4-Hydro­xy-3,6,9-tri­methyl-2,3-di­hydro­benzo­[de]­chromene-7,8-dione

The title compound, C₁₅H₁₄O₄, also known as mansonone H, crystallizes in the space group P2₁2₁2 with two mol­ecules in the asymmetric unit. In both mol­ecules, the tetra­hydro­pyran ring adopts an envelope conformation and the attached methyl group occupies an axial position. In the crystal structure, symmetry-related mol­ecules are linked by O—H...O and C—H...O hydrogen bonds, to form chains along the a and b axes. They are interlinked by C—H...O hydrogen bonds to form a network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.053
• wR factor = 0.148
• Data-to-parameter ratio = 9.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.31
         From the CIF: _reflns_number_total               3275
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         3515
         Completeness (_total/calc)             93.17%
          Alert C: < 95% complete

PLAT_213  Alert C Atom O4A     has ADP max/min Ratio ...........       3.40 prolate

PLAT_369  Alert C Long   C(sp2)-C(sp2) Bond  C(8B)  -   C(9B)  =       1.54 Ang.

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.31
         From the CIF: _reflns_number_total               3275
         Count of symmetry unique reflns         3515
         Completeness (_total/calc)             93.17%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured         0
         Fraction of Friedel pairs measured     0.000
         Are heavy atom types Z>Si present           no
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

---

S1. Comment

Mansonone H, (I), was isolated from the roots of Helicteres angustifolia (Sterculiaceae) known as anti-inflammatory and antitumour medicine (Jiangsu New Medical Colleges, 1986). This cadinane sesquiterpenoid quinine has been previously isolated from the wood sawdust of Mansonia altissima Chev (Tanaka et al., 1966), the root bark of Ulmus davidiana (Kim et al., 1996) and the heartwood of Mansonia gagei Drumm (Tiew et al., 2002). The structure of (I) was previously elucidated on the basis of spectroscopic analysis. Herein, we report the crystal structure of (I).

The X-ray study of (I) confirms the previously proposed molecular structure based on spectroscopic data (Fig. 1). The asymmetric unit of (I) consists of two independent molecules, A and B, linked by a C13B—H13D···O3A hydrogen bond (Table 1). Bond lengths and angles observed in these two molecules agree with each other, but a large deviation is observed in the corresponding torsion angles about the C4—C12 bond. The C8A—C9A [1.523 (4) Å] and C8B—C9B [1.536 (4) Å] bond lengths are longer than the mean value of 1.478 (12) Å reported for unconjugated C_sp²—C_sp² bonds by Allen et al. (1987). In both molecules, the tetrahydropyran ring adopts an envelope conformation and the methyl group occupies an axial position.

In the crystal, symmetry-related A molecules are linked by O1A—H1A···O3Aⁱ and C2A—H2A···O3Aⁱⁱ hydrogen bonds, forming chains along the b axis. Similarly, symmetry-related B molecules are linked by O1B—H1B···O3Bⁱ and C2B—H2B···O3Bⁱⁱ hydrogen bonds, forming chains along the a axis (symmetry codes are as in Table 1). The chains formed by molecules A and B are arranged alternately and C13B—H13D···O3A hydrogen bonds link them to form a network (Fig. 2).

S2. Experimental

Dried powder obtained from the roots of Helicteres angustifolia was extracted with EtOH. The EtOH extract was concentrated in vacuo, and the residue was extracted with EtOAc. The soluble portion of the EtOAc extract was subjected to silica-gel column chromatography, eluting with chloroform/menthol, yielded the title compound, mansonone H, (I). The compound was confirmed by the NMR spectra. Crystals of (I) were obtained from chloroform/menthol by solvent diffusion. ¹H NMR (500 MHz, DMSO-d₆): δ 6.78 (s, H5), 3.19 (m, H9), 4.43 (dd, J = 1.5, 5.0 Hz, H2a), 4.29 (dd, J = 1.5, 5.0 Hz, H2b), 1.83 (s, H9), 2.51 (s, H6), 1.20 (d, J = 7.0 Hz, H3).

S3. Refinement

The H atoms were positioned geometrically and were treated as riding on their parent C and O atoms, with C—H distances in the range 0.93–0.98 Å and O—H distance of 0.82 Å. The reflections (001) and (110) were omitted during the refinement as they fit very badly. One of the anisotropic displacement parameters (U₃₃) for the carbonyl atom O4A is large, indicating a possible disorder. Owing to a large fraction of weak data at higher angles, the completeness of tha data is slightly low. The Friedel opposites were merged during the refinement.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of two molecules in the asymmetric unit of (I), with ellipsoids at the 50% probability level.
	Fig. 2. The molecular packing of (I), viewed down the c axis.

4-Hydroxy-3,6,9-trimethyl-2,3-dihydrobenzo[de]chromene-7,8-dione

Crystal data

C15H14O4	F(000) = 1088
Mr = 258.26	Dx = 1.378 Mg m^−3
Orthorhombic, P21212	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 25 reflections
a = 17.917 (1) Å	θ = 25–31°
b = 18.126 (1) Å	µ = 0.10 mm^−1
c = 7.668 (1) Å	T = 293 K
V = 2490.3 (4) Å^3	Plate, red
Z = 8	0.28 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer	2108 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.056
Graphite monochromator	θmax = 28.3°, θmin = 2.3°
ω scans	h = −23→22
14655 measured reflections	k = −15→23
3275 independent reflections	l = −10→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0879P)^2] where P = (Fo^2 + 2Fc^2)/3
3275 reflections	(Δ/σ)max < 0.001
344 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.21 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. All H atoms were placed in calculated positions and refined as riding atoms.

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

	x	y	z	Uiso*/Ueq
O1A	0.15330 (11)	0.50699 (11)	0.0388 (4)	0.0529 (7)
H1A	0.1878	0.5367	0.0326	0.064*
O2A	0.02737 (10)	0.26301 (11)	−0.0102 (4)	0.0501 (7)
O3A	0.21760 (12)	0.09143 (11)	−0.0064 (5)	0.0635 (8)
O4A	0.31836 (13)	0.19491 (14)	−0.0393 (8)	0.1137 (17)
C1A	0.28303 (16)	0.35125 (17)	0.0013 (6)	0.0451 (8)
C2A	0.25568 (17)	0.42257 (16)	0.0183 (6)	0.0441 (8)
H2A	0.2894	0.4614	0.0278	0.053*
C3A	0.18026 (16)	0.43793 (15)	0.0215 (5)	0.0397 (8)
C4A	0.12793 (15)	0.38068 (15)	0.0105 (5)	0.0357 (7)
C5A	0.15449 (15)	0.30889 (15)	−0.0055 (5)	0.0355 (7)
C6A	0.10020 (15)	0.24810 (15)	−0.0057 (5)	0.0368 (7)
C7A	0.11884 (16)	0.17541 (16)	0.0072 (5)	0.0407 (8)
C8A	0.19548 (16)	0.15581 (16)	−0.0037 (6)	0.0423 (8)
C9A	0.25504 (17)	0.21539 (17)	−0.0189 (7)	0.0543 (10)
C10A	0.23180 (15)	0.29275 (16)	−0.0088 (6)	0.0416 (8)
C11A	0.36618 (16)	0.3408 (2)	−0.0053 (8)	0.0699 (13)
H11A	0.3903	0.3880	0.0011	0.105*
H11B	0.3796	0.3169	−0.1126	0.105*
H11C	0.3818	0.3109	0.0913	0.105*
C12A	0.04522 (15)	0.39532 (16)	0.0200 (5)	0.0406 (8)
H12A	0.0353	0.4420	−0.0403	0.049*
C13A	0.00502 (18)	0.33484 (16)	−0.0771 (5)	0.0481 (9)
H13A	−0.0485	0.3409	−0.0635	0.058*
H13B	0.0167	0.3379	−0.2004	0.058*
C14A	0.0173 (2)	0.4026 (2)	0.2046 (5)	0.0564 (10)
H14A	0.0441	0.4414	0.2625	0.085*
H14B	0.0251	0.3570	0.2655	0.085*
H14C	−0.0350	0.4141	0.2034	0.085*
C15A	0.05877 (17)	0.11781 (16)	0.0249 (6)	0.0532 (10)
H15A	0.0262	0.1201	−0.0744	0.080*
H15B	0.0306	0.1268	0.1292	0.080*
H15C	0.0812	0.0698	0.0312	0.080*
O1B	0.00578 (11)	0.15361 (12)	0.5081 (4)	0.0543 (7)
H1B	−0.0229	0.1879	0.4889	0.065*
O2B	0.24898 (11)	0.02368 (11)	0.4260 (4)	0.0539 (7)
O3B	0.42882 (11)	0.20679 (13)	0.4607 (4)	0.0594 (8)
O4B	0.32678 (13)	0.30978 (13)	0.4978 (6)	0.0781 (10)
C1B	0.16801 (16)	0.27748 (15)	0.5045 (5)	0.0393 (7)
C2B	0.09484 (16)	0.25227 (17)	0.5101 (5)	0.0425 (8)
H2B	0.0564	0.2865	0.5208	0.051*
C3B	0.07713 (15)	0.17825 (17)	0.5003 (5)	0.0407 (7)
C4B	0.13349 (16)	0.12540 (15)	0.4788 (5)	0.0376 (8)
C5B	0.20691 (16)	0.14961 (16)	0.4682 (5)	0.0354 (8)
C6B	0.26698 (16)	0.09563 (16)	0.4452 (5)	0.0391 (8)
C7B	0.34097 (17)	0.11184 (17)	0.4436 (5)	0.0412 (8)
C8B	0.36360 (16)	0.18669 (18)	0.4626 (5)	0.0419 (8)
C9B	0.30421 (16)	0.24721 (17)	0.4826 (6)	0.0431 (8)
C10B	0.22533 (15)	0.22597 (16)	0.4826 (5)	0.0374 (7)
C11B	0.18078 (19)	0.35934 (17)	0.5210 (7)	0.0552 (10)
H11D	0.1336	0.3842	0.5295	0.083*
H11E	0.2072	0.3769	0.4202	0.083*
H11F	0.2097	0.3692	0.6237	0.083*
C12B	0.11541 (16)	0.04380 (16)	0.4685 (5)	0.0425 (8)
H12B	0.0678	0.0384	0.4067	0.051*
C13B	0.17469 (17)	0.00636 (19)	0.3623 (5)	0.0506 (9)
H13C	0.1671	−0.0466	0.3666	0.061*
H13D	0.1704	0.0219	0.2417	0.061*
C14B	0.1069 (2)	0.0093 (2)	0.6477 (6)	0.0701 (12)
H14D	0.0953	−0.0421	0.6354	0.105*
H14E	0.0673	0.0336	0.7095	0.105*
H14F	0.1526	0.0147	0.7115	0.105*
C15B	0.39940 (18)	0.05296 (19)	0.4155 (6)	0.0547 (10)
H15D	0.3923	0.0139	0.4985	0.082*
H15E	0.4482	0.0740	0.4306	0.082*
H15F	0.3949	0.0336	0.2994	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0405 (12)	0.0181 (10)	0.100 (2)	−0.0003 (9)	0.0009 (14)	0.0011 (14)
O2A	0.0257 (10)	0.0260 (11)	0.0987 (19)	0.0006 (8)	−0.0043 (13)	−0.0045 (14)
O3A	0.0472 (12)	0.0202 (11)	0.123 (2)	0.0076 (9)	0.0027 (17)	−0.0009 (17)
O4A	0.0321 (13)	0.0338 (14)	0.275 (6)	0.0087 (11)	0.016 (2)	0.002 (3)
C1A	0.0301 (14)	0.0261 (15)	0.079 (3)	−0.0023 (12)	−0.0070 (19)	0.004 (2)
C2A	0.0359 (16)	0.0227 (14)	0.074 (2)	−0.0054 (12)	−0.0027 (18)	0.0024 (18)
C3A	0.0368 (15)	0.0205 (14)	0.062 (2)	−0.0011 (12)	0.0007 (17)	0.0042 (17)
C4A	0.0312 (14)	0.0209 (14)	0.055 (2)	−0.0005 (11)	−0.0035 (16)	0.0061 (16)
C5A	0.0302 (14)	0.0218 (14)	0.0545 (19)	0.0003 (11)	−0.0038 (16)	0.0017 (17)
C6A	0.0293 (14)	0.0233 (14)	0.058 (2)	0.0015 (11)	−0.0011 (17)	0.0015 (17)
C7A	0.0319 (15)	0.0222 (13)	0.068 (2)	−0.0035 (12)	−0.0029 (17)	−0.0019 (18)
C8A	0.0363 (15)	0.0199 (13)	0.071 (2)	0.0052 (12)	−0.0020 (18)	−0.0003 (19)
C9A	0.0298 (15)	0.0272 (15)	0.106 (3)	0.0047 (13)	0.000 (2)	0.004 (2)
C10A	0.0286 (14)	0.0232 (14)	0.073 (2)	−0.0012 (12)	0.0005 (18)	0.0034 (19)
C11A	0.0295 (16)	0.042 (2)	0.139 (4)	−0.0051 (15)	0.002 (3)	0.006 (3)
C12A	0.0337 (15)	0.0225 (14)	0.066 (2)	0.0037 (12)	−0.0027 (17)	0.0054 (17)
C13A	0.0324 (16)	0.0273 (17)	0.084 (3)	0.0071 (14)	−0.0089 (17)	−0.0004 (18)
C14A	0.052 (2)	0.046 (2)	0.072 (3)	0.0059 (18)	0.0054 (19)	−0.006 (2)
C15A	0.0382 (16)	0.0236 (15)	0.098 (3)	−0.0043 (13)	−0.002 (2)	−0.002 (2)
O1B	0.0264 (10)	0.0365 (12)	0.100 (2)	−0.0003 (9)	0.0027 (15)	−0.0013 (17)
O2B	0.0351 (12)	0.0198 (11)	0.107 (2)	0.0011 (9)	−0.0023 (13)	−0.0008 (12)
O3B	0.0277 (11)	0.0444 (13)	0.106 (2)	−0.0056 (10)	−0.0010 (13)	−0.0059 (15)
O4B	0.0440 (13)	0.0292 (13)	0.161 (3)	−0.0094 (10)	0.002 (2)	−0.012 (2)
C1B	0.0380 (15)	0.0206 (14)	0.059 (2)	0.0013 (12)	−0.0033 (18)	−0.0002 (18)
C2B	0.0347 (15)	0.0275 (15)	0.065 (2)	0.0077 (12)	0.0017 (18)	−0.0062 (18)
C3B	0.0284 (14)	0.0333 (15)	0.060 (2)	−0.0007 (13)	−0.0011 (17)	0.0003 (19)
C4B	0.0321 (14)	0.0241 (15)	0.057 (2)	−0.0010 (12)	−0.0003 (16)	−0.0007 (16)
C5B	0.0289 (14)	0.0239 (14)	0.053 (2)	0.0006 (12)	−0.0026 (14)	0.0018 (16)
C6B	0.0304 (15)	0.0230 (15)	0.064 (2)	0.0018 (12)	−0.0006 (15)	0.0013 (16)
C7B	0.0291 (15)	0.0311 (16)	0.063 (2)	0.0016 (13)	−0.0015 (14)	0.0050 (17)
C8B	0.0271 (15)	0.0339 (17)	0.065 (2)	−0.0012 (13)	0.0007 (15)	0.0014 (18)
C9B	0.0350 (16)	0.0266 (15)	0.068 (2)	−0.0022 (13)	−0.0012 (17)	0.0011 (18)
C10B	0.0311 (14)	0.0265 (15)	0.055 (2)	−0.0018 (12)	−0.0032 (16)	0.0002 (17)
C11B	0.0502 (19)	0.0236 (15)	0.092 (3)	0.0010 (14)	−0.002 (2)	−0.001 (2)
C12B	0.0322 (15)	0.0251 (15)	0.070 (2)	−0.0039 (12)	−0.0034 (17)	−0.0049 (17)
C13B	0.0375 (17)	0.0252 (17)	0.089 (3)	−0.0014 (15)	−0.0050 (18)	−0.0108 (19)
C14B	0.080 (3)	0.039 (2)	0.091 (3)	−0.011 (2)	0.006 (2)	0.011 (2)
C15B	0.0332 (17)	0.0374 (19)	0.093 (3)	0.0081 (15)	−0.0010 (18)	0.001 (2)

Geometric parameters (Å, º)

O1A—C3A	1.348 (3)	O1B—C3B	1.355 (3)
O1A—H1A	0.82	O1B—H1B	0.82
O2A—C6A	1.333 (3)	O2B—C6B	1.351 (4)
O2A—C13A	1.455 (4)	O2B—C13B	1.452 (4)
O3A—C8A	1.233 (3)	O3B—C8B	1.224 (3)
O4A—C9A	1.204 (4)	O4B—C9B	1.210 (4)
C1A—C2A	1.389 (4)	C1B—C2B	1.389 (4)
C1A—C10A	1.405 (4)	C1B—C10B	1.398 (4)
C1A—C11A	1.503 (4)	C1B—C11B	1.507 (4)
C2A—C3A	1.380 (4)	C2B—C3B	1.381 (4)
C2A—H2A	0.93	C2B—H2B	0.93
C3A—C4A	1.401 (4)	C3B—C4B	1.402 (4)
C4A—C5A	1.391 (4)	C4B—C5B	1.389 (4)
C4A—C12A	1.507 (4)	C4B—C12B	1.516 (4)
C5A—C10A	1.416 (4)	C5B—C10B	1.427 (4)
C5A—C6A	1.470 (4)	C5B—C6B	1.465 (4)
C6A—C7A	1.363 (4)	C6B—C7B	1.358 (4)
C7A—C8A	1.421 (4)	C7B—C8B	1.424 (4)
C7A—C15A	1.506 (4)	C7B—C15B	1.510 (5)
C8A—C9A	1.523 (4)	C8B—C9B	1.536 (4)
C9A—C10A	1.465 (4)	C9B—C10B	1.465 (4)
C11A—H11A	0.96	C11B—H11D	0.96
C11A—H11B	0.96	C11B—H11E	0.96
C11A—H11C	0.96	C11B—H11F	0.96
C12A—C14A	1.507 (5)	C12B—C13B	1.500 (5)
C12A—C13A	1.508 (4)	C12B—C14B	1.517 (6)
C12A—H12A	0.98	C12B—H12B	0.98
C13A—H13A	0.97	C13B—H13C	0.97
C13A—H13B	0.97	C13B—H13D	0.97
C14A—H14A	0.96	C14B—H14D	0.96
C14A—H14B	0.96	C14B—H14E	0.96
C14A—H14C	0.96	C14B—H14F	0.96
C15A—H15A	0.96	C15B—H15D	0.96
C15A—H15B	0.96	C15B—H15E	0.96
C15A—H15C	0.96	C15B—H15F	0.96
C3A—O1A—H1A	109.5	C3B—O1B—H1B	109.5
C6A—O2A—C13A	117.4 (2)	C6B—O2B—C13B	117.7 (2)
C2A—C1A—C10A	118.5 (3)	C2B—C1B—C10B	118.5 (3)
C2A—C1A—C11A	118.0 (3)	C2B—C1B—C11B	117.7 (3)
C10A—C1A—C11A	123.5 (3)	C10B—C1B—C11B	123.8 (3)
C3A—C2A—C1A	122.3 (3)	C3B—C2B—C1B	122.3 (3)
C3A—C2A—H2A	118.8	C3B—C2B—H2B	118.8
C1A—C2A—H2A	118.8	C1B—C2B—H2B	118.8
O1A—C3A—C2A	122.7 (3)	O1B—C3B—C2B	122.3 (3)
O1A—C3A—C4A	117.0 (2)	O1B—C3B—C4B	117.3 (3)
C2A—C3A—C4A	120.3 (3)	C2B—C3B—C4B	120.3 (3)
C5A—C4A—C3A	118.0 (2)	C5B—C4B—C3B	118.2 (3)
C5A—C4A—C12A	120.4 (2)	C5B—C4B—C12B	120.5 (3)
C3A—C4A—C12A	121.6 (2)	C3B—C4B—C12B	121.3 (3)
C4A—C5A—C10A	122.0 (2)	C4B—C5B—C10B	121.4 (3)
C4A—C5A—C6A	118.4 (2)	C4B—C5B—C6B	119.4 (3)
C10A—C5A—C6A	119.5 (2)	C10B—C5B—C6B	119.1 (3)
O2A—C6A—C7A	116.0 (2)	O2B—C6B—C7B	116.2 (3)
O2A—C6A—C5A	119.7 (2)	O2B—C6B—C5B	118.8 (2)
C7A—C6A—C5A	124.2 (2)	C7B—C6B—C5B	125.0 (3)
C6A—C7A—C8A	118.3 (3)	C6B—C7B—C8B	118.9 (3)
C6A—C7A—C15A	120.1 (3)	C6B—C7B—C15B	121.7 (3)
C8A—C7A—C15A	121.5 (3)	C8B—C7B—C15B	119.4 (3)
O3A—C8A—C7A	123.3 (3)	O3B—C8B—C7B	123.7 (3)
O3A—C8A—C9A	116.4 (3)	O3B—C8B—C9B	116.7 (3)
C7A—C8A—C9A	120.3 (3)	C7B—C8B—C9B	119.6 (3)
O4A—C9A—C10A	124.7 (3)	O4B—C9B—C10B	124.7 (3)
O4A—C9A—C8A	116.9 (3)	O4B—C9B—C8B	116.6 (3)
C10A—C9A—C8A	118.4 (2)	C10B—C9B—C8B	118.7 (3)
C1A—C10A—C5A	118.8 (3)	C1B—C10B—C5B	119.1 (3)
C1A—C10A—C9A	122.7 (3)	C1B—C10B—C9B	122.2 (3)
C5A—C10A—C9A	118.5 (2)	C5B—C10B—C9B	118.6 (3)
C1A—C11A—H11A	109.5	C1B—C11B—H11D	109.5
C1A—C11A—H11B	109.5	C1B—C11B—H11E	109.5
H11A—C11A—H11B	109.5	H11D—C11B—H11E	109.5
C1A—C11A—H11C	109.5	C1B—C11B—H11F	109.5
H11A—C11A—H11C	109.5	H11D—C11B—H11F	109.5
H11B—C11A—H11C	109.5	H11E—C11B—H11F	109.5
C14A—C12A—C4A	112.8 (3)	C13B—C12B—C4B	108.6 (3)
C14A—C12A—C13A	111.7 (3)	C13B—C12B—C14B	112.1 (3)
C4A—C12A—C13A	108.5 (3)	C4B—C12B—C14B	112.1 (3)
C14A—C12A—H12A	107.9	C13B—C12B—H12B	108.0
C4A—C12A—H12A	107.9	C4B—C12B—H12B	108.0
C13A—C12A—H12A	107.9	C14B—C12B—H12B	108.0
O2A—C13A—C12A	110.2 (3)	O2B—C13B—C12B	111.6 (3)
O2A—C13A—H13A	109.6	O2B—C13B—H13C	109.3
C12A—C13A—H13A	109.6	C12B—C13B—H13C	109.3
O2A—C13A—H13B	109.6	O2B—C13B—H13D	109.3
C12A—C13A—H13B	109.6	C12B—C13B—H13D	109.3
H13A—C13A—H13B	108.1	H13C—C13B—H13D	108.0
C12A—C14A—H14A	109.5	C12B—C14B—H14D	109.5
C12A—C14A—H14B	109.5	C12B—C14B—H14E	109.5
H14A—C14A—H14B	109.5	H14D—C14B—H14E	109.5
C12A—C14A—H14C	109.5	C12B—C14B—H14F	109.5
H14A—C14A—H14C	109.5	H14D—C14B—H14F	109.5
H14B—C14A—H14C	109.5	H14E—C14B—H14F	109.5
C7A—C15A—H15A	109.5	C7B—C15B—H15D	109.5
C7A—C15A—H15B	109.5	C7B—C15B—H15E	109.5
H15A—C15A—H15B	109.5	H15D—C15B—H15E	109.5
C7A—C15A—H15C	109.5	C7B—C15B—H15F	109.5
H15A—C15A—H15C	109.5	H15D—C15B—H15F	109.5
H15B—C15A—H15C	109.5	H15E—C15B—H15F	109.5
C10A—C1A—C2A—C3A	−1.5 (7)	C10B—C1B—C2B—C3B	2.1 (6)
C11A—C1A—C2A—C3A	178.5 (4)	C11B—C1B—C2B—C3B	−178.5 (4)
C1A—C2A—C3A—O1A	179.6 (4)	C1B—C2B—C3B—O1B	179.1 (4)
C1A—C2A—C3A—C4A	1.1 (7)	C1B—C2B—C3B—C4B	−1.9 (6)
O1A—C3A—C4A—C5A	−179.3 (3)	O1B—C3B—C4B—C5B	179.2 (3)
C2A—C3A—C4A—C5A	−0.7 (6)	C2B—C3B—C4B—C5B	0.2 (6)
O1A—C3A—C4A—C12A	−0.8 (6)	O1B—C3B—C4B—C12B	−1.2 (5)
C2A—C3A—C4A—C12A	177.8 (4)	C2B—C3B—C4B—C12B	179.7 (4)
C3A—C4A—C5A—C10A	0.8 (6)	C3B—C4B—C5B—C10B	1.4 (6)
C12A—C4A—C5A—C10A	−177.8 (4)	C12B—C4B—C5B—C10B	−178.2 (3)
C3A—C4A—C5A—C6A	176.1 (3)	C3B—C4B—C5B—C6B	−179.8 (3)
C12A—C4A—C5A—C6A	−2.4 (6)	C12B—C4B—C5B—C6B	0.6 (5)
C13A—O2A—C6A—C7A	−161.4 (3)	C13B—O2B—C6B—C7B	−157.4 (3)
C13A—O2A—C6A—C5A	21.8 (5)	C13B—O2B—C6B—C5B	23.4 (5)
C4A—C5A—C6A—O2A	7.4 (6)	C4B—C5B—C6B—O2B	3.3 (5)
C10A—C5A—C6A—O2A	−177.1 (4)	C10B—C5B—C6B—O2B	−177.9 (3)
C4A—C5A—C6A—C7A	−169.2 (4)	C4B—C5B—C6B—C7B	−175.8 (4)
C10A—C5A—C6A—C7A	6.3 (6)	C10B—C5B—C6B—C7B	3.0 (6)
O2A—C6A—C7A—C8A	174.3 (3)	O2B—C6B—C7B—C8B	179.7 (3)
C5A—C6A—C7A—C8A	−9.0 (6)	C5B—C6B—C7B—C8B	−1.1 (6)
O2A—C6A—C7A—C15A	−3.2 (6)	O2B—C6B—C7B—C15B	2.1 (5)
C5A—C6A—C7A—C15A	173.5 (4)	C5B—C6B—C7B—C15B	−178.7 (3)
C6A—C7A—C8A—O3A	−174.5 (4)	C6B—C7B—C8B—O3B	−179.1 (4)
C15A—C7A—C8A—O3A	3.0 (7)	C15B—C7B—C8B—O3B	−1.4 (6)
C6A—C7A—C8A—C9A	3.4 (6)	C6B—C7B—C8B—C9B	−0.6 (6)
C15A—C7A—C8A—C9A	−179.1 (4)	C15B—C7B—C8B—C9B	177.1 (3)
O3A—C8A—C9A—O4A	2.9 (7)	O3B—C8B—C9B—O4B	−1.2 (6)
C7A—C8A—C9A—O4A	−175.1 (5)	C7B—C8B—C9B—O4B	−179.8 (4)
O3A—C8A—C9A—C10A	−177.4 (4)	O3B—C8B—C9B—C10B	179.0 (4)
C7A—C8A—C9A—C10A	4.5 (7)	C7B—C8B—C9B—C10B	0.4 (6)
C2A—C1A—C10A—C5A	1.5 (6)	C2B—C1B—C10B—C5B	−0.5 (6)
C11A—C1A—C10A—C5A	−178.5 (4)	C11B—C1B—C10B—C5B	−179.9 (4)
C2A—C1A—C10A—C9A	−177.2 (4)	C2B—C1B—C10B—C9B	−177.4 (4)
C11A—C1A—C10A—C9A	2.9 (7)	C11B—C1B—C10B—C9B	3.2 (6)
C4A—C5A—C10A—C1A	−1.1 (7)	C4B—C5B—C10B—C1B	−1.2 (6)
C6A—C5A—C10A—C1A	−176.5 (4)	C6B—C5B—C10B—C1B	180.0 (3)
C4A—C5A—C10A—C9A	177.6 (4)	C4B—C5B—C10B—C9B	175.8 (3)
C6A—C5A—C10A—C9A	2.2 (6)	C6B—C5B—C10B—C9B	−3.0 (5)
O4A—C9A—C10A—C1A	−8.8 (8)	O4B—C9B—C10B—C1B	−1.4 (7)
C8A—C9A—C10A—C1A	171.5 (4)	C8B—C9B—C10B—C1B	178.4 (4)
O4A—C9A—C10A—C5A	172.5 (5)	O4B—C9B—C10B—C5B	−178.3 (4)
C8A—C9A—C10A—C5A	−7.1 (6)	C8B—C9B—C10B—C5B	1.5 (6)
C5A—C4A—C12A—C14A	96.0 (4)	C5B—C4B—C12B—C13B	−28.1 (5)
C3A—C4A—C12A—C14A	−82.5 (4)	C3B—C4B—C12B—C13B	152.4 (3)
C5A—C4A—C12A—C13A	−28.3 (5)	C5B—C4B—C12B—C14B	96.3 (4)
C3A—C4A—C12A—C13A	153.2 (4)	C3B—C4B—C12B—C14B	−83.3 (4)
C6A—O2A—C13A—C12A	−53.9 (4)	C6B—O2B—C13B—C12B	−52.8 (4)
C14A—C12A—C13A—O2A	−70.7 (3)	C4B—C12B—C13B—O2B	52.1 (4)
C4A—C12A—C13A—O2A	54.2 (4)	C14B—C12B—C13B—O2B	−72.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···O3A^i	0.82	1.97	2.785 (3)	169
O1B—H1B···O3B^ii	0.82	2.13	2.892 (3)	154
C2A—H2A···O3A^i	0.93	2.37	3.099 (4)	136
C2B—H2B···O3B^ii	0.93	2.29	3.074 (4)	141
C13B—H13D···O3A	0.97	2.43	3.311 (5)	150
C15A—H15C···O3A	0.96	2.49	2.896 (4)	105
C15B—H15E···O3B	0.96	2.44	2.859 (4)	106
C13A—H13A···O4A^iii	0.97	2.59	3.503 (4)	156

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