ent-5α,3,15-Dioxodolabr-4(18)-ene-16,18-diol

The title compound, C₂₀H₃₀O₄, is a dolabrane diterpenoid isolated from Ceriops tagal, in which one of the three fused cyclo­hexane rings adopts a half-chair conformation and the other two are in the standard chair conformations. The hy­droxy­methyl­idene substituent is attached to the half-chair cyclo­hexane. An intra­molecular O—H...O hydrogen bond generate an S(6) ring motif. In the crystal, mol­ecules are arranged into screw chains along the [001] direction. The crystal is stabilized by O—H...O hydrogen bonds and weaker C—H...O inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.052
• wR factor = 0.157
• Data-to-parameter ratio = 12.2

checkCIF/PLATON results

No syntax errors found



Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O2     --  C18     ..       5.71 su

Alert level G
REFLT03_ALERT_4_G 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.
           From the CIF: _diffrn_reflns_theta_max           29.00
           From the CIF: _reflns_number_total               2691
           Count of symmetry unique reflns         2692
           Completeness (_total/calc)             99.96%
           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
PLAT960_ALERT_3_G Number of Intensities with I .LT. - 2*sig(I) ..           3
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2
PLAT791_ALERT_4_G Note: The Model has Chirality at C5     (Verify)          S
PLAT791_ALERT_4_G Note: The Model has Chirality at C8     (Verify)          S
PLAT791_ALERT_4_G Note: The Model has Chirality at C9     (Verify)          R
PLAT791_ALERT_4_G Note: The Model has Chirality at C10    (Verify)          R
PLAT791_ALERT_4_G Note: The Model has Chirality at C13    (Verify)          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   8 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   7 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Ceriops tagal (Perr.) C. B. Robinson is a mangrove plant belonging to the Rhizophoraceae family. Diterpenoids and triterpenoids are the main secondary metabolites of C. tagal (Chantrapromma et al., 2007; Hu et al., 2010; Zhang et al., 2005). During the course of our studies on the chemical constituents and bioactive compounds from Thai medicinal plants, the title dolabrane diterpenoid compound (I), which is known as Tagalsin S (Hu et al., 2010), was isolated from the the stem barks of C. tagal. We have also previously reported the crystal structures of two diterpenoid compounds isolated from the same plant (Chantrapromma et al., 2007; Fun et al., 2006). We herein report the crystal structure of (I).

The molecule of the title compound contains a fused three-ring system A/B/C (Fig. 1). The A/B ring junction is cis-fused and B/C is trans-fused. The cyclohexane ring A adopts half-chair conformation with puckering parameters Q = 0.539 (3) Å, θ = 111.0 (3)° and φ = 92.5 (4)°, rings B and C are in standard chair conformations (Cremer & Pople 1975). The hydroxylmethylidine substituent is planarly attached to cyclohexane ring A at atom C4 as indicated by the torsion angle C3—C4—C18—O2 of 4.4 (5)° and the bond angles around atom C4 are indicative of sp² hybridization for this atom. The orientations of the carbonyl and alcohol substituent groups at atom C13 are described by the torsion angles C13–C15—C16—O4 = 166.3 (3)° and O3–C15–C16–O4 = -11.1 (5)°. Intramolecular O2—H1O2···O1 hydrogen bond (Table 1) generates S(6) ring motif (Fig. 1) (Bernstein et al., 1995). The bond distances are of normal values (Allen et al., 1987) and are comparable with the related structures (Chantrapromma et al., 2007; Fun et al., 2006).

In the crystal structure (Fig. 2), the molecules are arranged into screw chains along the [0 0 1] direction and the adjacent chains are further linked by weak C—H···O interactions (Table 1). The crystal packing of (I) is stabilized by intermolecular O—H···O hydrogen bonds and weak C—H···O interactions (Fig. 2 and Table 1).

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987). For ring conformations, see: Cremer & Pople (1975). For background to diterpenoids, see, for example: Hu et al. (2010); Zhang et al. (2005). For related structures, see: Chantrapromma et al. (2007); Fun et al. (2006). For the stability of the temperature controller used in the data collection, see Cosier & Glazer, (1986).

S2. Experimental

The air-dried and crushed stem barks of C. tagal (4.8 kg) were extracted with methylene chloride and then concentrated in vacuo to give a residue (17.4 g). This residue was subjected to quick column chromatography over silica gel using solvents of increasing polarity from hexane through 50% acetone/hexane. The eluates were collected and combined, based on TLC, to give 20 fractions (F1—F20). Fraction F14 was further purified by repeated quick column chromatography with CH₂Cl₂/acetone (9:1 v/v) yielding title compound (30.4 mg). Colorless block-shaped single crystals of the title compound suitable for x-ray structure determination were recrystallized from hexane/CH₂Cl₂ (1:1, v/v) after several days, Mp. 395–396 K.

S3. Refinement

All H atoms were placed in calculated positions with d(O—H) = 0.82 Å and d(C—H) = 0.93 Å for aromatic and CH, 0.97 for CH₂ and 0.96 Å for CH₃ atoms. The U_iso values were constrained to be 1.5U_eq of the carrier atom for hydroxy and methyl H atoms and 1.2U_eq for the remaining H atoms. A rotating group model was used for the methyl groups. The highest residual electron density peak is located at 0.18 Å from H1B and the deepest hole is located at 0.50 Å from O2. A total of 2024 Friedel pairs were merged before final refinement as there is no large anomalous dispersion for the determination of the absolute configuration.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen bonds was drawn as dash line.
	Fig. 2. The crystal packing of (I) viewed along the b axis, showing one dimensional chains along the [0 0 1] direction. Hydrogen bonds were shown as dashed lines.

ent-5α,3,15-Dioxodolabr-4(18)-ene-16,18-diol

Crystal data

C20H30O4	Dx = 1.249 Mg m^−3
Mr = 334.44	Melting point = 495–496 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2691 reflections
a = 7.9633 (3) Å	θ = 2.0–29.0°
b = 10.7166 (4) Å	µ = 0.09 mm^−1
c = 20.8338 (7) Å	T = 100 K
V = 1777.95 (11) Å^3	Plate, colourless
Z = 4	0.58 × 0.51 × 0.10 mm
F(000) = 728

Data collection

Bruker APEXII CCD area-detector diffractometer	2691 independent reflections
Radiation source: sealed tube	2084 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 29.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.952, Tmax = 0.992	k = −14→10
20568 measured reflections	l = −24→28

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.157	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.077P)^2 + 0.7994P] where P = (Fo^2 + 2Fc^2)/3
2691 reflections	(Δ/σ)max < 0.001
220 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
O1	0.9767 (3)	0.4254 (2)	0.05460 (11)	0.0420 (6)
O2	1.2362 (4)	0.3517 (3)	0.10215 (15)	0.0633 (8)
H1O2	1.1724	0.3988	0.0830	0.095*
O3	0.5983 (4)	0.4271 (2)	0.41250 (10)	0.0413 (6)
O4	0.6697 (4)	0.3378 (2)	0.52946 (11)	0.0552 (8)
H1O4	0.6102	0.4000	0.5273	0.083*
C1	0.6196 (4)	0.2200 (3)	0.09423 (15)	0.0360 (8)
H1A	0.5759	0.1550	0.0665	0.043*
H1B	0.5242	0.2658	0.1110	0.043*
C2	0.7243 (4)	0.3092 (3)	0.05327 (15)	0.0379 (8)
H2A	0.7218	0.2792	0.0094	0.045*
H2B	0.6696	0.3900	0.0537	0.045*
C3	0.9026 (4)	0.3276 (3)	0.07172 (13)	0.0294 (7)
C4	0.9885 (3)	0.2325 (3)	0.10845 (12)	0.0221 (5)
C5	0.8927 (4)	0.1186 (3)	0.13108 (13)	0.0230 (6)
C6	0.9782 (4)	0.0532 (3)	0.18765 (13)	0.0301 (7)
H6A	0.9239	−0.0267	0.1947	0.036*
H6B	1.0944	0.0370	0.1765	0.036*
C7	0.9731 (4)	0.1276 (3)	0.24997 (14)	0.0272 (6)
H7A	1.0337	0.2054	0.2446	0.033*
H7B	1.0269	0.0805	0.2840	0.033*
C8	0.7911 (4)	0.1547 (2)	0.26801 (13)	0.0226 (6)
H8A	0.7344	0.0737	0.2708	0.027*
C9	0.6987 (3)	0.2298 (2)	0.21580 (13)	0.0200 (5)
C10	0.7108 (4)	0.1569 (3)	0.15117 (13)	0.0241 (6)
H10A	0.6510	0.0783	0.1585	0.029*
C11	0.5122 (4)	0.2385 (3)	0.23683 (14)	0.0318 (7)
H11A	0.4514	0.2889	0.2059	0.038*
H11B	0.4636	0.1555	0.2363	0.038*
C12	0.4884 (4)	0.2955 (3)	0.30434 (14)	0.0338 (7)
H12A	0.5200	0.3828	0.3030	0.041*
H12B	0.3705	0.2912	0.3157	0.041*
C13	0.5915 (4)	0.2302 (3)	0.35673 (14)	0.0276 (6)
C14	0.7769 (4)	0.2146 (2)	0.33451 (13)	0.0227 (6)
H14A	0.8305	0.2958	0.3336	0.027*
H14B	0.8364	0.1633	0.3654	0.027*
C15	0.6017 (4)	0.3139 (3)	0.41616 (14)	0.0290 (6)
C16	0.6242 (5)	0.2539 (3)	0.48109 (14)	0.0394 (8)
H16A	0.5201	0.2133	0.4932	0.047*
H16B	0.7100	0.1900	0.4778	0.047*
C17	0.5129 (5)	0.1042 (3)	0.37320 (18)	0.0463 (9)
H17A	0.4050	0.1172	0.3926	0.070*
H17B	0.5844	0.0603	0.4026	0.070*
H17C	0.4998	0.0559	0.3347	0.070*
C18	1.1538 (4)	0.2500 (3)	0.11951 (15)	0.0342 (7)
H18A	1.2130	0.1872	0.1404	0.041*
C19	0.8839 (5)	0.0238 (3)	0.07522 (15)	0.0352 (7)
H19A	0.9938	−0.0099	0.0674	0.053*
H19B	0.8441	0.0649	0.0372	0.053*
H19C	0.8085	−0.0427	0.0864	0.053*
C20	0.7677 (4)	0.3630 (2)	0.21044 (13)	0.0236 (6)
H20A	0.7370	0.4095	0.2480	0.035*
H20B	0.7213	0.4026	0.1731	0.035*
H20C	0.8878	0.3602	0.2068	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0564 (16)	0.0328 (12)	0.0369 (12)	0.0036 (12)	0.0098 (12)	0.0126 (10)
O2	0.0435 (16)	0.0705 (19)	0.076 (2)	−0.0151 (15)	0.0071 (15)	0.0049 (17)
O3	0.0643 (16)	0.0281 (11)	0.0314 (11)	0.0050 (12)	−0.0030 (12)	−0.0080 (10)
O4	0.088 (2)	0.0437 (14)	0.0337 (12)	0.0225 (15)	−0.0180 (13)	−0.0096 (11)
C1	0.0222 (14)	0.056 (2)	0.0301 (15)	0.0036 (14)	−0.0107 (12)	−0.0167 (15)
C2	0.0410 (19)	0.0438 (19)	0.0290 (16)	0.0139 (16)	−0.0147 (14)	−0.0040 (14)
C3	0.0375 (16)	0.0331 (16)	0.0177 (13)	0.0076 (14)	0.0011 (12)	0.0008 (12)
C4	0.0231 (13)	0.0252 (13)	0.0180 (12)	0.0007 (11)	−0.0014 (10)	−0.0005 (10)
C5	0.0233 (13)	0.0212 (13)	0.0245 (13)	0.0021 (11)	−0.0020 (11)	−0.0020 (10)
C6	0.0374 (17)	0.0228 (14)	0.0303 (14)	0.0123 (13)	0.0022 (13)	0.0022 (12)
C7	0.0310 (15)	0.0272 (14)	0.0232 (12)	0.0127 (13)	−0.0015 (12)	0.0032 (11)
C8	0.0289 (14)	0.0133 (11)	0.0254 (13)	0.0001 (11)	0.0041 (11)	0.0011 (10)
C9	0.0154 (11)	0.0198 (12)	0.0248 (13)	−0.0013 (10)	−0.0024 (10)	−0.0051 (11)
C10	0.0212 (13)	0.0241 (14)	0.0269 (14)	−0.0030 (11)	−0.0016 (11)	−0.0068 (12)
C11	0.0190 (13)	0.0440 (18)	0.0325 (16)	−0.0016 (13)	−0.0016 (11)	−0.0148 (14)
C12	0.0187 (14)	0.0483 (18)	0.0345 (15)	0.0004 (14)	0.0012 (12)	−0.0138 (14)
C13	0.0288 (14)	0.0250 (14)	0.0290 (14)	−0.0062 (13)	0.0068 (12)	−0.0070 (12)
C14	0.0293 (14)	0.0145 (12)	0.0242 (13)	0.0027 (11)	0.0002 (11)	0.0009 (10)
C15	0.0265 (14)	0.0320 (15)	0.0286 (15)	0.0014 (13)	0.0044 (12)	−0.0051 (12)
C16	0.050 (2)	0.0347 (17)	0.0333 (18)	0.0056 (17)	0.0005 (15)	−0.0039 (15)
C17	0.057 (2)	0.0367 (18)	0.0451 (19)	−0.0219 (17)	0.0195 (18)	−0.0115 (15)
C18	0.0254 (14)	0.0401 (18)	0.0372 (17)	−0.0031 (14)	−0.0048 (13)	0.0034 (15)
C19	0.0434 (19)	0.0287 (15)	0.0335 (16)	0.0018 (15)	0.0058 (15)	−0.0086 (13)
C20	0.0285 (14)	0.0170 (12)	0.0253 (13)	0.0036 (11)	−0.0081 (11)	−0.0002 (11)

Geometric parameters (Å, º)

O1—C3	1.254 (4)	C9—C20	1.534 (4)
O2—C18	1.323 (4)	C9—C11	1.551 (4)
O2—H1O2	0.8200	C9—C10	1.560 (4)
O3—C15	1.216 (4)	C10—H10A	0.9800
O4—C16	1.398 (4)	C11—C12	1.545 (4)
O4—H1O4	0.8200	C11—H11A	0.9700
C1—C2	1.529 (5)	C11—H11B	0.9700
C1—C10	1.547 (4)	C12—C13	1.535 (4)
C1—H1A	0.9700	C12—H12A	0.9700
C1—H1B	0.9700	C12—H12B	0.9700
C2—C3	1.484 (5)	C13—C17	1.527 (4)
C2—H2A	0.9700	C13—C15	1.531 (4)
C2—H2B	0.9700	C13—C14	1.556 (4)
C3—C4	1.446 (4)	C14—H14A	0.9700
C4—C18	1.350 (4)	C14—H14B	0.9700
C4—C5	1.515 (4)	C15—C16	1.508 (4)
C5—C6	1.531 (4)	C16—H16A	0.9700
C5—C19	1.547 (4)	C16—H16B	0.9700
C5—C10	1.563 (4)	C17—H17A	0.9600
C6—C7	1.525 (4)	C17—H17B	0.9600
C6—H6A	0.9700	C17—H17C	0.9600
C6—H6B	0.9700	C18—H18A	0.9300
C7—C8	1.525 (4)	C19—H19A	0.9600
C7—H7A	0.9700	C19—H19B	0.9600
C7—H7B	0.9700	C19—H19C	0.9600
C8—C14	1.531 (4)	C20—H20A	0.9600
C8—C9	1.540 (4)	C20—H20B	0.9600
C8—H8A	0.9800	C20—H20C	0.9600
C18—O2—H1O2	109.5	C5—C10—H10A	105.5
C16—O4—H1O4	109.5	C12—C11—C9	113.5 (2)
C2—C1—C10	116.4 (3)	C12—C11—H11A	108.9
C2—C1—H1A	108.2	C9—C11—H11A	108.9
C10—C1—H1A	108.2	C12—C11—H11B	108.9
C2—C1—H1B	108.2	C9—C11—H11B	108.9
C10—C1—H1B	108.2	H11A—C11—H11B	107.7
H1A—C1—H1B	107.3	C13—C12—C11	113.7 (3)
C3—C2—C1	117.4 (3)	C13—C12—H12A	108.8
C3—C2—H2A	107.9	C11—C12—H12A	108.8
C1—C2—H2A	107.9	C13—C12—H12B	108.8
C3—C2—H2B	107.9	C11—C12—H12B	108.8
C1—C2—H2B	107.9	H12A—C12—H12B	107.7
H2A—C2—H2B	107.2	C17—C13—C15	111.0 (2)
O1—C3—C4	121.1 (3)	C17—C13—C12	110.1 (3)
O1—C3—C2	119.2 (3)	C15—C13—C12	109.7 (2)
C4—C3—C2	119.7 (3)	C17—C13—C14	111.2 (3)
C18—C4—C3	117.0 (3)	C15—C13—C14	104.7 (2)
C18—C4—C5	123.4 (3)	C12—C13—C14	110.2 (2)
C3—C4—C5	119.6 (3)	C8—C14—C13	112.6 (2)
C4—C5—C6	112.6 (2)	C8—C14—H14A	109.1
C4—C5—C19	108.5 (2)	C13—C14—H14A	109.1
C6—C5—C19	107.4 (2)	C8—C14—H14B	109.1
C4—C5—C10	109.8 (2)	C13—C14—H14B	109.1
C6—C5—C10	109.0 (2)	H14A—C14—H14B	107.8
C19—C5—C10	109.4 (2)	O3—C15—C16	118.9 (3)
C7—C6—C5	113.8 (2)	O3—C15—C13	122.2 (3)
C7—C6—H6A	108.8	C16—C15—C13	118.8 (3)
C5—C6—H6A	108.8	O4—C16—C15	113.8 (3)
C7—C6—H6B	108.8	O4—C16—H16A	108.8
C5—C6—H6B	108.8	C15—C16—H16A	108.8
H6A—C6—H6B	107.7	O4—C16—H16B	108.8
C6—C7—C8	109.5 (3)	C15—C16—H16B	108.8
C6—C7—H7A	109.8	H16A—C16—H16B	107.7
C8—C7—H7A	109.8	C13—C17—H17A	109.5
C6—C7—H7B	109.8	C13—C17—H17B	109.5
C8—C7—H7B	109.8	H17A—C17—H17B	109.5
H7A—C7—H7B	108.2	C13—C17—H17C	109.5
C7—C8—C14	111.9 (2)	H17A—C17—H17C	109.5
C7—C8—C9	112.3 (2)	H17B—C17—H17C	109.5
C14—C8—C9	112.6 (2)	O2—C18—C4	123.4 (3)
C7—C8—H8A	106.5	O2—C18—H18A	118.3
C14—C8—H8A	106.5	C4—C18—H18A	118.3
C9—C8—H8A	106.5	C5—C19—H19A	109.5
C20—C9—C8	111.5 (2)	C5—C19—H19B	109.5
C20—C9—C11	107.9 (2)	H19A—C19—H19B	109.5
C8—C9—C11	106.8 (2)	C5—C19—H19C	109.5
C20—C9—C10	112.4 (2)	H19A—C19—H19C	109.5
C8—C9—C10	108.6 (2)	H19B—C19—H19C	109.5
C11—C9—C10	109.5 (2)	C9—C20—H20A	109.5
C1—C10—C9	114.5 (2)	C9—C20—H20B	109.5
C1—C10—C5	110.2 (2)	H20A—C20—H20B	109.5
C9—C10—C5	114.9 (2)	C9—C20—H20C	109.5
C1—C10—H10A	105.5	H20A—C20—H20C	109.5
C9—C10—H10A	105.5	H20B—C20—H20C	109.5
C10—C1—C2—C3	−0.2 (4)	C8—C9—C10—C5	−52.4 (3)
C1—C2—C3—O1	−157.0 (3)	C11—C9—C10—C5	−168.7 (3)
C1—C2—C3—C4	23.7 (4)	C4—C5—C10—C1	57.8 (3)
O1—C3—C4—C18	−4.4 (4)	C6—C5—C10—C1	−178.4 (2)
C2—C3—C4—C18	175.0 (3)	C19—C5—C10—C1	−61.2 (3)
O1—C3—C4—C5	177.0 (2)	C4—C5—C10—C9	−73.3 (3)
C2—C3—C4—C5	−3.6 (4)	C6—C5—C10—C9	50.6 (3)
C18—C4—C5—C6	22.3 (4)	C19—C5—C10—C9	167.7 (2)
C3—C4—C5—C6	−159.2 (2)	C20—C9—C11—C12	−64.2 (3)
C18—C4—C5—C19	−96.4 (3)	C8—C9—C11—C12	55.8 (3)
C3—C4—C5—C19	82.1 (3)	C10—C9—C11—C12	173.2 (3)
C18—C4—C5—C10	144.0 (3)	C9—C11—C12—C13	−53.6 (4)
C3—C4—C5—C10	−37.5 (3)	C11—C12—C13—C17	−74.3 (3)
C4—C5—C6—C7	69.2 (3)	C11—C12—C13—C15	163.3 (3)
C19—C5—C6—C7	−171.3 (3)	C11—C12—C13—C14	48.6 (3)
C10—C5—C6—C7	−52.9 (3)	C7—C8—C14—C13	−174.0 (2)
C5—C6—C7—C8	58.1 (3)	C9—C8—C14—C13	58.3 (3)
C6—C7—C8—C14	172.7 (2)	C17—C13—C14—C8	71.3 (3)
C6—C7—C8—C9	−59.5 (3)	C15—C13—C14—C8	−168.8 (2)
C7—C8—C9—C20	−68.1 (3)	C12—C13—C14—C8	−51.0 (3)
C14—C8—C9—C20	59.3 (3)	C17—C13—C15—O3	−151.8 (4)
C7—C8—C9—C11	174.2 (2)	C12—C13—C15—O3	−30.0 (4)
C14—C8—C9—C11	−58.4 (3)	C14—C13—C15—O3	88.2 (4)
C7—C8—C9—C10	56.2 (3)	C17—C13—C15—C16	31.0 (4)
C14—C8—C9—C10	−176.4 (2)	C12—C13—C15—C16	152.8 (3)
C2—C1—C10—C9	91.3 (3)	C14—C13—C15—C16	−89.0 (3)
C2—C1—C10—C5	−40.0 (3)	O3—C15—C16—O4	−11.1 (5)
C20—C9—C10—C1	−57.5 (3)	C13—C15—C16—O4	166.3 (3)
C8—C9—C10—C1	178.7 (2)	C3—C4—C18—O2	4.4 (5)
C11—C9—C10—C1	62.4 (3)	C5—C4—C18—O2	−177.1 (3)
C20—C9—C10—C5	71.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···O1	0.82	1.69	2.424 (4)	148
O4—H1O4···O1^i	0.82	2.07	2.841 (3)	156
C1—H1B···O2^ii	0.97	2.48	3.368 (5)	152
C12—H12A···O3	0.97	2.41	2.799 (4)	103
C17—H17A···O4^iii	0.96	2.53	3.460 (5)	164

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