A diterpenoid from Isodon japonica var. glaucocalyx

The title compound, 7α,14β-dihydr­oxy-ent-kaur-16-ene-3,5-dione or glaucocalyxin A, C₂₀H₂₈O₄, a natural ent-kaurane diterpenoid, is composed of four rings with the expected cis and trans junctions. In the crystal structure, the mol­ecules are linked together by O—H...O hydrogen bonds to form double chains running along the shortest cell axis.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.044
• wR factor = 0.127
• Data-to-parameter ratio = 10.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.67 Ratio

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           27.47
           From the CIF: _reflns_number_total               2298
           Count of symmetry unique reflns         2303
           Completeness (_total/calc)             99.78%
           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
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C7     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C9     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C10    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C13    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C14    = .          R

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

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

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S1. Comment

The title compound(I), is a natural ent-kaurane diterpenoid isolated from the medicinal plant Isodon japonica var. glaucocalyx. This plant has been used as antibacterial, inflammation-diminishing and stomachic agents. The compound (I) has been isolated previously from the same source and its structure was postulated from spectroscopic methods (Kim et al.,1992). In order to further confirm the structure and conformation of (I), a crystal structure analysis has been undertaken.

The X-ray crystallographic analysis confirms the previously proposed molecular structure of (I). Fig.1 shows its conformation: two carbonyl groups locate at C3 and C15, while two hydrogen groups adopt α,β-orientations at C7 and C14 respectively. There is a trans junction between ring A (C1—C5/C10) and ring B (C5—C10); cis junctions are present between ring B and ring C (C8/C9/C11—C14), and ring C and ring D (C8/C13—C16).

Bond lengths and angles are within expected ranges (Allen et al., 1987), with average values (Å): Csp³—Csp³ = 1.541 (3), Csp³—Csp² = 1.517 (4), Csp²—Csp² (in C═C—C═O) = 1.500 (4), C═C = 1.326 (4), C═O = 1.209 (3), Csp³—O = 1.432 (3). Rings B and C have chair conformations, with average torsion angles of 54.6 (2) ° and 55.8 °, respectively. Ring A adopts a twist-boat conformation and ring D shows an evenlope conformation; the flap atom, C14, lies 0.69 (1) Å from the plane defined by atoms C8, C15, C16 and C13.

The molecule contains seven chiral centers at C5(R), C7(R), C8(R), C9(S), C10(R), C13(R) and C14(R). Although the absolute configuration could not be reliably determined from anomalous dispersion effects, the negative optical rotation showed this compound to be in the ent- kaurane series as reported in genus Isodon (Sun et al.,2001), rather than in the kaurane series, and so allowed us to assign the correct configuration. In the crystal structure the molecules are linked by O—H···O hydrogen bonds, to form double chains running along the shortest cell axis, a. (Table 1 and Fig. 2).

Related literature

For related literature, see: Allen et al. (1987); Kim et al. (1992); Sun et al. (2001).

S2. Experimental

The dried and crushed leaves of Isodon japonica var. glaucocalyx (10 kg, collected from Hui Prefecture, Henan Province, China) were extracted four times with Me₂CO/H₂O (7:3, v/v) at room temperature over a period of seven days. The extract was filtered and the solvent was removed under reduced pressure. The residue was then partitioned between water and AcOEt. After removal of the solvent, the AcOEt residue was separated by repeated silica gel (200–300 mesh) column chromatography and recrystallization from CHCl₃/Me₂CO(10:1), giving 900 mg of compound (I) (m.p. 493–495 K. Optical rotation: [α]_D²⁰ -183 ° (c 1/2, CHCl₃). Crystals suitable for X-ray analysis were obtained by slow evaporation of a solution of the compound (I) in Me₂CO at room temperature.

S3. Refinement

All H atoms were included in calculated positions and refined as riding atoms, with C—H = 0.96 Å (CH₃), 0.93 and 0.97 Å (CH₂), and 0.98 Å (CH), and with U_iso(H) = 1.2 U_eq(C). In the absence of significant anomalous scattering effects, Friedel pairs were merged. The choice of enantiomer was based on comparison of the optical rotation with that of related compounds with known stereochemistry.

Computing details

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1995); software used to prepare material for publication: SHELXTL (Siemens, 1995).

Figures

	Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of (I), viewed along the b axis. O—H···O hydrogen bonds are shown as dashed lines.

7α,14β-dihydroxy-ent-kaur-16-ene-3,5-dione

Crystal data

C20H28O4	Dx = 1.270 Mg m^−3
Mr = 332.42	Melting point: 493 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 13908 reflections
a = 6.6349 (19) Å	θ = 3.1–27.5°
b = 10.659 (4) Å	µ = 0.09 mm^−1
c = 24.586 (7) Å	T = 293 K
V = 1738.8 (10) Å^3	Block, colourless
Z = 4	0.41 × 0.20 × 0.18 mm
F(000) = 720

Data collection

Rigaku R-AXIS RAPID diffractometer	1946 reflections with I > 2σ(I)
Radiation source: Rotating Anode	Rint = 0.056
Graphite monochromator	θmax = 27.5°, θmin = 3.1°
ω scans	h = −8→8
17081 measured reflections	k = −13→13
2298 independent reflections	l = −31→31

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0826P)^2 + 0.1982P] where P = (Fo^2 + 2Fc^2)/3
2298 reflections	(Δ/σ)max = 0.001
228 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.16 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
O1	0.6082 (4)	0.8582 (2)	0.68057 (9)	0.0771 (8)
O2	0.1990 (3)	0.39429 (17)	0.49532 (6)	0.0379 (4)
O3	−0.1915 (3)	0.32770 (18)	0.57763 (8)	0.0441 (5)
O4	0.3435 (3)	0.19761 (17)	0.54776 (8)	0.0439 (5)
C1	0.2273 (5)	0.6432 (3)	0.70138 (10)	0.0479 (7)
H1A	0.0821	0.6336	0.7034	0.057*
H1B	0.2830	0.6163	0.7359	0.057*
C2	0.2764 (5)	0.7819 (3)	0.69317 (12)	0.0563 (8)
H2A	0.1662	0.8217	0.6738	0.068*
H2B	0.2884	0.8221	0.7284	0.068*
C3	0.4674 (5)	0.8012 (2)	0.66199 (10)	0.0477 (7)
C4	0.4690 (5)	0.7467 (2)	0.60447 (9)	0.0406 (6)
C5	0.3202 (4)	0.6329 (2)	0.60206 (8)	0.0309 (5)
H5	0.1860	0.6700	0.5977	0.037*
C6	0.3501 (4)	0.5498 (2)	0.55213 (8)	0.0311 (5)
H6A	0.3604	0.6019	0.5199	0.037*
H6B	0.4748	0.5030	0.5558	0.037*
C7	0.1754 (3)	0.4593 (2)	0.54579 (8)	0.0295 (5)
H7	0.0501	0.5078	0.5443	0.035*
C8	0.1644 (3)	0.3699 (2)	0.59436 (8)	0.0257 (4)
C9	0.1505 (3)	0.4486 (2)	0.64833 (8)	0.0302 (5)
H9	0.0210	0.4924	0.6457	0.036*
C10	0.3093 (3)	0.5555 (2)	0.65574 (8)	0.0300 (5)
C11	0.1273 (4)	0.3612 (3)	0.69854 (10)	0.0429 (6)
H11A	0.1696	0.4070	0.7307	0.052*
H11B	−0.0144	0.3412	0.7029	0.052*
C12	0.2459 (5)	0.2384 (3)	0.69599 (10)	0.0477 (7)
H12A	0.1948	0.1812	0.7234	0.057*
H12B	0.3865	0.2551	0.7041	0.057*
C13	0.2304 (4)	0.1762 (2)	0.63987 (11)	0.0407 (6)
H13	0.2960	0.0938	0.6395	0.049*
C14	0.3249 (3)	0.2652 (2)	0.59796 (9)	0.0322 (5)
H14	0.4551	0.2977	0.6104	0.039*
C15	−0.0298 (3)	0.2914 (2)	0.59443 (9)	0.0316 (5)
C16	0.0144 (4)	0.1678 (3)	0.62099 (13)	0.0478 (7)
C17	−0.1289 (6)	0.0875 (3)	0.63508 (14)	0.0688 (10)
H17A	−0.2634	0.1069	0.6286	0.083*
H17B	−0.0949	0.0117	0.6515	0.083*
C18	0.3899 (7)	0.8516 (3)	0.56763 (12)	0.0642 (10)
H18A	0.2557	0.8739	0.5785	0.077*
H18B	0.3883	0.8230	0.5306	0.077*
H18C	0.4761	0.9235	0.5706	0.077*
C19	0.6851 (5)	0.7164 (3)	0.58732 (14)	0.0623 (9)
H19A	0.6878	0.6962	0.5493	0.075*
H19B	0.7335	0.6461	0.6079	0.075*
H19C	0.7697	0.7879	0.5940	0.075*
C20	0.5169 (4)	0.5082 (2)	0.67412 (11)	0.0414 (6)
H20A	0.6002	0.5784	0.6837	0.050*
H20B	0.5791	0.4624	0.6450	0.050*
H20C	0.5012	0.4543	0.7051	0.050*
H2O	0.071 (5)	0.370 (3)	0.4827 (12)	0.049 (8)*
H4O	0.291 (6)	0.244 (4)	0.5241 (14)	0.076 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.104 (2)	0.0781 (16)	0.0495 (11)	−0.0581 (16)	−0.0082 (12)	−0.0065 (11)
O2	0.0415 (10)	0.0446 (9)	0.0275 (7)	−0.0064 (8)	0.0001 (7)	−0.0110 (7)
O3	0.0261 (8)	0.0535 (11)	0.0527 (10)	−0.0042 (9)	−0.0007 (8)	−0.0091 (9)
O4	0.0473 (11)	0.0401 (10)	0.0443 (10)	0.0112 (9)	0.0062 (9)	−0.0119 (8)
C1	0.0565 (17)	0.0494 (15)	0.0376 (12)	−0.0154 (13)	0.0139 (13)	−0.0167 (12)
C2	0.076 (2)	0.0440 (15)	0.0485 (15)	−0.0072 (15)	0.0103 (15)	−0.0207 (13)
C3	0.0726 (19)	0.0325 (13)	0.0379 (13)	−0.0175 (14)	−0.0048 (13)	−0.0050 (10)
C4	0.0582 (16)	0.0316 (12)	0.0321 (11)	−0.0162 (13)	−0.0016 (11)	−0.0012 (9)
C5	0.0351 (12)	0.0291 (10)	0.0284 (10)	−0.0040 (10)	−0.0003 (9)	−0.0034 (9)
C6	0.0387 (12)	0.0303 (10)	0.0243 (9)	−0.0089 (10)	0.0034 (9)	0.0009 (9)
C7	0.0296 (10)	0.0325 (11)	0.0265 (9)	−0.0017 (10)	−0.0005 (9)	−0.0047 (9)
C8	0.0229 (10)	0.0284 (10)	0.0260 (9)	−0.0021 (9)	0.0017 (8)	−0.0043 (8)
C9	0.0289 (11)	0.0328 (11)	0.0289 (10)	−0.0029 (10)	0.0065 (9)	−0.0049 (9)
C10	0.0329 (11)	0.0321 (11)	0.0250 (9)	−0.0067 (10)	0.0023 (9)	−0.0051 (9)
C11	0.0488 (14)	0.0479 (14)	0.0321 (11)	−0.0142 (13)	0.0120 (11)	0.0004 (11)
C12	0.0571 (17)	0.0456 (14)	0.0406 (13)	−0.0095 (13)	0.0029 (13)	0.0152 (12)
C13	0.0417 (13)	0.0283 (11)	0.0520 (14)	−0.0016 (11)	0.0021 (12)	0.0049 (10)
C14	0.0269 (11)	0.0339 (12)	0.0357 (11)	0.0007 (10)	0.0021 (9)	−0.0062 (9)
C15	0.0251 (11)	0.0360 (12)	0.0337 (10)	−0.0052 (10)	0.0041 (9)	−0.0094 (10)
C16	0.0392 (14)	0.0375 (13)	0.0669 (17)	−0.0096 (12)	0.0030 (13)	0.0031 (13)
C17	0.065 (2)	0.0606 (19)	0.081 (2)	−0.0317 (18)	−0.0093 (18)	0.0210 (18)
C18	0.107 (3)	0.0366 (14)	0.0493 (16)	−0.0186 (18)	−0.0143 (18)	0.0071 (13)
C19	0.0580 (18)	0.068 (2)	0.0604 (17)	−0.0345 (17)	0.0166 (15)	−0.0077 (16)
C20	0.0380 (13)	0.0431 (14)	0.0432 (13)	−0.0094 (12)	−0.0094 (11)	0.0064 (11)

Geometric parameters (Å, º)

O1—C3	1.205 (3)	C9—C11	1.554 (3)
O2—C7	1.430 (2)	C9—C10	1.562 (3)
O2—H2O	0.94 (3)	C9—H9	0.9800
O3—C15	1.213 (3)	C10—C20	1.535 (3)
O4—C14	1.434 (3)	C11—C12	1.529 (4)
O4—H4O	0.84 (4)	C11—H11A	0.9700
C1—C2	1.527 (4)	C11—H11B	0.9700
C1—C10	1.558 (3)	C12—C13	1.534 (4)
C1—H1A	0.9700	C12—H12A	0.9700
C1—H1B	0.9700	C12—H12B	0.9700
C2—C3	1.495 (4)	C13—C16	1.509 (4)
C2—H2A	0.9700	C13—C14	1.534 (3)
C2—H2B	0.9700	C13—H13	0.9800
C3—C4	1.529 (3)	C14—H14	0.9800
C4—C19	1.529 (4)	C15—C16	1.500 (4)
C4—C18	1.531 (4)	C16—C17	1.325 (4)
C4—C5	1.566 (3)	C17—H17A	0.9300
C5—C6	1.527 (3)	C17—H17B	0.9300
C5—C10	1.558 (3)	C18—H18A	0.9600
C5—H5	0.9800	C18—H18B	0.9600
C6—C7	1.516 (3)	C18—H18C	0.9600
C6—H6A	0.9700	C19—H19A	0.9600
C6—H6B	0.9700	C19—H19B	0.9600
C7—C8	1.529 (3)	C19—H19C	0.9600
C7—H7	0.9800	C20—H20A	0.9600
C8—C15	1.537 (3)	C20—H20B	0.9600
C8—C14	1.545 (3)	C20—H20C	0.9600
C8—C9	1.572 (3)
C7—O2—H2O	108.7 (17)	C5—C10—C1	107.96 (19)
C14—O4—H4O	105 (3)	C20—C10—C9	113.58 (19)
C2—C1—C10	114.3 (2)	C5—C10—C9	108.58 (17)
C2—C1—H1A	108.7	C1—C10—C9	106.63 (18)
C10—C1—H1A	108.7	C12—C11—C9	115.4 (2)
C2—C1—H1B	108.7	C12—C11—H11A	108.4
C10—C1—H1B	108.7	C9—C11—H11A	108.4
H1A—C1—H1B	107.6	C12—C11—H11B	108.4
C3—C2—C1	112.5 (2)	C9—C11—H11B	108.4
C3—C2—H2A	109.1	H11A—C11—H11B	107.5
C1—C2—H2A	109.1	C11—C12—C13	111.9 (2)
C3—C2—H2B	109.1	C11—C12—H12A	109.2
C1—C2—H2B	109.1	C13—C12—H12A	109.2
H2A—C2—H2B	107.8	C11—C12—H12B	109.2
O1—C3—C2	122.2 (2)	C13—C12—H12B	109.2
O1—C3—C4	122.5 (3)	H12A—C12—H12B	107.9
C2—C3—C4	115.3 (2)	C16—C13—C12	111.5 (2)
C3—C4—C19	110.0 (2)	C16—C13—C14	102.6 (2)
C3—C4—C18	105.5 (2)	C12—C13—C14	108.0 (2)
C19—C4—C18	108.2 (3)	C16—C13—H13	111.5
C3—C4—C5	108.96 (19)	C12—C13—H13	111.5
C19—C4—C5	114.7 (2)	C14—C13—H13	111.5
C18—C4—C5	109.1 (2)	O4—C14—C13	107.62 (19)
C6—C5—C10	112.34 (18)	O4—C14—C8	111.89 (18)
C6—C5—C4	113.44 (19)	C13—C14—C8	101.75 (18)
C10—C5—C4	114.07 (17)	O4—C14—H14	111.7
C6—C5—H5	105.3	C13—C14—H14	111.7
C10—C5—H5	105.3	C8—C14—H14	111.7
C4—C5—H5	105.3	O3—C15—C16	127.0 (2)
C7—C6—C5	110.63 (18)	O3—C15—C8	124.6 (2)
C7—C6—H6A	109.5	C16—C15—C8	108.4 (2)
C5—C6—H6A	109.5	C17—C16—C15	122.8 (3)
C7—C6—H6B	109.5	C17—C16—C13	129.7 (3)
C5—C6—H6B	109.5	C15—C16—C13	105.5 (2)
H6A—C6—H6B	108.1	C16—C17—H17A	120.0
O2—C7—C6	108.30 (18)	C16—C17—H17B	120.0
O2—C7—C8	112.40 (18)	H17A—C17—H17B	120.0
C6—C7—C8	110.64 (17)	C4—C18—H18A	109.5
O2—C7—H7	108.5	C4—C18—H18B	109.5
C6—C7—H7	108.5	H18A—C18—H18B	109.5
C8—C7—H7	108.5	C4—C18—H18C	109.5
C7—C8—C15	112.33 (18)	H18A—C18—H18C	109.5
C7—C8—C14	117.52 (17)	H18B—C18—H18C	109.5
C15—C8—C14	100.63 (18)	C4—C19—H19A	109.5
C7—C8—C9	109.23 (17)	C4—C19—H19B	109.5
C15—C8—C9	103.89 (16)	H19A—C19—H19B	109.5
C14—C8—C9	112.18 (17)	C4—C19—H19C	109.5
C11—C9—C10	114.28 (19)	H19A—C19—H19C	109.5
C11—C9—C8	110.87 (18)	H19B—C19—H19C	109.5
C10—C9—C8	116.61 (17)	C10—C20—H20A	109.5
C11—C9—H9	104.5	C10—C20—H20B	109.5
C10—C9—H9	104.5	H20A—C20—H20B	109.5
C8—C9—H9	104.5	C10—C20—H20C	109.5
C20—C10—C5	112.43 (19)	H20A—C20—H20C	109.5
C20—C10—C1	107.4 (2)	H20B—C20—H20C	109.5
C10—C1—C2—C3	−28.6 (4)	C2—C1—C10—C5	−28.6 (3)
C1—C2—C3—O1	−120.8 (3)	C2—C1—C10—C9	−145.1 (3)
C1—C2—C3—C4	60.8 (4)	C11—C9—C10—C20	52.7 (3)
O1—C3—C4—C19	28.0 (4)	C8—C9—C10—C20	−78.8 (2)
C2—C3—C4—C19	−153.5 (3)	C11—C9—C10—C5	178.57 (19)
O1—C3—C4—C18	−88.5 (4)	C8—C9—C10—C5	47.0 (3)
C2—C3—C4—C18	89.9 (3)	C11—C9—C10—C1	−65.3 (3)
O1—C3—C4—C5	154.5 (3)	C8—C9—C10—C1	163.1 (2)
C2—C3—C4—C5	−27.1 (3)	C10—C9—C11—C12	−97.4 (3)
C3—C4—C5—C6	−164.4 (2)	C8—C9—C11—C12	36.9 (3)
C19—C4—C5—C6	−40.7 (3)	C9—C11—C12—C13	−43.5 (3)
C18—C4—C5—C6	80.8 (3)	C11—C12—C13—C16	−49.4 (3)
C3—C4—C5—C10	−34.1 (3)	C11—C12—C13—C14	62.6 (3)
C19—C4—C5—C10	89.7 (3)	C16—C13—C14—O4	−72.6 (2)
C18—C4—C5—C10	−148.8 (2)	C12—C13—C14—O4	169.6 (2)
C10—C5—C6—C7	61.0 (2)	C16—C13—C14—C8	45.2 (2)
C4—C5—C6—C7	−167.78 (19)	C12—C13—C14—C8	−72.7 (2)
C5—C6—C7—O2	173.36 (18)	C7—C8—C14—O4	−49.4 (3)
C5—C6—C7—C8	−63.0 (2)	C15—C8—C14—O4	72.9 (2)
O2—C7—C8—C15	−68.3 (2)	C9—C8—C14—O4	−177.24 (17)
C6—C7—C8—C15	170.46 (18)	C7—C8—C14—C13	−164.03 (19)
O2—C7—C8—C14	47.7 (3)	C15—C8—C14—C13	−41.8 (2)
C6—C7—C8—C14	−73.5 (2)	C9—C8—C14—C13	68.1 (2)
O2—C7—C8—C9	176.95 (18)	C7—C8—C15—O3	−33.0 (3)
C6—C7—C8—C9	55.7 (2)	C14—C8—C15—O3	−158.9 (2)
C7—C8—C9—C11	176.91 (19)	C9—C8—C15—O3	84.9 (3)
C15—C8—C9—C11	56.9 (2)	C7—C8—C15—C16	149.7 (2)
C14—C8—C9—C11	−51.0 (2)	C14—C8—C15—C16	23.9 (2)
C7—C8—C9—C10	−50.0 (2)	C9—C8—C15—C16	−92.3 (2)
C15—C8—C9—C10	−170.04 (19)	O3—C15—C16—C17	−8.3 (5)
C14—C8—C9—C10	82.1 (2)	C8—C15—C16—C17	168.9 (3)
C6—C5—C10—C20	75.4 (2)	O3—C15—C16—C13	−173.6 (2)
C4—C5—C10—C20	−55.5 (3)	C8—C15—C16—C13	3.6 (3)
C6—C5—C10—C1	−166.4 (2)	C12—C13—C16—C17	−78.6 (4)
C4—C5—C10—C1	62.8 (3)	C14—C13—C16—C17	166.1 (3)
C6—C5—C10—C9	−51.1 (3)	C12—C13—C16—C15	85.3 (3)
C4—C5—C10—C9	177.98 (19)	C14—C13—C16—C15	−30.0 (3)
C2—C1—C10—C20	92.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O4^i	0.94 (3)	1.83 (3)	2.765 (3)	171 (3)
O4—H4O···O2	0.84 (4)	1.85 (4)	2.641 (3)	156 (4)

Symmetry code: (i) x−1/2, −y+1/2, −z+1.