Trilobolide-6-O-isobutyrate, a eudesmanolide from Wedelia trilobata

The structure of trilobolide-6-O-isobutyrate, C₂₃H₃₂O₉, isolated from the flower of Wedelia trilobata, shows an eudesmanolide sesquiterpene skeleton constructed from the fusion of two cyclo­hexane rings and a lactone ring.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.051
• wR factor = 0.153
• Data-to-parameter ratio = 7.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level A:



TYPE_089  Alert A _refine_ls_abs_structure_Flack is not of type numb.

REFI_021  Alert A _refine_ls_abs_structure_details is missing
          Absolute structure method and Friedel-pair number.
          This should be present as the _refine_ls_abs_structure_Flack or Roger
          field has been filled out.


 Alert Level C:



REFNR_01  Alert C Ratio of reflections to parameters is < 8 for a
          non-centrosymmetric structure, where ZMAX < 18
          sine(theta)/lambda                0.5946
          Proportion of unique data used    0.5079
          Ratio reflections to parameters   7.5679

PLAT_737  Alert C D...A   Calc    2.985(7), Rep    2.986(3) ....       2.33 su-Ratio
                     O5   -O9      1.555   1.545

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.00
         From the CIF: _reflns_number_total               4172
         Count of symmetry unique reflns         2123
         Completeness (_total/calc)            196.51%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      2049
         Fraction of Friedel pairs measured     0.965
         Are heavy atom types Z>Si present           no
          ALERT: MoKa measured Friedel data cannot be used to
                 determine absolute structure in a light-atom
                 study EXCEPT under VERY special conditions.
                 It is preferred that Friedel data is merged in such cases.


 2 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

Wedelia is a large genus of the Compositae family from which many eudesmanolide sesquiterpenes have been isolated in recent years (Bohlmann et al., 1981; Farag et al., 1996; Ferreira et al., 1994; Ragasa et al., 1993). Wedelia trilobata, a vigorous creeping herb native to tropical areas, was introduced into Hong Kong and utilized as a substitute of W. chinensis, a Traditional Chinese medicine used for the treatment of the common cold, hepatitis, indigestion and infections (Jiangsu New Medical College, 1977). As part of our effort to search for antitumor agents from natural sources, the investigation of the chemical components of W. trilobata flowers has been undertaken. In this connection, the title compound, trilobolide-6-O-isobutyrate, (I), has been isolated and studied by X-ray crystallography. Compound (I) was previously isolated from W. trilobata (Bohlmann et al., 1981) and W. prostrata (Farag et al., 1996) and its chemical structure elucidated based on spectroscopic methods.

Compound (I) (Fig. 1 and Table 1) is characterized by the fusion of two cyclohexane rings (ring A and B) with a lactone ring (ring C). Rings A and B are trans-fused and rings B and C are cis-fused. Ring A exists in a chair conformation, with a mean torsion angle of 56° (ideal angle = 56°). Ring B exists in a twist-chair conformation, as indicated by the mean torsion angle of 47°. Finally, the five-membered lactone ring C adopts an envelope conformation with atom C8 displaced by 0.42 Å from the least-squares plane of the remaining four atoms. The acetoxyl group at C1 and the hydroxy group at C4 adopt equatorial positions. The methyl groups at C4 and C10, the isobutyrate group at C6 and the acetoxyl group at C9 occupy axial positions.

An intermolecular hydrogen bond, involving O5—H and O9ⁱ, with an O5···O9 distance of 2.986 (3) Å, is noted [symmetry code: (i) x, y − 1, z].

S2. Experimental

The flowers of Wedelia trilobata growing in Hong Kong were collected in April, 2002. The pulverized dried flowers (500 g) were extracted with MeOH three times under reflux temperature. The extract was concentrated in vacuo to give a residue (98.8 g). A large portion of the residue (90 g) was suspended in distilled water and partitioned with petroleum ether, CHCl₃, EtOAc and n-BuOH successively. The CHCl₃ fraction (4.58 g) was subjected to column chromatography over silica gel (Merck, 60 g) and eluted with a gradient hexane–EtOAc system (from 0:100 to 100:0) to afford 26 fractions. rilobolide-6-O-isobutyrate (80 mg) was obtained from fraction 23 and further recrystallized from an acetone solution of the compound.

S3. Refinement

H atoms were included in the riding model approximation and assigned 1.2U_eq (CH and CH₂) and 1.5U_eq (CH₃) of the atom to which they were bonded. The hydroxy H atom was located from a difference map and its O—H distance was restrained to 0.82 Å. Terminal atoms C22 and C23 exhibit significant thermal motion and were refined isotropically.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART and SAINT (Bruker, 1998); data reduction: SHELXS97 (Sheldrick, 1990); program(s) used to solve structure: SHELXTL/PC (Sheldrick, 1997); program(s) used to refine structure: SHELXTL/PC; molecular graphics: XP (Bruker, 1998); software used to prepare material for publication: SHELXTL/PC.

Figures

Fig. 1. The molecular structure of (I), showing the atom-labeling scheme and ellipsoids drawn at the 30% probability level (Bruker, 1998).

(I)

Crystal data

C23H32O9	Dx = 1.267 Mg m^−3
Mr = 452.49	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P65	Cell parameters from 4824 reflections
a = 9.8368 (8) Å	θ = 2.4–20.8°
c = 42.455 (5) Å	µ = 0.10 mm^−1
V = 3557.6 (6) Å^3	T = 293 K
Z = 6	Block, colorless
F(000) = 1452	0.62 × 0.34 × 0.29 mm

Data collection

Siemens SMART/CCD diffractometer	3029 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.063
Graphite monochromator	θmax = 25.0°, θmin = 2.4°
ω scans	h = −11→7
19275 measured reflections	k = −11→11
4172 independent reflections	l = −50→50

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.153	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.105P)^2 + 0.2647P] where P = (Fo^2 + 2Fc^2)/3
2119 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.30 e Å^−3
1 restraint	Δρmin = −0.31 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	1.0229 (4)	0.4731 (4)	0.15271 (7)	0.0534 (8)
O2	0.7978 (6)	0.3943 (7)	0.17972 (11)	0.0958 (16)
O3	0.8361 (4)	0.5346 (4)	0.08709 (7)	0.0448 (7)
O4	0.8481 (7)	0.6893 (8)	0.12673 (14)	0.122 (2)
O5	0.8084 (5)	0.0559 (4)	0.05076 (10)	0.0687 (11)
H5A	0.8146	−0.0236	0.0484	0.08 (2)*
O6	1.1286 (4)	0.3798 (4)	0.02784 (7)	0.0486 (8)
O7	1.0525 (5)	0.3461 (6)	−0.02266 (8)	0.0718 (11)
O8	1.0362 (5)	0.7789 (4)	0.05164 (8)	0.0556 (9)
O9	0.8391 (7)	0.7867 (5)	0.02710 (11)	0.0889 (15)
C1	0.9351 (6)	0.3630 (6)	0.12733 (11)	0.0501 (11)
H1A	0.8296	0.3499	0.1265	0.060*
C2	0.9204 (7)	0.2058 (6)	0.13451 (12)	0.0619 (14)
H2A	0.8634	0.1644	0.1541	0.074*
H2B	1.0238	0.2174	0.1368	0.074*
C3	0.8322 (7)	0.0934 (6)	0.10729 (13)	0.0634 (14)
H3A	0.8211	−0.0083	0.1119	0.076*
H3B	0.7277	0.0797	0.1059	0.076*
C4	0.9140 (6)	0.1505 (5)	0.07540 (11)	0.0519 (12)
C5	0.9342 (5)	0.3163 (5)	0.06973 (10)	0.0412 (10)
H5B	0.8265	0.2969	0.0710	0.049*
C6	0.9848 (5)	0.3804 (5)	0.03632 (10)	0.0409 (9)
H6A	0.9019	0.3098	0.0218	0.049*
C7	1.0154 (6)	0.5468 (5)	0.03049 (11)	0.0449 (10)
H7A	1.0960	0.5926	0.0141	0.054*
C8	1.0765 (6)	0.6583 (5)	0.05857 (11)	0.0449 (10)
H8A	1.1908	0.7060	0.0600	0.054*
C9	1.0026 (5)	0.5819 (5)	0.08962 (10)	0.0412 (10)
H9A	1.0509	0.6586	0.1067	0.049*
C10	1.0203 (5)	0.4385 (5)	0.09645 (10)	0.0408 (10)
C11	0.8805 (6)	0.5655 (6)	0.01966 (11)	0.0540 (12)
C12	0.9120 (7)	0.7198 (6)	0.03235 (12)	0.0562 (13)
C13	0.7620 (9)	0.4789 (9)	0.00149 (15)	0.085 (2)
H13A	0.6921	0.5125	−0.0041	0.102*
H13B	0.7469	0.3833	−0.0059	0.102*
C14	1.0630 (7)	0.1371 (7)	0.07467 (14)	0.0659 (15)
H14A	1.0356	0.0302	0.0785	0.099*
H14B	1.1345	0.2035	0.0906	0.099*
H14C	1.1120	0.1692	0.0544	0.099*
C15	1.1982 (6)	0.4990 (6)	0.09873 (11)	0.0510 (11)
H15A	1.2420	0.5723	0.1158	0.076*
H15B	1.2482	0.5501	0.0794	0.076*
H15C	1.2150	0.4122	0.1024	0.076*
C16	0.9365 (8)	0.4699 (8)	0.17795 (13)	0.0657 (14)
C17	1.0411 (10)	0.5783 (9)	0.20335 (16)	0.087 (2)
H17A	0.9782	0.5753	0.2209	0.131*
H17B	1.0986	0.6834	0.1953	0.131*
H17C	1.1133	0.5452	0.2101	0.131*
C18	0.7774 (7)	0.6038 (7)	0.10565 (13)	0.0645 (15)
C19	0.6121 (8)	0.5561 (10)	0.09579 (19)	0.089 (2)
H19A	0.5719	0.6066	0.1092	0.133*
H19B	0.5468	0.4442	0.0976	0.133*
H19C	0.6123	0.5870	0.0743	0.133*
C20	1.1473 (6)	0.3604 (7)	−0.00316 (12)	0.0548 (12)
C21	1.2954 (8)	0.3593 (9)	−0.00938 (14)	0.0805 (19)
H21A	1.3739	0.4137	0.0071	0.097*
C22	1.2545 (19)	0.194 (2)	−0.0127 (5)	0.221 (8)*
H22A	1.2169	0.1408	0.0071	0.331*
H22B	1.3459	0.1892	−0.0190	0.331*
H22C	1.1741	0.1437	−0.0284	0.331*
C23	1.3581 (19)	0.4185 (17)	−0.0409 (4)	0.182 (6)*
H23A	1.3908	0.5281	−0.0422	0.273*
H23B	1.2781	0.3617	−0.0564	0.273*
H23C	1.4463	0.4043	−0.0449	0.273*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.069 (2)	0.063 (2)	0.0340 (16)	0.0379 (18)	−0.0070 (15)	−0.0044 (14)
O2	0.082 (3)	0.132 (4)	0.076 (3)	0.055 (3)	0.012 (2)	−0.018 (3)
O3	0.0487 (17)	0.0510 (18)	0.0449 (16)	0.0325 (15)	−0.0010 (13)	−0.0038 (13)
O4	0.121 (4)	0.164 (6)	0.123 (5)	0.102 (4)	−0.031 (4)	−0.086 (4)
O5	0.090 (3)	0.0450 (19)	0.078 (3)	0.039 (2)	−0.025 (2)	−0.0193 (18)
O6	0.0532 (18)	0.0615 (19)	0.0426 (17)	0.0373 (16)	−0.0063 (14)	−0.0113 (14)
O7	0.073 (3)	0.110 (3)	0.0447 (19)	0.055 (3)	−0.0066 (18)	−0.014 (2)
O8	0.078 (2)	0.0415 (18)	0.0532 (19)	0.0340 (17)	−0.0072 (17)	0.0003 (14)
O9	0.141 (4)	0.091 (3)	0.078 (3)	0.091 (3)	−0.034 (3)	−0.016 (2)
C1	0.065 (3)	0.047 (3)	0.039 (2)	0.028 (2)	−0.005 (2)	−0.0015 (19)
C2	0.088 (4)	0.054 (3)	0.052 (3)	0.041 (3)	0.001 (3)	0.011 (2)
C3	0.076 (4)	0.044 (3)	0.067 (3)	0.027 (3)	−0.003 (3)	0.008 (2)
C4	0.065 (3)	0.040 (2)	0.055 (3)	0.029 (2)	−0.011 (2)	−0.007 (2)
C5	0.046 (2)	0.039 (2)	0.046 (2)	0.027 (2)	−0.0029 (18)	−0.0043 (18)
C6	0.042 (2)	0.044 (2)	0.041 (2)	0.025 (2)	−0.0068 (18)	−0.0043 (17)
C7	0.057 (3)	0.044 (2)	0.041 (2)	0.031 (2)	0.004 (2)	0.0014 (19)
C8	0.048 (2)	0.039 (2)	0.050 (2)	0.023 (2)	−0.0058 (19)	−0.0022 (19)
C9	0.047 (2)	0.037 (2)	0.041 (2)	0.022 (2)	−0.0097 (18)	−0.0086 (17)
C10	0.050 (3)	0.040 (2)	0.036 (2)	0.025 (2)	−0.0054 (18)	−0.0039 (17)
C11	0.075 (3)	0.062 (3)	0.043 (2)	0.048 (3)	−0.012 (2)	−0.008 (2)
C12	0.084 (4)	0.060 (3)	0.047 (3)	0.052 (3)	−0.007 (2)	0.003 (2)
C13	0.119 (6)	0.102 (5)	0.072 (4)	0.083 (5)	−0.052 (4)	−0.036 (4)
C14	0.095 (4)	0.060 (3)	0.067 (3)	0.057 (3)	−0.014 (3)	−0.010 (3)
C15	0.059 (3)	0.056 (3)	0.047 (2)	0.036 (3)	−0.012 (2)	−0.009 (2)
C16	0.082 (4)	0.086 (4)	0.047 (3)	0.056 (4)	0.003 (3)	−0.005 (3)
C17	0.114 (5)	0.107 (5)	0.059 (4)	0.070 (5)	−0.017 (3)	−0.029 (4)
C18	0.077 (4)	0.077 (4)	0.059 (3)	0.053 (3)	−0.002 (3)	−0.007 (3)
C19	0.077 (4)	0.118 (6)	0.095 (5)	0.067 (4)	0.014 (4)	0.004 (4)
C20	0.059 (3)	0.066 (3)	0.047 (3)	0.037 (3)	−0.002 (2)	−0.011 (2)
C21	0.080 (4)	0.122 (6)	0.061 (3)	0.067 (4)	0.001 (3)	−0.015 (3)

Geometric parameters (Å, º)

O1—C16	1.359 (7)	C8—C9	1.512 (7)
O1—C1	1.464 (6)	C8—H8A	0.9800
O2—C16	1.185 (8)	C9—C10	1.534 (6)
O3—C18	1.346 (6)	C9—H9A	0.9800
O3—C9	1.465 (6)	C10—C15	1.544 (7)
O4—C18	1.186 (7)	C11—C13	1.299 (8)
O5—C4	1.439 (6)	C11—C12	1.490 (7)
O5—H5A	0.8200	C13—H13A	0.9300
O6—C20	1.355 (6)	C13—H13B	0.9300
O6—C6	1.463 (5)	C14—H14A	0.9600
O7—C20	1.201 (6)	C14—H14B	0.9600
O8—C12	1.338 (6)	C14—H14C	0.9600
O8—C8	1.456 (5)	C15—H15A	0.9600
O9—C12	1.211 (6)	C15—H15B	0.9600
C1—C2	1.510 (7)	C15—H15C	0.9600
C1—C10	1.533 (7)	C16—C17	1.504 (9)
C1—H1A	0.9800	C17—H17A	0.9600
C2—C3	1.534 (8)	C17—H17B	0.9600
C2—H2A	0.9700	C17—H17C	0.9600
C2—H2B	0.9700	C18—C19	1.509 (9)
C3—C4	1.531 (8)	C19—H19A	0.9600
C3—H3A	0.9700	C19—H19B	0.9600
C3—H3B	0.9700	C19—H19C	0.9600
C4—C14	1.536 (8)	C20—C21	1.487 (8)
C4—C5	1.560 (6)	C21—C23	1.468 (18)
C5—C6	1.531 (6)	C21—C22	1.48 (2)
C5—C10	1.559 (6)	C21—H21A	0.9800
C5—H5B	0.9800	C22—H22A	0.9600
C6—C7	1.529 (6)	C22—H22B	0.9600
C6—H6A	0.9800	C22—H22C	0.9600
C7—C11	1.500 (7)	C23—H23A	0.9600
C7—C8	1.525 (6)	C23—H23B	0.9600
C7—H7A	0.9800	C23—H23C	0.9600
C16—O1—C1	115.6 (4)	C9—C10—C5	107.7 (3)
C18—O3—C9	119.4 (4)	C15—C10—C5	114.6 (4)
C4—O5—H5A	109.5	C13—C11—C12	123.0 (5)
C20—O6—C6	116.0 (3)	C13—C11—C7	131.4 (5)
C12—O8—C8	109.3 (3)	C12—C11—C7	105.5 (4)
O1—C1—C2	109.1 (4)	O9—C12—O8	122.4 (5)
O1—C1—C10	107.1 (4)	O9—C12—C11	127.5 (5)
C2—C1—C10	114.7 (4)	O8—C12—C11	110.1 (4)
O1—C1—H1A	108.6	C11—C13—H13A	120.0
C2—C1—H1A	108.6	C11—C13—H13B	120.0
C10—C1—H1A	108.6	H13A—C13—H13B	120.0
C1—C2—C3	108.5 (4)	C4—C14—H14A	109.5
C1—C2—H2A	110.0	C4—C14—H14B	109.5
C3—C2—H2A	110.0	H14A—C14—H14B	109.5
C1—C2—H2B	110.0	C4—C14—H14C	109.5
C3—C2—H2B	110.0	H14A—C14—H14C	109.5
H2A—C2—H2B	108.4	H14B—C14—H14C	109.5
C4—C3—C2	113.4 (4)	C10—C15—H15A	109.5
C4—C3—H3A	108.9	C10—C15—H15B	109.5
C2—C3—H3A	108.9	H15A—C15—H15B	109.5
C4—C3—H3B	108.9	C10—C15—H15C	109.5
C2—C3—H3B	108.9	H15A—C15—H15C	109.5
H3A—C3—H3B	107.7	H15B—C15—H15C	109.5
O5—C4—C3	109.2 (4)	O2—C16—O1	125.1 (6)
O5—C4—C14	109.9 (4)	O2—C16—C17	124.4 (6)
C3—C4—C14	109.6 (4)	O1—C16—C17	110.5 (6)
O5—C4—C5	103.7 (4)	C16—C17—H17A	109.5
C3—C4—C5	106.8 (4)	C16—C17—H17B	109.5
C14—C4—C5	117.3 (4)	H17A—C17—H17B	109.5
C6—C5—C10	114.6 (3)	C16—C17—H17C	109.5
C6—C5—C4	114.8 (4)	H17A—C17—H17C	109.5
C10—C5—C4	115.5 (3)	H17B—C17—H17C	109.5
C6—C5—H5B	103.2	O4—C18—O3	123.5 (6)
C10—C5—H5B	103.2	O4—C18—C19	126.0 (6)
C4—C5—H5B	103.2	O3—C18—C19	110.4 (5)
O6—C6—C7	106.9 (4)	C18—C19—H19A	109.5
O6—C6—C5	110.0 (3)	C18—C19—H19B	109.5
C7—C6—C5	116.2 (4)	H19A—C19—H19B	109.5
O6—C6—H6A	107.8	C18—C19—H19C	109.5
C7—C6—H6A	107.8	H19A—C19—H19C	109.5
C5—C6—H6A	107.8	H19B—C19—H19C	109.5
C11—C7—C8	101.9 (3)	O7—C20—O6	122.3 (5)
C11—C7—C6	117.9 (4)	O7—C20—C21	125.7 (5)
C8—C7—C6	116.1 (4)	O6—C20—C21	112.0 (4)
C11—C7—H7A	106.7	C23—C21—C22	100.3 (11)
C8—C7—H7A	106.7	C23—C21—C20	112.2 (8)
C6—C7—H7A	106.7	C22—C21—C20	107.3 (9)
O8—C8—C9	108.8 (4)	C23—C21—H21A	112.1
O8—C8—C7	104.9 (3)	C22—C21—H21A	112.1
C9—C8—C7	113.9 (4)	C20—C21—H21A	112.1
O8—C8—H8A	109.7	C21—C22—H22A	109.5
C9—C8—H8A	109.7	C21—C22—H22B	109.5
C7—C8—H8A	109.7	H22A—C22—H22B	109.5
O3—C9—C8	106.1 (3)	C21—C22—H22C	109.5
O3—C9—C10	110.2 (4)	H22A—C22—H22C	109.5
C8—C9—C10	112.0 (4)	H22B—C22—H22C	109.5
O3—C9—H9A	109.5	C21—C23—H23A	109.5
C8—C9—H9A	109.5	C21—C23—H23B	109.5
C10—C9—H9A	109.5	H23A—C23—H23B	109.5
C1—C10—C9	108.7 (4)	C21—C23—H23C	109.5
C1—C10—C15	111.9 (4)	H23A—C23—H23C	109.5
C9—C10—C15	106.6 (4)	H23B—C23—H23C	109.5
C1—C10—C5	107.1 (4)
C16—O1—C1—C2	−85.8 (5)	C2—C1—C10—C9	170.8 (4)
C16—O1—C1—C10	149.6 (4)	O1—C1—C10—C15	49.4 (5)
O1—C1—C2—C3	−178.4 (4)	C2—C1—C10—C15	−71.8 (5)
C10—C1—C2—C3	−58.4 (6)	O1—C1—C10—C5	175.9 (3)
C1—C2—C3—C4	59.3 (6)	C2—C1—C10—C5	54.7 (5)
C2—C3—C4—O5	−168.2 (4)	O3—C9—C10—C1	−59.2 (4)
C2—C3—C4—C14	71.4 (6)	C8—C9—C10—C1	−177.0 (4)
C2—C3—C4—C5	−56.6 (6)	O3—C9—C10—C15	−180.0 (3)
O5—C4—C5—C6	−53.4 (5)	C8—C9—C10—C15	62.2 (4)
C3—C4—C5—C6	−168.7 (4)	O3—C9—C10—C5	56.6 (4)
C14—C4—C5—C6	68.0 (5)	C8—C9—C10—C5	−61.3 (5)
O5—C4—C5—C10	169.8 (4)	C6—C5—C10—C1	170.0 (4)
C3—C4—C5—C10	54.5 (5)	C4—C5—C10—C1	−53.2 (5)
C14—C4—C5—C10	−68.8 (5)	C6—C5—C10—C9	53.2 (5)
C20—O6—C6—C7	−83.2 (5)	C4—C5—C10—C9	−169.9 (4)
C20—O6—C6—C5	149.9 (4)	C6—C5—C10—C15	−65.2 (5)
C10—C5—C6—O6	82.3 (4)	C4—C5—C10—C15	71.7 (5)
C4—C5—C6—O6	−54.8 (5)	C8—C7—C11—C13	−162.7 (7)
C10—C5—C6—C7	−39.3 (5)	C6—C7—C11—C13	−34.5 (9)
C4—C5—C6—C7	−176.4 (4)	C8—C7—C11—C12	21.5 (5)
O6—C6—C7—C11	146.6 (4)	C6—C7—C11—C12	149.8 (4)
C5—C6—C7—C11	−90.2 (5)	C8—O8—C12—O9	167.6 (5)
O6—C6—C7—C8	−92.2 (4)	C8—O8—C12—C11	−11.7 (6)
C5—C6—C7—C8	31.0 (6)	C13—C11—C12—O9	−2.6 (10)
C12—O8—C8—C9	−96.6 (4)	C7—C11—C12—O9	173.6 (6)
C12—O8—C8—C7	25.6 (5)	C13—C11—C12—O8	176.7 (6)
C11—C7—C8—O8	−28.3 (5)	C7—C11—C12—O8	−7.2 (6)
C6—C7—C8—O8	−157.7 (4)	C1—O1—C16—O2	−5.4 (8)
C11—C7—C8—C9	90.6 (5)	C1—O1—C16—C17	175.5 (5)
C6—C7—C8—C9	−38.8 (6)	C9—O3—C18—O4	−8.9 (9)
C18—O3—C9—C8	−114.3 (4)	C9—O3—C18—C19	171.4 (5)
C18—O3—C9—C10	124.3 (4)	C6—O6—C20—O7	0.7 (7)
O8—C8—C9—O3	51.9 (4)	C6—O6—C20—C21	−179.2 (5)
C7—C8—C9—O3	−64.8 (4)	O7—C20—C21—C23	29.4 (11)
O8—C8—C9—C10	172.1 (3)	O6—C20—C21—C23	−150.7 (8)
C7—C8—C9—C10	55.5 (5)	O7—C20—C21—C22	−79.8 (12)
O1—C1—C10—C9	−68.0 (4)	O6—C20—C21—C22	100.1 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O9^i	0.82	2.19	2.986 (3)	163

Symmetry code: (i) x, y−1, z.