)
C4	0.0233 (13)	0.0229 (12)	0.0270 (12)	0.0034 (10)	0.0065 (10)	0.0099 (10)
C5	0.0238 (13)	0.0239 (12)	0.0212 (12)	0.0032 (10)	0.0056 (10)	0.0065 (10)
C6	0.0236 (13)	0.0227 (12)	0.0237 (12)	0.0030 (10)	0.0061 (10)	0.0074 (10)
C7	0.0208 (12)	0.0227 (12)	0.0245 (12)	0.0018 (10)	0.0050 (10)	0.0076 (10)
C8	0.0232 (13)	0.0221 (12)	0.0264 (12)	0.0045 (10)	0.0063 (10)	0.0091 (10)
C9	0.0238 (13)	0.0222 (12)	0.0284 (12)	0.0005 (10)	0.0061 (11)	0.0067 (10)
C10	0.0231 (13)	0.0207 (12)	0.0321 (13)	0.0025 (10)	0.0046 (11)	0.0083 (10)
C11	0.0237 (13)	0.0261 (13)	0.0301 (13)	0.0030 (10)	0.0057 (11)	0.0139 (10)
C12	0.0243 (13)	0.0279 (13)	0.0266 (12)	0.0041 (10)	0.0067 (10)	0.0108 (10)
C13	0.0206 (13)	0.0259 (12)	0.0260 (12)	0.0037 (10)	0.0072 (10)	0.0096 (10)
C14	0.0246 (13)	0.0245 (13)	0.0233 (12)	0.0024 (10)	0.0065 (10)	0.0059 (10)
C15	0.0243 (13)	0.0226 (12)	0.0248 (12)	0.0023 (10)	0.0071 (10)	0.0088 (10)
C16	0.0299 (14)	0.0240 (12)	0.0241 (12)	0.0046 (10)	0.0095 (11)	0.0080 (10)
C17	0.0281 (14)	0.0218 (12)	0.0310 (13)	0.0053 (10)	0.0080 (11)	0.0084 (10)
C18	0.055 (2)	0.0458 (17)	0.0454 (17)	−0.0039 (15)	−0.0032 (15)	0.0207 (14)
C19	0.063 (2)	0.0366 (16)	0.0481 (17)	0.0264 (14)	0.0138 (15)	0.0131 (13)
C20	0.0345 (15)	0.0311 (14)	0.0287 (13)	0.0050 (12)	0.0037 (12)	0.0129 (11)
C21	0.053 (2)	0.0341 (16)	0.071 (2)	0.0217 (14)	0.0164 (16)	0.0229 (15)
C22	0.0397 (16)	0.0339 (14)	0.0365 (14)	0.0070 (12)	0.0093 (12)	0.0188 (12)
C23	0.0480 (18)	0.0236 (13)	0.0411 (15)	0.0041 (12)	0.0049 (13)	0.0180 (12)
C24	0.0464 (17)	0.0383 (16)	0.0457 (16)	0.0127 (13)	0.0159 (14)	0.0275 (13)
C25	0.0425 (16)	0.0369 (15)	0.0356 (14)	0.0122 (12)	0.0154 (13)	0.0190 (12)
C26	0.0218 (13)	0.0284 (13)	0.0284 (12)	0.0043 (10)	0.0054 (10)	0.0137 (10)
C27	0.0236 (13)	0.0281 (13)	0.0205 (11)	0.0045 (10)	0.0050 (10)	0.0084 (10)
C28	0.0212 (13)	0.0223 (12)	0.0217 (11)	0.0024 (10)	0.0024 (10)	0.0073 (10)
C29	0.0208 (13)	0.0262 (13)	0.0232 (12)	0.0024 (10)	0.0043 (10)	0.0067 (10)
C30	0.0230 (13)	0.0228 (12)	0.0242 (12)	0.0017 (10)	0.0039 (10)	0.0075 (10)
C31	0.0249 (14)	0.0269 (13)	0.0240 (12)	0.0034 (10)	0.0039 (10)	0.0067 (10)
C32	0.0245 (13)	0.0209 (12)	0.0317 (13)	0.0031 (10)	0.0038 (11)	0.0095 (10)
C33	0.0222 (13)	0.0268 (13)	0.0285 (12)	0.0017 (10)	0.0031 (10)	0.0121 (10)
C34	0.0243 (13)	0.0293 (13)	0.0251 (12)	0.0041 (10)	0.0069 (10)	0.0112 (10)
C35	0.0186 (12)	0.0249 (12)	0.0246 (12)	0.0024 (10)	0.0041 (10)	0.0075 (10)
C36	0.0199 (12)	0.0273 (13)	0.0233 (12)	0.0022 (10)	0.0051 (10)	0.0087 (10)
C37	0.0211 (12)	0.0231 (12)	0.0235 (12)	0.0014 (10)	0.0064 (10)	0.0081 (10)
C38	0.0241 (13)	0.0238 (12)	0.0254 (12)	0.0016 (10)	0.0049 (10)	0.0067 (10)
C39	0.0229 (13)	0.0209 (12)	0.0326 (13)	0.0039 (10)	0.0067 (11)	0.0084 (10)
C40	0.085 (3)	0.073 (2)	0.075 (2)	−0.041 (2)	−0.019 (2)	0.045 (2)
C41	0.098 (3)	0.070 (2)	0.0523 (19)	0.059 (2)	0.0272 (19)	0.0272 (17)
C42	0.0387 (16)	0.0264 (14)	0.0319 (14)	0.0052 (12)	0.0070 (12)	0.0126 (11)
C43	0.061 (2)	0.0297 (15)	0.0617 (19)	0.0253 (14)	0.0266 (16)	0.0164 (13)
C44	0.0368 (15)	0.0319 (14)	0.0375 (14)	0.0086 (11)	0.0103 (12)	0.0185 (12)

O2—H2O	0.88 (3)	C22—H22B	0.9800
O4—H4O	0.91 (3)	C22—H22C	0.9800
O9—H9O	0.92 (3)	C23—O8	1.467 (3)
O11—H11O	0.88 (3)	C23—C24	1.491 (3)
C1—O1	1.475 (3)	C23—C40	1.509 (4)
C1—C2	1.500 (3)	C23—C41	1.514 (4)
C1—C19	1.515 (3)	C24—C25	1.323 (3)
C1—C18	1.520 (3)	C24—H24	0.9500
C2—C3	1.329 (3)	C25—C26	1.457 (3)
C2—H2	0.9500	C25—H25	0.9500
C3—C4	1.455 (3)	C26—C39	1.395 (3)
C3—H3	0.9500	C26—C27	1.401 (3)
C4—C17	1.395 (3)	C27—O9	1.345 (2)
C4—C5	1.401 (3)	C27—C28	1.413 (3)
C5—O2	1.347 (2)	C28—C37	1.417 (3)
C5—C6	1.407 (3)	C28—C29	1.444 (3)
C6—C15	1.417 (3)	C29—O10	1.259 (2)
C6—C7	1.449 (3)	C29—C30	1.462 (3)
C7—O3	1.260 (2)	C30—C31	1.402 (3)
C7—C8	1.467 (3)	C30—C35	1.415 (3)
C8—C9	1.407 (3)	C31—O11	1.353 (3)
C8—C13	1.413 (3)	C31—C32	1.400 (3)
C9—O4	1.346 (3)	C32—C33	1.390 (3)
C9—C10	1.392 (3)	C32—C42	1.499 (3)
C10—C11	1.396 (3)	C33—C34	1.398 (3)
C10—C20	1.503 (3)	C33—C44	1.508 (3)
C11—C12	1.395 (3)	C34—C35	1.380 (3)
C11—C22	1.511 (3)	C34—H34	0.9500
C12—C13	1.387 (3)	C35—C36	1.488 (3)
C12—H12	0.9500	C36—O14	1.223 (2)
C13—C14	1.485 (3)	C36—C37	1.492 (3)
C14—O7	1.223 (2)	C37—C38	1.383 (3)
C14—C15	1.495 (3)	C38—C39	1.391 (3)
C15—C16	1.382 (3)	C38—H38	0.9500
C16—C17	1.394 (3)	C39—O8	1.356 (3)
C16—H16	0.9500	C40—H40A	0.9800
C17—O1	1.360 (3)	C40—H40B	0.9800
C18—H18A	0.9800	C40—H40C	0.9800
C18—H18B	0.9800	C41—H41A	0.9800
C18—H18C	0.9800	C41—H41B	0.9800
C19—H19A	0.9800	C41—H41C	0.9800
C19—H19B	0.9800	C42—O12	1.197 (3)
C19—H19C	0.9800	C42—O13	1.322 (3)
C20—O5	1.201 (3)	C43—O13	1.444 (3)
C20—O6	1.322 (3)	C43—H43A	0.9800
C21—O6	1.446 (3)	C43—H43B	0.9800
C21—H21A	0.9800	C43—H43C	0.9800
C21—H21B	0.9800	C44—H44A	0.9800
C21—H21C	0.9800	C44—H44B	0.9800
C22—H22A	0.9800	C44—H44C	0.9800
C17—O1—C1	120.10 (17)	H22A—C22—H22B	109.5
C5—O2—H2O	107.1 (19)	C11—C22—H22C	109.5
C9—O4—H4O	104 (2)	H22A—C22—H22C	109.5
C20—O6—C21	116.6 (2)	H22B—C22—H22C	109.5
C39—O8—C23	121.75 (17)	O8—C23—C24	112.24 (19)
C27—O9—H9O	106.2 (19)	O8—C23—C40	106.2 (2)
C31—O11—H11O	103 (2)	C24—C23—C40	110.8 (2)
C42—O13—C43	117.9 (2)	O8—C23—C41	104.3 (2)
O1—C1—C2	111.49 (18)	C24—C23—C41	111.3 (2)
O1—C1—C19	104.25 (18)	C40—C23—C41	111.8 (3)
C2—C1—C19	111.7 (2)	C25—C24—C23	124.1 (2)
O1—C1—C18	107.4 (2)	C25—C24—H24	118.0
C2—C1—C18	109.5 (2)	C23—C24—H24	118.0
C19—C1—C18	112.2 (2)	C24—C25—C26	119.1 (2)
C3—C2—C1	122.0 (2)	C24—C25—H25	120.4
C3—C2—H2	119.0	C26—C25—H25	120.4
C1—C2—H2	119.0	C39—C26—C27	118.0 (2)
C2—C3—C4	119.8 (2)	C39—C26—C25	119.2 (2)
C2—C3—H3	120.1	C27—C26—C25	122.8 (2)
C4—C3—H3	120.1	O9—C27—C26	116.96 (19)
C17—C4—C5	118.0 (2)	O9—C27—C28	121.5 (2)
C17—C4—C3	118.7 (2)	C26—C27—C28	121.56 (19)
C5—C4—C3	123.07 (19)	C27—C28—C37	117.9 (2)
O2—C5—C4	116.25 (19)	C27—C28—C29	120.72 (19)
O2—C5—C6	122.1 (2)	C37—C28—C29	121.40 (19)
C4—C5—C6	121.58 (19)	O10—C29—C28	121.0 (2)
C5—C6—C15	118.1 (2)	O10—C29—C30	119.8 (2)
C5—C6—C7	120.50 (19)	C28—C29—C30	119.24 (18)
C15—C6—C7	121.4 (2)	C31—C30—C35	118.1 (2)
O3—C7—C6	120.89 (19)	C31—C30—C29	120.71 (19)
O3—C7—C8	119.7 (2)	C35—C30—C29	121.2 (2)
C6—C7—C8	119.38 (19)	O11—C31—C32	116.6 (2)
C9—C8—C13	118.7 (2)	O11—C31—C30	122.8 (2)
C9—C8—C7	120.59 (19)	C32—C31—C30	120.61 (19)
C13—C8—C7	120.6 (2)	C33—C32—C31	120.7 (2)
O4—C9—C10	117.4 (2)	C33—C32—C42	121.7 (2)
O4—C9—C8	122.6 (2)	C31—C32—C42	117.63 (19)
C10—C9—C8	119.9 (2)	C32—C33—C34	118.9 (2)
C9—C10—C11	121.2 (2)	C32—C33—C44	120.5 (2)
C9—C10—C20	119.4 (2)	C34—C33—C44	120.6 (2)
C11—C10—C20	119.4 (2)	C35—C34—C33	121.0 (2)
C12—C11—C10	119.0 (2)	C35—C34—H34	119.5
C12—C11—C22	120.5 (2)	C33—C34—H34	119.5
C10—C11—C22	120.5 (2)	C34—C35—C30	120.7 (2)
C13—C12—C11	120.8 (2)	C34—C35—C36	119.22 (19)
C13—C12—H12	119.6	C30—C35—C36	120.04 (19)
C11—C12—H12	119.6	O14—C36—C35	121.2 (2)
C12—C13—C8	120.4 (2)	O14—C36—C37	120.8 (2)
C12—C13—C14	118.95 (19)	C35—C36—C37	117.98 (18)
C8—C13—C14	120.66 (19)	C38—C37—C28	121.0 (2)
O7—C14—C13	121.5 (2)	C38—C37—C36	118.88 (19)
O7—C14—C15	120.6 (2)	C28—C37—C36	120.08 (19)
C13—C14—C15	117.95 (18)	C37—C38—C39	119.4 (2)
C16—C15—C6	121.0 (2)	C37—C38—H38	120.3
C16—C15—C14	119.04 (19)	C39—C38—H38	120.3
C6—C15—C14	119.9 (2)	O8—C39—C38	116.58 (19)
C15—C16—C17	119.2 (2)	O8—C39—C26	121.3 (2)
C15—C16—H16	120.4	C38—C39—C26	122.1 (2)
C17—C16—H16	120.4	C23—C40—H40A	109.5
O1—C17—C16	116.38 (19)	C23—C40—H40B	109.5
O1—C17—C4	121.5 (2)	H40A—C40—H40B	109.5
C16—C17—C4	122.0 (2)	C23—C40—H40C	109.5
C1—C18—H18A	109.5	H40A—C40—H40C	109.5
C1—C18—H18B	109.5	H40B—C40—H40C	109.5
H18A—C18—H18B	109.5	C23—C41—H41A	109.5
C1—C18—H18C	109.5	C23—C41—H41B	109.5
H18A—C18—H18C	109.5	H41A—C41—H41B	109.5
H18B—C18—H18C	109.5	C23—C41—H41C	109.5
C1—C19—H19A	109.5	H41A—C41—H41C	109.5
C1—C19—H19B	109.5	H41B—C41—H41C	109.5
H19A—C19—H19B	109.5	O12—C42—O13	124.1 (2)
C1—C19—H19C	109.5	O12—C42—C32	125.5 (2)
H19A—C19—H19C	109.5	O13—C42—C32	110.3 (2)
H19B—C19—H19C	109.5	O13—C43—H43A	109.5
O5—C20—O6	124.5 (2)	O13—C43—H43B	109.5
O5—C20—C10	124.8 (2)	H43A—C43—H43B	109.5
O6—C20—C10	110.6 (2)	O13—C43—H43C	109.5
O6—C21—H21A	109.5	H43A—C43—H43C	109.5
O6—C21—H21B	109.5	H43B—C43—H43C	109.5
H21A—C21—H21B	109.5	C33—C44—H44A	109.5
O6—C21—H21C	109.5	C33—C44—H44B	109.5
H21A—C21—H21C	109.5	H44A—C44—H44B	109.5
H21B—C21—H21C	109.5	C33—C44—H44C	109.5
C11—C22—H22A	109.5	H44A—C44—H44C	109.5
C11—C22—H22B	109.5	H44B—C44—H44C	109.5
O1—C1—C2—C3	24.9 (3)	C25—C26—C27—O9	2.3 (3)
C19—C1—C2—C3	141.1 (2)	C39—C26—C27—C28	1.6 (3)
C18—C1—C2—C3	−93.9 (3)	C25—C26—C27—C28	−178.3 (2)
C1—C2—C3—C4	−7.6 (4)	O9—C27—C28—C37	177.5 (2)
C2—C3—C4—C17	−7.6 (3)	C26—C27—C28—C37	−1.9 (3)
C2—C3—C4—C5	178.3 (2)	O9—C27—C28—C29	−2.9 (3)
C17—C4—C5—O2	−178.06 (19)	C26—C27—C28—C29	177.7 (2)
C3—C4—C5—O2	−3.9 (3)	C27—C28—C29—O10	1.4 (3)
C17—C4—C5—C6	0.1 (3)	C37—C28—C29—O10	−179.1 (2)
C3—C4—C5—C6	174.2 (2)	C27—C28—C29—C30	−179.2 (2)
O2—C5—C6—C15	177.2 (2)	C37—C28—C29—C30	0.4 (3)
C4—C5—C6—C15	−0.9 (3)	O10—C29—C30—C31	−1.2 (3)
O2—C5—C6—C7	−1.6 (3)	C28—C29—C30—C31	179.4 (2)
C4—C5—C6—C7	−179.6 (2)	O10—C29—C30—C35	178.2 (2)
C5—C6—C7—O3	0.0 (3)	C28—C29—C30—C35	−1.2 (3)
C15—C6—C7—O3	−178.8 (2)	C35—C30—C31—O11	179.8 (2)
C5—C6—C7—C8	178.9 (2)	C29—C30—C31—O11	−0.8 (3)
C15—C6—C7—C8	0.2 (3)	C35—C30—C31—C32	−1.3 (3)
O3—C7—C8—C9	−1.1 (3)	C29—C30—C31—C32	178.1 (2)
C6—C7—C8—C9	180.0 (2)	O11—C31—C32—C33	178.9 (2)
O3—C7—C8—C13	177.3 (2)	C30—C31—C32—C33	−0.1 (3)
C6—C7—C8—C13	−1.6 (3)	O11—C31—C32—C42	−0.8 (3)
C13—C8—C9—O4	−179.94 (19)	C30—C31—C32—C42	−179.7 (2)
C7—C8—C9—O4	−1.6 (3)	C31—C32—C33—C34	1.3 (3)
C13—C8—C9—C10	−1.5 (3)	C42—C32—C33—C34	−179.1 (2)
C7—C8—C9—C10	176.9 (2)	C31—C32—C33—C44	−178.2 (2)
O4—C9—C10—C11	179.6 (2)	C42—C32—C33—C44	1.4 (3)
C8—C9—C10—C11	1.1 (3)	C32—C33—C34—C35	−1.1 (3)
O4—C9—C10—C20	−0.5 (3)	C44—C33—C34—C35	178.4 (2)
C8—C9—C10—C20	−179.1 (2)	C33—C34—C35—C30	−0.3 (3)
C9—C10—C11—C12	0.0 (3)	C33—C34—C35—C36	179.7 (2)
C20—C10—C11—C12	−179.9 (2)	C31—C30—C35—C34	1.5 (3)
C9—C10—C11—C22	−179.3 (2)	C29—C30—C35—C34	−177.9 (2)
C20—C10—C11—C22	0.9 (3)	C31—C30—C35—C36	−178.5 (2)
C10—C11—C12—C13	−0.6 (3)	C29—C30—C35—C36	2.1 (3)
C22—C11—C12—C13	178.6 (2)	C34—C35—C36—O14	−2.6 (3)
C11—C12—C13—C8	0.2 (3)	C30—C35—C36—O14	177.4 (2)
C11—C12—C13—C14	−179.5 (2)	C34—C35—C36—C37	177.9 (2)
C9—C8—C13—C12	0.9 (3)	C30—C35—C36—C37	−2.1 (3)
C7—C8—C13—C12	−177.5 (2)	C27—C28—C37—C38	0.3 (3)
C9—C8—C13—C14	−179.4 (2)	C29—C28—C37—C38	−179.3 (2)
C7—C8—C13—C14	2.2 (3)	C27—C28—C37—C36	179.1 (2)
C12—C13—C14—O7	−1.5 (3)	C29—C28—C37—C36	−0.5 (3)
C8—C13—C14—O7	178.8 (2)	O14—C36—C37—C38	0.6 (3)
C12—C13—C14—C15	178.4 (2)	C35—C36—C37—C38	−179.8 (2)
C8—C13—C14—C15	−1.3 (3)	O14—C36—C37—C28	−178.2 (2)
C5—C6—C15—C16	0.4 (3)	C35—C36—C37—C28	1.3 (3)
C7—C6—C15—C16	179.2 (2)	C28—C37—C38—C39	1.6 (3)
C5—C6—C15—C14	−178.1 (2)	C36—C37—C38—C39	−177.2 (2)
C7—C6—C15—C14	0.7 (3)	C37—C38—C39—O8	179.2 (2)
O7—C14—C15—C16	1.2 (3)	C37—C38—C39—C26	−2.0 (3)
C13—C14—C15—C16	−178.7 (2)	C27—C26—C39—O8	179.2 (2)
O7—C14—C15—C6	179.8 (2)	C25—C26—C39—O8	−0.9 (3)
C13—C14—C15—C6	−0.2 (3)	C27—C26—C39—C38	0.5 (3)
C6—C15—C16—C17	0.7 (3)	C25—C26—C39—C38	−179.7 (2)
C14—C15—C16—C17	179.2 (2)	C33—C32—C42—O12	−86.8 (3)
C15—C16—C17—O1	−178.1 (2)	C31—C32—C42—O12	92.8 (3)
C15—C16—C17—C4	−1.5 (4)	C33—C32—C42—O13	92.9 (3)
C5—C4—C17—O1	177.5 (2)	C31—C32—C42—O13	−87.5 (3)
C3—C4—C17—O1	3.1 (3)	C16—C17—O1—C1	−166.9 (2)
C5—C4—C17—C16	1.1 (3)	C4—C17—O1—C1	16.5 (3)
C3—C4—C17—C16	−173.3 (2)	C2—C1—O1—C17	−29.0 (3)
C9—C10—C20—O5	96.9 (3)	C19—C1—O1—C17	−149.8 (2)
C11—C10—C20—O5	−83.2 (3)	C18—C1—O1—C17	91.0 (3)
C9—C10—C20—O6	−85.6 (3)	O5—C20—O6—C21	5.9 (4)
C11—C10—C20—O6	94.3 (2)	C10—C20—O6—C21	−171.6 (2)
O8—C23—C24—C25	12.5 (4)	C38—C39—O8—C23	−168.0 (2)
C40—C23—C24—C25	−106.0 (3)	C26—C39—O8—C23	13.3 (3)
C41—C23—C24—C25	129.0 (3)	C24—C23—O8—C39	−18.1 (3)
C23—C24—C25—C26	−1.7 (4)	C40—C23—O8—C39	103.1 (3)
C24—C25—C26—C39	−4.8 (4)	C41—C23—O8—C39	−138.7 (2)
C24—C25—C26—C27	175.0 (2)	O12—C42—O13—C43	−2.1 (4)
C39—C26—C27—O9	−177.88 (19)	C32—C42—O13—C43	178.22 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O3	0.91 (3)	1.72 (3)	2.567 (2)	152 (3)
O11—H11O···O10	0.88 (3)	1.75 (4)	2.568 (2)	153 (3)
O9—H9O···O10	0.92 (3)	1.72 (3)	2.558 (2)	150 (3)
O2—H2O···O3	0.88 (3)	1.77 (3)	2.562 (2)	148 (3)
O2—H20···O9i	0.88 (3)	2.31 (3)	2.654 (2)	103 (2)
C34—H34···O7ii	0.95	2.59	3.441 (2)	150
C44—H44B···O7ii	0.98	2.51	3.423 (2)	155
C44—H44C···O8ii	0.98	2.58	3.419 (2)	144

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4O⋯O3	0.91 (3)	1.72 (3)	2.567 (2)	152 (3)
O11—H11O⋯O10	0.88 (3)	1.75 (4)	2.568 (2)	153 (3)
O9—H9O⋯O10	0.92 (3)	1.72 (3)	2.558 (2)	150 (3)
O2—H2O⋯O3	0.88 (3)	1.77 (3)	2.562 (2)	148 (3)
O2—H20⋯O9i	0.88 (3)	2.31 (3)	2.654 (2)	103 (2)
C34—H34⋯O7ii	0.95	2.59	3.441 (2)	150
C44—H44B⋯O7ii	0.98	2.51	3.423 (2)	155
C44—H44C⋯O8ii	0.98	2.58	3.419 (2)	144

Symmetry codes: (i) ; (ii) .