8-Hydr­oxy-13-meth­oxy-17,17-dimethyl-15-(3-methyl-2-buten­yl)-3,16-dioxapenta­cyclo­[11.4.1.0^2,11.0^2,15.0^4,9]octa­deca-4,6,8,11-tetra­ene-10,14-dione

The title compound, C₂₄H₂₆O₆, is a caged-polyprenylated xanthone which has been isolated for the first time from the roots of C. cochinchinese. The cyclo­hexane ring adopts a standard boat conformation, the cyclo­hexene rings are in twisted boat and twist-boat conformations, and the tetra­hydro­furan ring has an envelope conformation. The structure is stabilized by intra­molecular C—H...O and O—H...O hydrogen bonds. C—H...O inter­molecular hydrogen bonds and C—H...π stacking inter­actions link the mol­ecules into mol­ecular sheets parallel to the bc plane.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.063
• wR factor = 0.183
• Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.29 Ratio

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.98 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C21
PLAT480_ALERT_4_C Long H...A H-Bond Reported H23B   ..  CG1     ..       2.92 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C24 H26 O6

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

   1 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

The title compound, (I), is a caged-polyprenylated xanthone which has been isolated for the first time from Cratoxylum cochinchinese which was collected from Nhongkhai province in the northeastern part of Thailand. More importantly, (I) has never before been isolated from any natural product resources.

This plant is a medicinal plant belonging to the genus Cratoxylum (Bennett & Lee, 1989) and widely distributed, mainly in Southeast Asia. Some species of this genus have been used as traditional medicines (Usher, 1984). The bark, root and leaves of C. cochinchinese are used in folk medicines to treat fevers, coughs, diarrhea, itches, ulcers and abdominal complaints (Vo, 1997). As part of our research on bioactive compounds from medicinal plants (Chantrapromma et al., 2003, 2004; Chantrapromma, Boonnak et al., 2005; Chantrapromma, Fun et al., 2005; Boonnak et al., 2005; Fun et al., 2005), we have undertaken the X-ray crystal structure analysis of (I) in order to establish its molecular structure and relative stereochemistry.

Compound (I) is a chiral molecule, which crystallized in the centrosymmetric space group P2₁/c. This indicates that (I) was produced by non-enzymatic reactions during the chromatographic process (Chantrapromma, Boonnak et al., 2005; Chantrapromma, Fun et al., 2005).

The molecular structure of (I) is illustrated in Fig. 1, and selected bond distances and angles are given in Table 1. The bond lengths in (I) show normal values (Allen et al., 1987). In the xanthone skeleton (C1–C13/O2/O3), there are two cyclohexene rings, viz. C8–C13 and C8–C9/C12–C15. The former adopts a slightly twisted boat conformation and the latter has a twist–boat conformation, with puckering parameters Q = 0.778 (3), θ = 88.092)°, ϕ = 240.00 (18)° and Q = 0.765 (3), θ = 96.7 (2)°, ϕ = 49.62 (19)°, respectively (Cremer & Pople, 1975). The cyclohexane ring (C9–C12/C14–C15) is in a boat conformation; the tetrahydrofuran ring (O5/C10/C9/C15/C16) has an envelope conformation, with C9 as the most puckered atom [0.291 (2) Å] and Q = 0.463 (3) (Cremer & Pople, 1975). The hydroxyl group is coplanar with the attached benzene ring. The methoxy group is in a (+)-anti-periplanar conformation (Fig. 1), as evidenced by the torsion angle O6—C12—C13—C8 of 175.0 (2)°, The orientation of C11═O4 is defined by the C9—C10—C11—O4 torsion angle of 179.3 (2)°. The 3-methyl-2-butenyl (C19–C23) substituent group involves the C9—C10—C19—C20 torsion angle of −58.5 (3)°, indicating a (-)-synclinal conformation. The two methyl groups are axially and bisectionally attached to the tetrahydrofuran ring at atom C16.

The molecular structure is stabilized by intramolecular C—H···O interactions and O—H···O hydrogen bonds (Table 2). C—H···O intermolecular interactions link the molecules into molecular sheets parallel to the bc plane (Fig. 2). In addition, the molecular packing is stabilized by C—H···π interactions involving Cg1 where Cg1 is the centroid of the cyclohexene ring (C8–C13) (Table 2).

S2. Experimental

Air-dried roots of C. cochinchinese (2 kg) were extracted successively with hexane. The hexane extract (17 g) was subjected to QCC over silica gel and eluted with a gradient of hexane-EtOAc to afford nine fractions (A1–A9). Fraction A2 was subjected to column chromatography using 20% EtOAc–hexane as eluent to give seve sub-fractions. Subfractions A2–2 (1.2 g) was crystallized from 20% EtOAc–hexane to yield compound (I) (0.5 g). Compound (I) was recrystallized from CHCl₃/CH₃OH (8:2 v/v) to give pale-yellow single crystals after several days (m.p. 431–432 K).

S3. Refinement

H atoms were placed in calculated positions, with an O—H distance of 0.82 Å and C—H distances in the range 0.93–0.97 Å. The U_iso(H) values were constrained to be 1.5U_eq of the carrier atom for hydroxyl and methyl H atoms and 1.2U_eq for the remaining H atoms.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

Figures

	Fig. 1. The asymmetric unit of (I), showing 50% probability displacement ellipsoids and the atomic numbering.
	Fig. 2. The crystal packing of (I), viewed down the a axis. Hydrogen bonds are shown as dashed lines.

8-hydroxy-13-methoxy-17,17-dimethyl-15-(3-methyl-2-butenyl)-3,16- dioxapentacyclo[11.4.1.0^2,11.0^2,15.0^4,9]octadeca-4,6,8,11- tetraene-10–14-dione

Crystal data

C24H26O6	F(000) = 872
Mr = 410.45	Dx = 1.287 Mg m^−3
Monoclinic, P21/c	Melting point = 431–432 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.4622 (4) Å	Cell parameters from 4636 reflections
b = 7.3284 (2) Å	θ = 1.6–27.0°
c = 26.7829 (9) Å	µ = 0.09 mm^−1
β = 109.709 (2)°	T = 273 K
V = 2117.96 (12) Å^3	Block, pale yellow
Z = 4	0.55 × 0.44 × 0.34 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer	4636 independent reflections
Radiation source: fine-focus sealed tube	4048 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 8.33 pixels mm^-1	θmax = 27.0°, θmin = 1.6°
ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −9→9
Tmin = 0.953, Tmax = 0.969	l = −34→34
35056 measured reflections

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.183	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.063P)^2 + 2.6144P] where P = (Fo^2 + 2Fc^2)/3
4636 reflections	(Δ/σ)max < 0.001
303 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.28 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	0.6190 (2)	−0.6835 (3)	−0.13501 (10)	0.0576 (6)
H1A	0.5544	−0.6274	−0.1393	0.066 (11)*
O2	0.40119 (18)	−0.6213 (3)	−0.12947 (9)	0.0537 (5)
O3	0.39197 (16)	−1.1553 (2)	−0.08179 (8)	0.0461 (5)
O4	−0.04623 (18)	−1.0618 (3)	−0.15914 (9)	0.0595 (6)
O5	0.15662 (16)	−1.3063 (2)	−0.09733 (7)	0.0381 (4)
O6	−0.01450 (16)	−0.7477 (3)	−0.09680 (8)	0.0464 (5)
C1	0.4906 (2)	−1.0896 (3)	−0.09332 (9)	0.0350 (5)
C2	0.5843 (2)	−1.2138 (4)	−0.08862 (11)	0.0446 (6)
H2A	0.5783	−1.3332	−0.0780	0.047 (8)*
C3	0.6883 (3)	−1.1566 (5)	−0.10003 (12)	0.0543 (7)
H3A	0.7514	−1.2400	−0.0971	0.059 (9)*
C4	0.7006 (3)	−0.9800 (5)	−0.11545 (13)	0.0567 (8)
H4A	0.7712	−0.9451	−0.1227	0.070 (10)*
C5	0.6070 (2)	−0.8560 (4)	−0.12005 (11)	0.0437 (6)
C6	0.4988 (2)	−0.9086 (3)	−0.10913 (9)	0.0342 (5)
C7	0.3982 (2)	−0.7818 (3)	−0.11517 (10)	0.0358 (5)
C8	0.2896 (2)	−0.8545 (3)	−0.10443 (9)	0.0322 (5)
C9	0.2842 (2)	−1.0490 (3)	−0.08752 (9)	0.0310 (5)
C10	0.1699 (2)	−1.1477 (3)	−0.12578 (9)	0.0328 (5)
C11	0.0565 (2)	−1.0232 (3)	−0.13146 (9)	0.0357 (5)
C12	0.0888 (2)	−0.8519 (3)	−0.09569 (10)	0.0341 (5)
C13	0.1888 (2)	−0.7545 (3)	−0.10999 (9)	0.0327 (5)
H13A	0.1809	−0.6342	−0.1217	0.042 (7)*
C14	0.1520 (2)	−0.9211 (3)	−0.03821 (10)	0.0383 (5)
H14A	0.1915	−0.8197	−0.0156	0.046 (8)*
H14B	0.0898	−0.9716	−0.0250	0.056 (9)*
C15	0.2490 (2)	−1.0677 (3)	−0.03622 (9)	0.0346 (5)
H15A	0.3224	−1.0525	−0.0045	0.055 (9)*
C16	0.2001 (3)	−1.2680 (3)	−0.04028 (10)	0.0412 (6)
C17	0.0911 (4)	−1.3012 (5)	−0.02121 (15)	0.0668 (10)
H17A	0.0678	−1.4275	−0.0260	0.081 (12)*
H17B	0.0223	−1.2269	−0.0413	0.093 (15)*
H17C	0.1143	−1.2702	0.0157	0.092 (13)*
C18	0.3051 (4)	−1.4007 (4)	−0.01289 (12)	0.0600 (8)
H18A	0.2740	−1.5234	−0.0180	0.084 (12)*
H18B	0.3372	−1.3741	0.0244	0.076 (11)*
H18C	0.3700	−1.3880	−0.0278	0.110 (17)*
C19	0.1767 (3)	−1.2086 (4)	−0.17904 (10)	0.0437 (6)
H19A	0.2428	−1.2975	−0.1730	0.064 (10)*
H19B	0.0995	−1.2681	−0.1991	0.062 (10)*
C20	0.2000 (3)	−1.0542 (4)	−0.21134 (10)	0.0446 (6)
H20A	0.1449	−0.9568	−0.2175	0.061 (9)*
C21	0.2895 (3)	−1.0405 (5)	−0.23209 (10)	0.0554 (8)
C22	0.3017 (5)	−0.8699 (7)	−0.26135 (15)	0.0923 (16)
H22A	0.2281	−0.7975	−0.2685	0.18 (3)*
H22B	0.3128	−0.9026	−0.2942	0.101 (14)*
H22C	0.3721	−0.8010	−0.2400	0.14 (2)*
C23	0.3839 (4)	−1.1860 (8)	−0.22836 (15)	0.0895 (15)
H23A	0.3759	−1.2808	−0.2050	0.13 (2)*
H23B	0.4655	−1.1342	−0.2148	0.116 (18)*
H23C	0.3707	−1.2361	−0.2629	0.15 (2)*
C24	−0.0719 (3)	−0.6452 (5)	−0.14425 (15)	0.0605 (9)
H24A	−0.1568	−0.6214	−0.1479	0.099 (14)*
H24B	−0.0686	−0.7138	−0.1743	0.099 (15)*
H24C	−0.0288	−0.5317	−0.1423	0.093 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0473 (12)	0.0597 (13)	0.0757 (14)	−0.0090 (10)	0.0340 (11)	0.0095 (11)
O2	0.0518 (11)	0.0338 (10)	0.0863 (15)	−0.0036 (8)	0.0374 (11)	0.0110 (10)
O3	0.0370 (9)	0.0300 (9)	0.0766 (13)	0.0048 (7)	0.0260 (9)	0.0103 (8)
O4	0.0355 (10)	0.0641 (14)	0.0708 (14)	−0.0091 (9)	0.0074 (9)	−0.0163 (11)
O5	0.0511 (10)	0.0286 (8)	0.0377 (9)	−0.0112 (7)	0.0191 (8)	−0.0033 (7)
O6	0.0383 (9)	0.0463 (10)	0.0609 (12)	0.0096 (8)	0.0248 (9)	0.0047 (9)
C1	0.0290 (11)	0.0370 (12)	0.0372 (12)	−0.0011 (9)	0.0088 (9)	−0.0053 (10)
C2	0.0382 (13)	0.0458 (15)	0.0459 (14)	0.0070 (11)	0.0091 (11)	−0.0017 (12)
C3	0.0341 (13)	0.069 (2)	0.0597 (17)	0.0117 (13)	0.0152 (12)	−0.0053 (15)
C4	0.0348 (13)	0.078 (2)	0.0637 (18)	−0.0018 (14)	0.0253 (13)	−0.0060 (16)
C5	0.0375 (13)	0.0525 (16)	0.0451 (14)	−0.0077 (11)	0.0189 (11)	−0.0041 (12)
C6	0.0295 (11)	0.0386 (12)	0.0354 (11)	−0.0025 (9)	0.0120 (9)	−0.0031 (10)
C7	0.0345 (12)	0.0313 (11)	0.0438 (13)	−0.0050 (9)	0.0164 (10)	0.0004 (10)
C8	0.0324 (11)	0.0266 (11)	0.0395 (12)	−0.0015 (9)	0.0147 (9)	0.0011 (9)
C9	0.0296 (11)	0.0255 (10)	0.0396 (12)	0.0001 (8)	0.0138 (9)	0.0015 (9)
C10	0.0375 (12)	0.0287 (11)	0.0353 (11)	−0.0046 (9)	0.0164 (9)	−0.0016 (9)
C11	0.0328 (11)	0.0386 (12)	0.0370 (12)	−0.0062 (10)	0.0135 (10)	−0.0005 (10)
C12	0.0310 (11)	0.0326 (11)	0.0417 (12)	0.0014 (9)	0.0159 (9)	0.0008 (10)
C13	0.0332 (11)	0.0291 (11)	0.0364 (11)	−0.0022 (9)	0.0124 (9)	0.0010 (9)
C14	0.0491 (14)	0.0345 (12)	0.0363 (12)	−0.0015 (10)	0.0211 (11)	−0.0026 (10)
C15	0.0414 (12)	0.0288 (11)	0.0321 (11)	−0.0033 (9)	0.0102 (10)	0.0004 (9)
C16	0.0597 (16)	0.0313 (12)	0.0361 (12)	−0.0069 (11)	0.0206 (11)	−0.0002 (10)
C17	0.099 (3)	0.0504 (18)	0.075 (2)	−0.0242 (19)	0.060 (2)	−0.0057 (17)
C18	0.091 (2)	0.0316 (14)	0.0495 (16)	−0.0005 (14)	0.0130 (16)	0.0071 (12)
C19	0.0554 (16)	0.0416 (14)	0.0389 (13)	−0.0034 (12)	0.0224 (12)	−0.0072 (11)
C20	0.0501 (15)	0.0512 (15)	0.0341 (12)	−0.0006 (12)	0.0164 (11)	−0.0020 (11)
C21	0.0509 (16)	0.086 (2)	0.0312 (12)	−0.0106 (15)	0.0164 (11)	−0.0034 (14)
C22	0.106 (3)	0.126 (4)	0.0492 (19)	−0.049 (3)	0.032 (2)	0.006 (2)
C23	0.067 (2)	0.157 (5)	0.054 (2)	0.022 (3)	0.0313 (18)	−0.011 (3)
C24	0.0412 (15)	0.0550 (18)	0.083 (2)	0.0129 (13)	0.0178 (15)	0.0206 (17)

Geometric parameters (Å, º)

O1—C5	1.347 (3)	C13—H13A	0.9300
O1—H1A	0.8200	C14—C15	1.534 (3)
O2—C7	1.241 (3)	C14—H14A	0.9693
O3—C1	1.356 (3)	C14—H14B	0.9699
O3—C9	1.425 (3)	C15—C16	1.561 (3)
O4—C11	1.195 (3)	C15—H15A	0.9796
O5—C10	1.426 (3)	C16—C17	1.521 (4)
O5—C16	1.466 (3)	C16—C18	1.529 (4)
O6—C12	1.401 (3)	C17—H17A	0.9600
O6—C24	1.431 (4)	C17—H17B	0.9600
C1—C2	1.381 (3)	C17—H17C	0.9600
C1—C6	1.405 (3)	C18—H18A	0.9600
C2—C3	1.391 (4)	C18—H18B	0.9600
C2—H2A	0.9302	C18—H18C	0.9600
C3—C4	1.380 (5)	C19—C20	1.502 (4)
C3—H3A	0.9300	C19—H19A	0.9701
C4—C5	1.380 (4)	C19—H19B	0.9706
C4—H4A	0.9297	C20—C21	1.325 (4)
C5—C6	1.420 (3)	C20—H20A	0.9300
C6—C7	1.446 (3)	C21—C23	1.499 (5)
C7—C8	1.469 (3)	C21—C22	1.507 (5)
C8—C13	1.334 (3)	C22—H22A	0.9600
C8—C9	1.503 (3)	C22—H22B	0.9600
C9—C10	1.544 (3)	C22—H22C	0.9600
C9—C15	1.563 (3)	C23—H23A	0.9600
C10—C19	1.522 (3)	C23—H23B	0.9600
C10—C11	1.553 (3)	C23—H23C	0.9600
C11—C12	1.546 (3)	C24—H24A	0.9600
C12—C13	1.505 (3)	C24—H24B	0.9600
C12—C14	1.549 (3)	C24—H24C	0.9600
C5—O1—H1A	109.5	C12—C14—H14B	109.5
C1—O3—C9	122.71 (18)	H14A—C14—H14B	108.1
C10—O5—C16	109.93 (17)	C14—C15—C16	114.6 (2)
C12—O6—C24	115.9 (2)	C14—C15—C9	107.85 (18)
O3—C1—C2	115.3 (2)	C16—C15—C9	102.37 (18)
O3—C1—C6	123.3 (2)	C14—C15—H15A	110.5
C2—C1—C6	121.3 (2)	C16—C15—H15A	110.5
C1—C2—C3	118.7 (3)	C9—C15—H15A	110.6
C1—C2—H2A	120.8	O5—C16—C17	106.9 (2)
C3—C2—H2A	120.6	O5—C16—C18	108.3 (2)
C4—C3—C2	122.0 (3)	C17—C16—C18	109.9 (3)
C4—C3—H3A	119.1	O5—C16—C15	103.93 (18)
C2—C3—H3A	118.9	C17—C16—C15	116.3 (2)
C5—C4—C3	119.3 (3)	C18—C16—C15	111.0 (2)
C5—C4—H4A	120.4	C16—C17—H17A	109.5
C3—C4—H4A	120.3	C16—C17—H17B	109.5
O1—C5—C4	119.4 (2)	H17A—C17—H17B	109.5
O1—C5—C6	120.0 (2)	C16—C17—H17C	109.5
C4—C5—C6	120.6 (3)	H17A—C17—H17C	109.5
C1—C6—C5	118.1 (2)	H17B—C17—H17C	109.5
C1—C6—C7	120.5 (2)	C16—C18—H18A	109.5
C5—C6—C7	121.4 (2)	C16—C18—H18B	109.5
O2—C7—C6	122.7 (2)	H18A—C18—H18B	109.5
O2—C7—C8	121.1 (2)	C16—C18—H18C	109.5
C6—C7—C8	116.2 (2)	H18A—C18—H18C	109.5
C13—C8—C7	122.6 (2)	H18B—C18—H18C	109.5
C13—C8—C9	115.6 (2)	C20—C19—C10	113.2 (2)
C7—C8—C9	121.8 (2)	C20—C19—H19A	108.8
O3—C9—C8	115.36 (18)	C10—C19—H19A	109.0
O3—C9—C10	109.02 (18)	C20—C19—H19B	109.0
C8—C9—C10	110.89 (19)	C10—C19—H19B	108.9
O3—C9—C15	109.18 (18)	H19A—C19—H19B	107.8
C8—C9—C15	113.42 (18)	C21—C20—C19	127.7 (3)
C10—C9—C15	97.45 (17)	C21—C20—H20A	116.2
O5—C10—C19	108.08 (19)	C19—C20—H20A	116.1
O5—C10—C9	104.29 (18)	C20—C21—C23	124.2 (3)
C19—C10—C9	117.3 (2)	C20—C21—C22	120.1 (4)
O5—C10—C11	107.16 (18)	C23—C21—C22	115.7 (3)
C19—C10—C11	112.8 (2)	C21—C22—H22A	109.5
C9—C10—C11	106.50 (18)	C21—C22—H22B	109.5
O4—C11—C12	123.8 (2)	H22A—C22—H22B	109.5
O4—C11—C10	122.6 (2)	C21—C22—H22C	109.5
C12—C11—C10	113.51 (18)	H22A—C22—H22C	109.5
O6—C12—C13	116.5 (2)	H22B—C22—H22C	109.5
O6—C12—C11	113.90 (19)	C21—C23—H23A	109.5
C13—C12—C11	105.72 (18)	C21—C23—H23B	109.5
O6—C12—C14	107.96 (19)	H23A—C23—H23B	109.5
C13—C12—C14	105.51 (19)	C21—C23—H23C	109.5
C11—C12—C14	106.49 (19)	H23A—C23—H23C	109.5
C8—C13—C12	114.6 (2)	H23B—C23—H23C	109.5
C8—C13—H13A	122.7	O6—C24—H24A	109.5
C12—C13—H13A	122.7	O6—C24—H24B	109.5
C15—C14—C12	110.76 (19)	H24A—C24—H24B	109.5
C15—C14—H14A	109.5	O6—C24—H24C	109.5
C12—C14—H14A	109.5	H24A—C24—H24C	109.5
C15—C14—H14B	109.5	H24B—C24—H24C	109.5
C9—O3—C1—C2	−176.3 (2)	C19—C10—C11—O4	49.2 (3)
C9—O3—C1—C6	3.6 (4)	C9—C10—C11—O4	179.3 (2)
O3—C1—C2—C3	179.7 (2)	O5—C10—C11—C12	107.2 (2)
C6—C1—C2—C3	−0.2 (4)	C19—C10—C11—C12	−134.0 (2)
C1—C2—C3—C4	0.5 (4)	C9—C10—C11—C12	−4.0 (2)
C2—C3—C4—C5	−0.4 (5)	C24—O6—C12—C13	50.8 (3)
C3—C4—C5—O1	179.9 (3)	C24—O6—C12—C11	−72.8 (3)
C3—C4—C5—C6	−0.1 (4)	C24—O6—C12—C14	169.2 (2)
O3—C1—C6—C5	179.9 (2)	O4—C11—C12—O6	2.4 (3)
C2—C1—C6—C5	−0.2 (4)	C10—C11—C12—O6	−174.33 (19)
O3—C1—C6—C7	−1.5 (4)	O4—C11—C12—C13	−126.8 (3)
C2—C1—C6—C7	178.4 (2)	C10—C11—C12—C13	56.4 (2)
O1—C5—C6—C1	−179.6 (2)	O4—C11—C12—C14	121.3 (3)
C4—C5—C6—C1	0.3 (4)	C10—C11—C12—C14	−55.5 (2)
O1—C5—C6—C7	1.8 (4)	C7—C8—C13—C12	−178.5 (2)
C4—C5—C6—C7	−178.3 (3)	C9—C8—C13—C12	2.9 (3)
C1—C6—C7—O2	−179.4 (2)	O6—C12—C13—C8	175.0 (2)
C5—C6—C7—O2	−0.8 (4)	C11—C12—C13—C8	−57.4 (3)
C1—C6—C7—C8	−0.6 (3)	C14—C12—C13—C8	55.2 (3)
C5—C6—C7—C8	178.0 (2)	O6—C12—C14—C15	168.21 (19)
O2—C7—C8—C13	0.9 (4)	C13—C12—C14—C15	−66.5 (2)
C6—C7—C8—C13	−177.9 (2)	C11—C12—C14—C15	45.5 (2)
O2—C7—C8—C9	179.5 (2)	C12—C14—C15—C16	−93.7 (2)
C6—C7—C8—C9	0.7 (3)	C12—C14—C15—C9	19.6 (3)
C1—O3—C9—C8	−3.2 (3)	O3—C9—C15—C14	167.66 (18)
C1—O3—C9—C10	122.3 (2)	C8—C9—C15—C14	37.5 (3)
C1—O3—C9—C15	−132.3 (2)	C10—C9—C15—C14	−79.2 (2)
C13—C8—C9—O3	179.8 (2)	O3—C9—C15—C16	−71.1 (2)
C7—C8—C9—O3	1.1 (3)	C8—C9—C15—C16	158.7 (2)
C13—C8—C9—C10	55.3 (3)	C10—C9—C15—C16	42.1 (2)
C7—C8—C9—C10	−123.4 (2)	C10—O5—C16—C17	120.7 (2)
C13—C8—C9—C15	−53.2 (3)	C10—O5—C16—C18	−121.0 (2)
C7—C8—C9—C15	128.1 (2)	C10—O5—C16—C15	−2.9 (3)
C16—O5—C10—C19	156.7 (2)	C14—C15—C16—O5	90.6 (2)
C16—O5—C10—C9	31.1 (2)	C9—C15—C16—O5	−25.8 (2)
C16—O5—C10—C11	−81.6 (2)	C14—C15—C16—C17	−26.5 (3)
O3—C9—C10—O5	68.3 (2)	C9—C15—C16—C17	−143.0 (3)
C8—C9—C10—O5	−163.64 (17)	C14—C15—C16—C18	−153.1 (2)
C15—C9—C10—O5	−45.0 (2)	C9—C15—C16—C18	90.4 (2)
O3—C9—C10—C19	−51.2 (3)	O5—C10—C19—C20	−175.9 (2)
C8—C9—C10—C19	76.9 (3)	C9—C10—C19—C20	−58.5 (3)
C15—C9—C10—C19	−164.5 (2)	C11—C10—C19—C20	65.8 (3)
O3—C9—C10—C11	−178.57 (17)	C10—C19—C20—C21	125.5 (3)
C8—C9—C10—C11	−50.5 (2)	C19—C20—C21—C23	2.5 (5)
C15—C9—C10—C11	68.1 (2)	C19—C20—C21—C22	−177.1 (3)
O5—C10—C11—O4	−69.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.82	1.86	2.591 (3)	147
C13—H13A···O5^i	0.93	2.53	3.335 (3)	145
C18—H18C···O3	0.96	2.30	2.978 (4)	127
C24—H24B···O4	0.96	2.58	3.106 (4)	115
C15—H15A···Cg1^ii	0.98	2.82	3.66	144
C23—H23B···Cg1	0.96	2.92	3.56	125

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