Dibothrioclinin I and II, epimers from Gerbera piloselloides (L.) Cass

Dibothrioclinin I and II, namely (+)-(11R,12S,25R,27S)- and (±)-­(11RS,12RS,25RS,27SR)-3,3,7,17,21-penta­methyl-4,12,18,26-tetraoxahepta­cyclo­[15.11.1.0^2,15.0^5,14.0^6,11.0^19,28.0^20,25]­nona­cosa-5(14),6,8,10,19(28),20,22,24-octaene-13,27-dione, respectively, are C₃₀H₂₈O₆ epimers which are derived from two bothrioclinin moieties joined so as to create an additional six-membered ring. Structurally, the epimers differ only by inversion at one C atom of a central ring junction and the corresponding six-membered rings have similar conformations in each mol­ecule, except for one ring adjacent to this inversion site.

S1. Comment

Most coumarins are widely distributed among higher plants, while only a few occur in animals and microorganisms, e.g. aflatoxin from Aspergillus and armillarisin from Armillarialla tabescens. Coumarins and their derivatives are active natural products which have many biological activities, such as anticoagulant, antimicrobial (Kwon et al., 2002) and non-specific spasmolytic action (Oliveira et al., 2001). In recent years, further investigations have indicated that they have anti-HIV activity (Yang, 2001). Therefore, these compounds are widely applied in food, chemical engineering and medical fields and extensive future research into cumarin derivatives is likely.

Gerbera piloselloides (L.) Cass has been used as an antipyretic and alexipharmic agent, and for regulating the flow of vital energy and the condition of the blood in traditional Chinese medicine (Jiangsu New Medical College, 1977). Besides 15 known compounds (Xiao et al.,. 2002), two novel coumarin dimers, dibothrioclinin I and II, hereinafter (I) and (II), respectively, have been isolated from Gerbera piloselloides (L.) Cass. The structures and relative stereochemistry of these two compounds have been established by spectroscopy. The present study reports their crystal structures, which confirms the relative stereochemistry and establishes the conformations of all rings in the molecules. \sch

Dibothrioclinin I, (I) (Fig. 1a), is enantiopure ([α]_D = 24°, c 0.05, CHCl₃), although the absolute configuration has not been established, while dibothrioclinin II, (II) (Fig. 1 b), is racemic. The compounds are epimers and their skeletons differ only by inversion of the configuration at C12, so that the stereochemistry of the ring C/D junction is cis in (I) and trans in (II). Each compound incorporates two structural units of bothrioclinin (Ferdinand & Christa, 1977) at opposite ends of the molecule. These units are dimerized by the formation of two single bonds, one of which is a direct connection between rings C and E via C11—C27, while the second connects ring C, via C12—C29, to one of the methyl substituents on ring E, thereby building a seventh six-membered ring, D.

The two coumarin skeletons in each structure, rings A/B and F/G, are each almost planar, with a mean deviation of 0.014 (3) Å in (I) and 0.019 (2) Å in (II). The dihedral angles between rings A and B, and between rings F and G, are 2.1 (1) and 3.7 (1)°, respectively, for (I), and 4.1 (1) and 3.7 (1)°, respectively, for (II). These properties are similar to those observed in the structure of ethuliacoumarin A (Larsen et al., 1992).

The corresponding six-membered rings in each compound have similar conformations, except for differences in the conformations of rings C, D and E because of the effect of the inversion at C12. The 2H-dihydropyran ring C adopts a half-chair conformation in (I), with puckering parameters (Cremer & Pople, 1975) Q = 0.444 (3) Å, θ = 128.1 (4)° and ϕ = 98.9 (5)° for the atom sequence O3, C3, C2, C12, C11, C10. In (II), ring C adopts a distorted envelope conformation, with puckering parameters for the corresponding atom sequence Q = 0.525 (3) Å, θ = 122.1 (3)° and ϕ = 46.5 (3)°. The 2H-dihydropyran ring E has an almost ideal envelope form in (I), with puckering parameters Q = 0.544 (3) Å, θ = 55.1 (3)° and ϕ = 240.0 (4)° for the atom sequence O6, C18, C17, C27, C26, C25. In (II), this ring is halfway between an envelope and a half-chair conformation, with puckering parameters for the corresponding atom sequence Q = 0.574 (3) Å, θ = 53.9 (3)° and ϕ = 259.8 (3)°.

The greatest difference between the two compounds lies in the conformation of ring D. In dibothrioclinin I, ring D has a slightly twisted chair conformation owing to the cis fusion with ring C. The puckering parameters are Q = 0.537 (3) Å, θ = 13.5 (4)° and ϕ =241 (2)° for the atom sequence C11, C12, C29, C25, C26, C27. This is also indicated by the smaller C27—C11—C12—C29 and C11—C12—C29—C25 torsion angles of −41.7 (3) and 43.8 (4)°, respectively. The mean of the other four torsion angles is 55.7 (5)° (the torsion angle of the normal chair form of cyclohexane is 56°). In (II), the trans C/D ring junction imposes a conformation on ring D that is halfway between a boat and a twisted boat. The puckering parameters are Q = 0.815 (3) Å, θ = 87.4 (2)° and ϕ = 255.5 (2)°, for the same atom sequence as in (I). This is supported by the C12—C11—C27—C26 and C26—C25—C29—C12 torsion angles of 20.8 (3) and 13.6 (3)°, repsectively. The mean of the other four torsion angles is 55.6 (4)° (the torsion angles of the normal boat form of cyclohexane are 0 and 56°).

Compounds (I) and (II) also exhibit different molecular stereo structures. The dihedral angle between the plane of rings A/B and the least-squares plane through ring C (including puckered atoms) is 4.8 (1)° for (I) and 16.8 (1)° for (II). The dihedral angle between the least-squares planes through rings A/B/C and E/F/G is 72.4 (1)° for (I) and 80.4 (1)° for (II). However, while the inversion at C12 influences the stereochemistry of the ring C/D junction, the stereo structure of rings E, F and G remains unaffected. This can be inferred from the dihedral angle between the plane of rings F/G and the least-squares plane through ring E (including puckered atoms), which is 8.9 (1)° for (I) and 10.9 (1)° for (II).

S2. Experimental

The roots and rhizomes of Gerbera piloselloides (L.) Cass were collected from DALI, Yunnan Province, China. The air-dried roots and rhizomes (1 kg) were ground to a fine powder and extracted with ethanol, and the ethanol extract was partitioned between an aqueous solution and petroleum ether. The petroleum ether fraction was chromatographed repeatedly on silica gel, eluted with petroleum ether-acetylacetate (9:1), and gave colourless crystals. Purification of the crystals on a preparative high-performance liquid chromatography column afforded compounds (I) (18 mg) and (II) (30 mg). Compound (I) was dissolved in methanol and chloroform (1:1) and stored at room temperature, and transparent block-shaped crystals were obtained after 4 d. Compound (II) was dissolved in chloroform and stored at room temperature, and transparent plate-like crystals were obtained after 7 d.

S3. Refinement

Due to the absence of any significant anomalous scatterers in (I), attempts to confirm the absolute structure by refinement of the Flack parameter (Flack, 1983) led to an inconclusive value (Flack & Bernardinelli, 2000) for this parameter. Therefore, the enantiomer used in the model was chosen arbitrarily and the Friedel pairs were merged before the final refinement. For both compounds, the methyl H atoms were constrained to an ideal geometry, with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the C—C bonds. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Computing details

For both compounds, data collection: DENZO (Otwinowski & Minor, 1997); cell refinement: SCALE (Otwinowski & Minor, 1997); data reduction: SCALE; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PLATON.

Figures

Fig. 1. The molecular structures and atomic numbering schemes for (a) (I) and (b) (II). Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity.

(I) (+)-(11R,12S,25R,27S)-3,3,7,17,21-pentamethyl-4,12,18,26- tetraoxaheptacyclo[15.11.1.0^2,15.0^5,14.0^6,11.0^19,28.0^20,25] nonacosa-5(14),6,8,10,19 (28),20,22,24-octaene-13,27-dione

Crystal data

C30H28O6	F(000) = 512
Mr = 484.52	Dx = 1.321 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 5888 reflections
a = 11.001 (2) Å	θ = 2.4–27.3°
b = 8.307 (2) Å	µ = 0.09 mm^−1
c = 13.332 (3) Å	T = 296 K
β = 90.39 (3)°	Block, colourless
V = 1218.3 (4) Å^3	0.4 × 0.2 × 0.1 mm
Z = 2

Data collection

MAC DIP 2030K area-detector diffractometer	2715 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.024
Graphite monochromator	θmax = 27.3°, θmin = 2.4°
ω scans	h = 0→14
5888 measured reflections	k = 0→10
2725 independent reflections	l = −17→17

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H-atom parameters constrained
S = 1.23	w = 1/[σ^2(Fo^2) + (0.0589P)^2 + 0.4086P] where P = (Fo^2 + 2Fc^2)/3
2725 reflections	(Δ/σ)max = 0.014
325 parameters	Δρmax = 0.17 e Å^−3
1 restraint	Δρmin = −0.26 e Å^−3

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

	x	y	z	Uiso*/Ueq
O1	0.7355 (3)	0.2776 (4)	−0.14454 (18)	0.0643 (8)
O2	0.8216 (3)	0.1374 (4)	−0.0228 (2)	0.0693 (8)
O3	0.6770 (2)	0.6634 (3)	0.04218 (18)	0.0505 (6)
O4	0.6584 (2)	0.2453 (4)	0.45755 (18)	0.0531 (6)
O5	0.6168 (2)	0.4948 (4)	0.4124 (2)	0.0649 (8)
O6	0.9704 (2)	0.2404 (3)	0.29082 (16)	0.0428 (5)
C1	0.7763 (4)	0.2653 (5)	−0.0467 (2)	0.0530 (9)
C2	0.7620 (3)	0.4032 (4)	0.0175 (2)	0.0402 (7)
C3	0.6996 (3)	0.5345 (5)	−0.0158 (2)	0.0430 (7)
C4	0.6504 (3)	0.5440 (5)	−0.1176 (2)	0.0491 (8)
C5	0.5853 (3)	0.6767 (6)	−0.1592 (3)	0.0615 (11)
C6	0.5506 (4)	0.6651 (8)	−0.2605 (3)	0.0756 (15)
H6A	0.5078	0.7500	−0.2893	0.091*
C7	0.5773 (4)	0.5335 (9)	−0.3187 (3)	0.0811 (17)
H7A	0.5533	0.5318	−0.3857	0.097*
C8	0.6390 (4)	0.4043 (8)	−0.2791 (3)	0.0715 (13)
H8A	0.6568	0.3148	−0.3182	0.086*
C9	0.6741 (3)	0.4114 (6)	−0.1787 (3)	0.0569 (10)
C10	0.7515 (3)	0.6904 (4)	0.1339 (2)	0.0434 (7)
C11	0.7614 (3)	0.5278 (4)	0.1887 (2)	0.0366 (6)
H11A	0.6776	0.4980	0.2052	0.044*
C12	0.8097 (3)	0.3885 (4)	0.1239 (2)	0.0372 (6)
H12A	0.7751	0.2893	0.1514	0.045*
C13	0.5560 (5)	0.8283 (8)	−0.1029 (4)	0.0867 (17)
H13A	0.5109	0.8998	−0.1458	0.130*
H13B	0.6301	0.8795	−0.0819	0.130*
H13C	0.5083	0.8023	−0.0451	0.130*
C14	0.8674 (4)	0.7694 (5)	0.0978 (3)	0.0600 (10)
H14A	0.8480	0.8691	0.0650	0.090*
H14B	0.9077	0.6991	0.0515	0.090*
H14C	0.9200	0.7900	0.1541	0.090*
C15	0.6741 (5)	0.8099 (6)	0.1928 (3)	0.0711 (13)
H15A	0.6698	0.9100	0.1570	0.107*
H15B	0.7102	0.8275	0.2576	0.107*
H15C	0.5937	0.7671	0.2008	0.107*
C16	0.6883 (3)	0.3854 (5)	0.4071 (2)	0.0472 (8)
C17	0.7993 (3)	0.3854 (4)	0.3504 (2)	0.0394 (6)
C18	0.8705 (3)	0.2522 (4)	0.3484 (2)	0.0368 (6)
C19	0.8438 (3)	0.1088 (4)	0.4075 (2)	0.0409 (7)
C20	0.9172 (3)	−0.0313 (4)	0.4168 (2)	0.0460 (7)
C21	0.8725 (4)	−0.1588 (5)	0.4723 (3)	0.0560 (9)
H21A	0.9206	−0.2500	0.4804	0.067*
C22	0.7584 (4)	−0.1556 (5)	0.5163 (3)	0.0619 (11)
H22A	0.7297	−0.2460	0.5498	0.074*
C23	0.6882 (4)	−0.0202 (6)	0.5106 (3)	0.0598 (10)
H23A	0.6125	−0.0163	0.5413	0.072*
C24	0.7323 (3)	0.1118 (5)	0.4580 (2)	0.0473 (8)
C25	1.0080 (3)	0.3801 (4)	0.2292 (2)	0.0405 (7)
C26	0.9692 (3)	0.5335 (4)	0.2813 (2)	0.0424 (7)
H26A	0.9952	0.6263	0.2428	0.051*
H26B	1.0065	0.5396	0.3473	0.051*
C27	0.8302 (3)	0.5333 (4)	0.2907 (2)	0.0398 (7)
H27A	0.8047	0.6291	0.3280	0.048*
C28	1.0431 (4)	−0.0474 (5)	0.3722 (3)	0.0549 (9)
H28A	1.0755	−0.1518	0.3878	0.082*
H28B	1.0953	0.0342	0.3998	0.082*
H28C	1.0381	−0.0348	0.3007	0.082*
C29	0.9487 (3)	0.3673 (4)	0.1257 (2)	0.0406 (7)
H29A	0.9680	0.2627	0.0976	0.049*
H29B	0.9843	0.4482	0.0824	0.049*
C30	1.1448 (3)	0.3621 (6)	0.2214 (3)	0.0552 (9)
H30A	1.1808	0.3710	0.2869	0.083*
H30B	1.1764	0.4453	0.1789	0.083*
H30C	1.1638	0.2588	0.1933	0.083*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0834 (19)	0.0721 (19)	0.0375 (12)	−0.0012 (17)	−0.0058 (12)	−0.0085 (13)
O2	0.102 (2)	0.0495 (16)	0.0560 (15)	0.0131 (16)	−0.0114 (15)	−0.0132 (13)
O3	0.0520 (13)	0.0516 (15)	0.0478 (12)	0.0145 (12)	−0.0099 (10)	0.0030 (11)
O4	0.0447 (12)	0.0690 (17)	0.0458 (12)	−0.0008 (13)	0.0114 (10)	0.0099 (12)
O5	0.0554 (15)	0.074 (2)	0.0653 (16)	0.0142 (15)	0.0178 (12)	−0.0005 (15)
O6	0.0416 (11)	0.0459 (13)	0.0410 (11)	0.0060 (10)	0.0097 (9)	0.0082 (10)
C1	0.066 (2)	0.057 (2)	0.0369 (15)	0.0011 (19)	−0.0031 (14)	−0.0067 (16)
C2	0.0416 (14)	0.0441 (17)	0.0347 (14)	0.0015 (14)	−0.0004 (11)	0.0002 (13)
C3	0.0380 (14)	0.0526 (19)	0.0385 (14)	−0.0010 (14)	0.0024 (11)	0.0016 (14)
C4	0.0349 (14)	0.072 (2)	0.0401 (15)	−0.0041 (16)	−0.0005 (12)	0.0096 (17)
C5	0.0353 (15)	0.095 (3)	0.0542 (19)	0.0025 (19)	−0.0031 (14)	0.025 (2)
C6	0.0463 (19)	0.122 (4)	0.058 (2)	−0.001 (2)	−0.0114 (17)	0.034 (3)
C7	0.054 (2)	0.147 (5)	0.0418 (18)	−0.019 (3)	−0.0100 (16)	0.020 (3)
C8	0.064 (2)	0.112 (4)	0.0389 (17)	−0.019 (3)	−0.0048 (16)	0.000 (2)
C9	0.0471 (18)	0.083 (3)	0.0407 (16)	−0.011 (2)	−0.0017 (13)	0.0060 (18)
C10	0.0494 (17)	0.0422 (17)	0.0387 (15)	0.0101 (14)	0.0012 (12)	0.0009 (13)
C11	0.0341 (12)	0.0411 (16)	0.0345 (13)	0.0047 (12)	0.0023 (10)	0.0012 (12)
C12	0.0389 (14)	0.0399 (15)	0.0329 (13)	0.0027 (13)	0.0031 (10)	−0.0017 (12)
C13	0.074 (3)	0.107 (4)	0.078 (3)	0.043 (3)	−0.007 (2)	0.024 (3)
C14	0.061 (2)	0.047 (2)	0.072 (2)	−0.0025 (18)	−0.0037 (18)	0.0141 (19)
C15	0.091 (3)	0.058 (3)	0.064 (2)	0.039 (2)	0.001 (2)	−0.0062 (19)
C16	0.0432 (16)	0.063 (2)	0.0356 (14)	−0.0014 (17)	0.0065 (12)	−0.0004 (16)
C17	0.0421 (15)	0.0465 (17)	0.0295 (12)	0.0019 (15)	0.0035 (11)	−0.0021 (13)
C18	0.0370 (13)	0.0433 (16)	0.0302 (12)	−0.0047 (13)	0.0016 (10)	0.0033 (12)
C19	0.0466 (16)	0.0460 (18)	0.0301 (13)	−0.0047 (14)	−0.0012 (11)	0.0021 (12)
C20	0.0574 (18)	0.0438 (18)	0.0368 (15)	−0.0058 (16)	−0.0084 (13)	−0.0015 (14)
C21	0.074 (2)	0.049 (2)	0.0451 (18)	−0.0082 (19)	−0.0086 (16)	0.0045 (16)
C22	0.079 (3)	0.058 (2)	0.0483 (19)	−0.022 (2)	−0.0058 (18)	0.0136 (17)
C23	0.056 (2)	0.079 (3)	0.0441 (17)	−0.021 (2)	0.0030 (15)	0.0102 (19)
C24	0.0467 (16)	0.060 (2)	0.0353 (14)	−0.0066 (16)	−0.0005 (13)	0.0051 (15)
C25	0.0366 (14)	0.0464 (17)	0.0385 (14)	0.0014 (14)	0.0042 (11)	0.0071 (14)
C26	0.0417 (15)	0.0445 (17)	0.0411 (15)	−0.0029 (14)	−0.0009 (12)	0.0035 (14)
C27	0.0420 (15)	0.0423 (17)	0.0349 (14)	0.0025 (14)	0.0000 (11)	−0.0024 (13)
C28	0.061 (2)	0.046 (2)	0.057 (2)	0.0079 (17)	0.0001 (16)	0.0012 (16)
C29	0.0397 (14)	0.0477 (18)	0.0344 (13)	0.0071 (14)	0.0071 (11)	0.0041 (13)
C30	0.0347 (15)	0.074 (3)	0.0568 (19)	0.0051 (17)	0.0041 (13)	0.0174 (19)

Geometric parameters (Å, º)

O1—C9	1.376 (6)	C14—H14A	0.9600
O1—C1	1.380 (4)	C14—H14B	0.9600
O2—C1	1.215 (5)	C14—H14C	0.9600
O3—C3	1.344 (4)	C15—H15A	0.9600
O3—C10	1.484 (4)	C15—H15B	0.9600
O4—C24	1.375 (5)	C15—H15C	0.9600
O4—C16	1.385 (5)	C16—C17	1.440 (4)
O5—C16	1.205 (5)	C17—C18	1.356 (5)
O6—C18	1.348 (3)	C17—C27	1.505 (5)
O6—C25	1.482 (4)	C18—C19	1.460 (4)
C1—C2	1.440 (5)	C19—C24	1.403 (5)
C2—C3	1.362 (5)	C19—C20	1.421 (5)
C2—C12	1.514 (4)	C20—C21	1.384 (5)
C3—C4	1.461 (4)	C20—C28	1.517 (5)
C4—C9	1.395 (6)	C21—C22	1.389 (6)
C4—C5	1.425 (6)	C21—H21A	0.9300
C5—C6	1.404 (6)	C22—C23	1.367 (7)
C5—C13	1.502 (8)	C22—H22A	0.9300
C6—C7	1.374 (8)	C23—C24	1.391 (5)
C6—H6A	0.9300	C23—H23A	0.9300
C7—C8	1.373 (8)	C25—C26	1.514 (5)
C7—H7A	0.9300	C25—C30	1.517 (4)
C8—C9	1.392 (5)	C25—C29	1.526 (4)
C8—H8A	0.9300	C26—C27	1.535 (4)
C10—C14	1.516 (5)	C26—H26A	0.9700
C10—C15	1.529 (5)	C26—H26B	0.9700
C10—C11	1.539 (4)	C27—H27A	0.9800
C11—C12	1.540 (4)	C28—H28A	0.9600
C11—C27	1.552 (4)	C28—H28B	0.9600
C11—H11A	0.9800	C28—H28C	0.9600
C12—C29	1.539 (4)	C29—H29A	0.9700
C12—H12A	0.9800	C29—H29B	0.9700
C13—H13A	0.9600	C30—H30A	0.9600
C13—H13B	0.9600	C30—H30B	0.9600
C13—H13C	0.9600	C30—H30C	0.9600
C9—O1—C1	121.9 (3)	H15A—C15—H15C	109.5
C3—O3—C10	119.3 (2)	H15B—C15—H15C	109.5
C24—O4—C16	122.5 (2)	O5—C16—O4	116.6 (3)
C18—O6—C25	119.3 (2)	O5—C16—C17	126.0 (4)
O2—C1—O1	116.3 (3)	O4—C16—C17	117.4 (3)
O2—C1—C2	125.9 (3)	C18—C17—C16	120.2 (3)
O1—C1—C2	117.8 (3)	C18—C17—C27	121.5 (2)
C3—C2—C1	120.1 (3)	C16—C17—C27	118.2 (3)
C3—C2—C12	122.7 (3)	O6—C18—C17	123.0 (3)
C1—C2—C12	117.0 (3)	O6—C18—C19	114.6 (3)
O3—C3—C2	123.1 (3)	C17—C18—C19	122.5 (3)
O3—C3—C4	115.0 (3)	C24—C19—C20	118.1 (3)
C2—C3—C4	121.9 (3)	C24—C19—C18	115.1 (3)
C9—C4—C5	118.6 (3)	C20—C19—C18	126.8 (3)
C9—C4—C3	115.5 (3)	C21—C20—C19	118.0 (3)
C5—C4—C3	125.8 (4)	C21—C20—C28	118.1 (3)
C6—C5—C4	117.0 (5)	C19—C20—C28	123.9 (3)
C6—C5—C13	118.7 (4)	C20—C21—C22	122.5 (4)
C4—C5—C13	124.3 (3)	C20—C21—H21A	118.8
C7—C6—C5	122.7 (5)	C22—C21—H21A	118.8
C7—C6—H6A	118.7	C23—C22—C21	120.3 (4)
C5—C6—H6A	118.7	C23—C22—H22A	119.9
C8—C7—C6	120.8 (4)	C21—C22—H22A	119.9
C8—C7—H7A	119.6	C22—C23—C24	118.5 (3)
C6—C7—H7A	119.6	C22—C23—H23A	120.7
C7—C8—C9	118.0 (5)	C24—C23—H23A	120.7
C7—C8—H8A	121.0	O4—C24—C23	115.4 (3)
C9—C8—H8A	121.0	O4—C24—C19	122.1 (3)
O1—C9—C8	114.6 (4)	C23—C24—C19	122.5 (4)
O1—C9—C4	122.5 (3)	O6—C25—C26	108.9 (2)
C8—C9—C4	122.9 (4)	O6—C25—C30	104.0 (3)
O3—C10—C14	105.4 (3)	C26—C25—C30	113.4 (3)
O3—C10—C15	102.4 (3)	O6—C25—C29	109.1 (3)
C14—C10—C15	110.8 (4)	C26—C25—C29	110.7 (3)
O3—C10—C11	107.2 (3)	C30—C25—C29	110.5 (3)
C14—C10—C11	118.3 (3)	C25—C26—C27	108.7 (3)
C15—C10—C11	111.3 (3)	C25—C26—H26A	110.0
C10—C11—C12	114.6 (2)	C27—C26—H26A	110.0
C10—C11—C27	115.0 (3)	C25—C26—H26B	110.0
C12—C11—C27	110.2 (2)	C27—C26—H26B	110.0
C10—C11—H11A	105.3	H26A—C26—H26B	108.3
C12—C11—H11A	105.3	C17—C27—C26	105.8 (3)
C27—C11—H11A	105.3	C17—C27—C11	109.2 (3)
C2—C12—C29	111.2 (2)	C26—C27—C11	114.1 (2)
C2—C12—C11	110.3 (3)	C17—C27—H27A	109.2
C29—C12—C11	115.1 (3)	C26—C27—H27A	109.2
C2—C12—H12A	106.6	C11—C27—H27A	109.2
C29—C12—H12A	106.6	C20—C28—H28A	109.5
C11—C12—H12A	106.6	C20—C28—H28B	109.5
C5—C13—H13A	109.5	H28A—C28—H28B	109.5
C5—C13—H13B	109.5	C20—C28—H28C	109.5
H13A—C13—H13B	109.5	H28A—C28—H28C	109.5
C5—C13—H13C	109.5	H28B—C28—H28C	109.5
H13A—C13—H13C	109.5	C25—C29—C12	115.1 (2)
H13B—C13—H13C	109.5	C25—C29—H29A	108.5
C10—C14—H14A	109.5	C12—C29—H29A	108.5
C10—C14—H14B	109.5	C25—C29—H29B	108.5
H14A—C14—H14B	109.5	C12—C29—H29B	108.5
C10—C14—H14C	109.5	H29A—C29—H29B	107.5
H14A—C14—H14C	109.5	C25—C30—H30A	109.5
H14B—C14—H14C	109.5	C25—C30—H30B	109.5
C10—C15—H15A	109.5	H30A—C30—H30B	109.5
C10—C15—H15B	109.5	C25—C30—H30C	109.5
H15A—C15—H15B	109.5	H30A—C30—H30C	109.5
C10—C15—H15C	109.5	H30B—C30—H30C	109.5
C9—O1—C1—O2	174.9 (4)	O5—C16—C17—C18	−178.1 (3)
C9—O1—C1—C2	−5.1 (5)	O4—C16—C17—C18	−0.5 (4)
O2—C1—C2—C3	−173.9 (4)	O5—C16—C17—C27	−0.7 (5)
O1—C1—C2—C3	6.1 (5)	O4—C16—C17—C27	176.9 (3)
O2—C1—C2—C12	1.2 (6)	C25—O6—C18—C17	2.3 (4)
O1—C1—C2—C12	−178.8 (3)	C25—O6—C18—C19	−178.6 (3)
C10—O3—C3—C2	19.3 (5)	C16—C17—C18—O6	174.8 (3)
C10—O3—C3—C4	−161.6 (3)	C27—C17—C18—O6	−2.5 (5)
C1—C2—C3—O3	176.1 (3)	C16—C17—C18—C19	−4.2 (4)
C12—C2—C3—O3	1.3 (5)	C27—C17—C18—C19	178.5 (3)
C1—C2—C3—C4	−2.9 (5)	O6—C18—C19—C24	−172.4 (3)
C12—C2—C3—C4	−177.7 (3)	C17—C18—C19—C24	6.7 (4)
O3—C3—C4—C9	179.6 (3)	O6—C18—C19—C20	6.2 (4)
C2—C3—C4—C9	−1.4 (5)	C17—C18—C19—C20	−174.7 (3)
O3—C3—C4—C5	1.6 (5)	C24—C19—C20—C21	2.2 (4)
C2—C3—C4—C5	−179.3 (3)	C18—C19—C20—C21	−176.4 (3)
C9—C4—C5—C6	−0.9 (5)	C24—C19—C20—C28	−175.9 (3)
C3—C4—C5—C6	177.0 (3)	C18—C19—C20—C28	5.5 (5)
C9—C4—C5—C13	−178.6 (4)	C19—C20—C21—C22	1.7 (5)
C3—C4—C5—C13	−0.7 (6)	C28—C20—C21—C22	179.9 (3)
C4—C5—C6—C7	−0.2 (6)	C20—C21—C22—C23	−3.6 (6)
C13—C5—C6—C7	177.7 (4)	C21—C22—C23—C24	1.5 (6)
C5—C6—C7—C8	0.8 (7)	C16—O4—C24—C23	−178.9 (3)
C6—C7—C8—C9	−0.4 (6)	C16—O4—C24—C19	0.3 (5)
C1—O1—C9—C8	−179.9 (3)	C22—C23—C24—O4	−178.3 (3)
C1—O1—C9—C4	0.8 (5)	C22—C23—C24—C19	2.4 (5)
C7—C8—C9—O1	−180.0 (4)	C20—C19—C24—O4	176.5 (3)
C7—C8—C9—C4	−0.7 (6)	C18—C19—C24—O4	−4.7 (4)
C5—C4—C9—O1	−179.4 (3)	C20—C19—C24—C23	−4.3 (5)
C3—C4—C9—O1	2.5 (5)	C18—C19—C24—C23	174.4 (3)
C5—C4—C9—C8	1.3 (5)	C18—O6—C25—C26	29.9 (3)
C3—C4—C9—C8	−176.8 (3)	C18—O6—C25—C30	151.1 (3)
C3—O3—C10—C14	81.3 (4)	C18—O6—C25—C29	−91.0 (3)
C3—O3—C10—C15	−162.8 (3)	O6—C25—C26—C27	−61.2 (3)
C3—O3—C10—C11	−45.5 (4)	C30—C25—C26—C27	−176.4 (3)
O3—C10—C11—C12	54.3 (3)	C29—C25—C26—C27	58.8 (3)
C14—C10—C11—C12	−64.6 (4)	C18—C17—C27—C26	−28.6 (4)
C15—C10—C11—C12	165.5 (3)	C16—C17—C27—C26	154.0 (3)
O3—C10—C11—C27	−176.5 (2)	C18—C17—C27—C11	94.6 (3)
C14—C10—C11—C27	64.6 (4)	C16—C17—C27—C11	−82.7 (3)
C15—C10—C11—C27	−65.3 (4)	C25—C26—C27—C17	59.2 (3)
C3—C2—C12—C29	−120.7 (3)	C25—C26—C27—C11	−60.9 (4)
C1—C2—C12—C29	64.4 (4)	C10—C11—C27—C17	161.9 (2)
C3—C2—C12—C11	8.2 (4)	C12—C11—C27—C17	−66.7 (3)
C1—C2—C12—C11	−166.7 (3)	C10—C11—C27—C26	−79.9 (3)
C10—C11—C12—C2	−36.9 (4)	C12—C11—C27—C26	51.4 (4)
C27—C11—C12—C2	−168.4 (2)	O6—C25—C29—C12	67.9 (4)
C10—C11—C12—C29	89.9 (3)	C26—C25—C29—C12	−51.9 (4)
C27—C11—C12—C29	−41.7 (3)	C30—C25—C29—C12	−178.3 (3)
C24—O4—C16—O5	−179.7 (3)	C2—C12—C29—C25	170.0 (3)
C24—O4—C16—C17	2.5 (5)	C11—C12—C29—C25	43.8 (4)

(II) (±)-(11RS,12RS,25RS,27SR)-3,3,7,17,21-pentamethyl-4,12,18,26- tetraoxaheptacyclo[15.11.1.0^2,15.0^5,14.0^6,11.0^19,28.0^20,25] nonacosa-5(14),6,8,10,19 (28),20,22,24-octaene-13,27-dione

Crystal data

C30H28O6	F(000) = 1024
Mr = 484.52	Dx = 1.377 Mg m^−3
Monoclinic, P121/c1	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 15334 reflections
a = 15.517 (3) Å	θ = 2.5–27.4°
b = 19.411 (4) Å	µ = 0.10 mm^−1
c = 7.963 (2) Å	T = 296 K
β = 102.90 (3)°	Block, colourless
V = 2337.9 (9) Å^3	0.5 × 0.3 × 0.1 mm
Z = 4

Data collection

Rigaku RAXIS-RAPID area-detector diffractometer	2479 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.070
Graphite monochromator	θmax = 27.4°, θmin = 1.4°
ω scans	h = −20→19
15334 measured reflections	k = −25→0
5186 independent reflections	l = 0→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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.161	H-atom parameters constrained
S = 0.84	w = 1/[σ^2(Fo^2) + (0.0719P)^2] where P = (Fo^2 + 2Fc^2)/3
5186 reflections	(Δ/σ)max = 0.001
325 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.30 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.

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

	x	y	z	Uiso*/Ueq
O1	0.03621 (11)	0.47239 (9)	0.7275 (2)	0.0259 (4)
O2	0.15966 (12)	0.52699 (10)	0.8351 (2)	0.0386 (5)
O3	0.05187 (11)	0.35392 (9)	1.1577 (2)	0.0313 (5)
O4	0.43745 (11)	0.22477 (9)	1.1862 (2)	0.0263 (4)
O5	0.31980 (13)	0.21359 (9)	1.2955 (3)	0.0361 (5)
O6	0.43873 (11)	0.43504 (9)	1.2440 (2)	0.0228 (4)
C1	0.10974 (17)	0.48231 (14)	0.8602 (3)	0.0261 (6)
C2	0.11841 (16)	0.43835 (13)	1.0101 (3)	0.0204 (6)
C3	0.05082 (16)	0.39516 (13)	1.0219 (3)	0.0212 (6)
C4	−0.02983 (16)	0.38913 (13)	0.8876 (3)	0.0211 (6)
C5	−0.10339 (17)	0.34695 (13)	0.8915 (3)	0.0261 (6)
C6	−0.17184 (17)	0.34547 (14)	0.7468 (4)	0.0312 (7)
H6A	−0.2216	0.3190	0.7491	0.037*
C7	−0.16915 (18)	0.38181 (14)	0.5988 (4)	0.0308 (7)
H7A	−0.2156	0.3782	0.5026	0.037*
C8	−0.09805 (17)	0.42330 (14)	0.5931 (3)	0.0263 (6)
H8A	−0.0955	0.4479	0.4941	0.032*
C9	−0.03088 (16)	0.42733 (13)	0.7378 (3)	0.0220 (6)
C10	0.13262 (16)	0.34270 (13)	1.2957 (3)	0.0217 (6)
C11	0.21214 (15)	0.36568 (12)	1.2283 (3)	0.0189 (6)
H11A	0.2149	0.3355	1.1310	0.023*
C12	0.19930 (15)	0.43949 (12)	1.1563 (3)	0.0197 (6)
H12A	0.1858	0.4690	1.2470	0.024*
C13	−0.11279 (18)	0.30387 (14)	1.0449 (4)	0.0384 (8)
H13A	−0.1677	0.2791	1.0175	0.058*
H13B	−0.1119	0.3334	1.1420	0.058*
H13C	−0.0647	0.2717	1.0725	0.058*
C14	0.11824 (19)	0.38248 (14)	1.4530 (3)	0.0318 (7)
H14A	0.0670	0.3648	1.4872	0.048*
H14B	0.1096	0.4304	1.4244	0.048*
H14C	0.1691	0.3772	1.5461	0.048*
C15	0.13023 (18)	0.26571 (13)	1.3266 (3)	0.0277 (6)
H15A	0.1394	0.2416	1.2268	0.042*
H15B	0.0738	0.2533	1.3481	0.042*
H15C	0.1761	0.2536	1.4246	0.042*
C16	0.37286 (17)	0.25337 (14)	1.2595 (3)	0.0249 (6)
C17	0.37308 (16)	0.32691 (13)	1.2810 (3)	0.0198 (6)
C18	0.43707 (16)	0.36570 (13)	1.2355 (3)	0.0213 (6)
C19	0.51009 (16)	0.33507 (14)	1.1732 (3)	0.0214 (6)
C20	0.58517 (17)	0.36972 (14)	1.1419 (3)	0.0260 (6)
C21	0.64612 (18)	0.33189 (15)	1.0763 (3)	0.0296 (7)
H21A	0.6951	0.3543	1.0529	0.036*
C22	0.63622 (18)	0.26188 (15)	1.0448 (3)	0.0312 (7)
H22A	0.6774	0.2384	0.9975	0.037*
C23	0.56672 (17)	0.22700 (14)	1.0823 (3)	0.0277 (7)
H23A	0.5608	0.1797	1.0640	0.033*
C24	0.50492 (17)	0.26356 (14)	1.1483 (3)	0.0230 (6)
C25	0.36000 (16)	0.46824 (13)	1.2812 (3)	0.0207 (6)
C26	0.33610 (16)	0.42898 (12)	1.4302 (3)	0.0214 (6)
H26A	0.2905	0.4533	1.4723	0.026*
H26B	0.3876	0.4241	1.5243	0.026*
C27	0.30265 (16)	0.35833 (12)	1.3606 (3)	0.0209 (6)
H27A	0.2946	0.3293	1.4566	0.025*
C28	0.60413 (18)	0.44519 (14)	1.1780 (4)	0.0330 (7)
H28A	0.6582	0.4574	1.1458	0.050*
H28B	0.6098	0.4540	1.2986	0.050*
H28C	0.5565	0.4722	1.1125	0.050*
C29	0.28511 (16)	0.46543 (13)	1.1169 (3)	0.0218 (6)
H29A	0.2758	0.5111	1.0667	0.026*
H29B	0.3025	0.4352	1.0333	0.026*
C30	0.38962 (17)	0.54159 (13)	1.3277 (3)	0.0285 (7)
H30A	0.4357	0.5415	1.4308	0.043*
H30B	0.3404	0.5681	1.3467	0.043*
H30C	0.4115	0.5617	1.2352	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0253 (10)	0.0285 (11)	0.0227 (10)	−0.0034 (8)	0.0029 (8)	0.0051 (8)
O2	0.0364 (12)	0.0387 (13)	0.0368 (12)	−0.0130 (10)	0.0001 (10)	0.0183 (10)
O3	0.0210 (10)	0.0423 (13)	0.0296 (11)	−0.0046 (9)	0.0037 (8)	0.0168 (9)
O4	0.0249 (10)	0.0233 (10)	0.0305 (10)	0.0026 (8)	0.0057 (9)	−0.0056 (8)
O5	0.0371 (12)	0.0228 (11)	0.0523 (13)	−0.0039 (9)	0.0185 (10)	−0.0036 (10)
O6	0.0196 (9)	0.0197 (10)	0.0310 (10)	−0.0005 (8)	0.0098 (8)	−0.0011 (8)
C1	0.0247 (15)	0.0248 (15)	0.0288 (15)	0.0023 (12)	0.0062 (13)	0.0018 (12)
C2	0.0221 (14)	0.0182 (14)	0.0231 (14)	0.0012 (11)	0.0092 (11)	0.0009 (11)
C3	0.0223 (14)	0.0207 (14)	0.0228 (14)	0.0045 (11)	0.0094 (12)	0.0024 (11)
C4	0.0200 (14)	0.0210 (15)	0.0223 (14)	0.0030 (11)	0.0045 (12)	−0.0014 (11)
C5	0.0232 (15)	0.0232 (15)	0.0326 (16)	0.0020 (12)	0.0079 (13)	0.0009 (12)
C6	0.0171 (14)	0.0272 (16)	0.0501 (19)	−0.0042 (12)	0.0090 (14)	−0.0021 (14)
C7	0.0244 (15)	0.0310 (16)	0.0334 (16)	0.0018 (12)	−0.0014 (13)	−0.0063 (13)
C8	0.0265 (15)	0.0280 (16)	0.0241 (15)	0.0055 (12)	0.0055 (13)	−0.0006 (12)
C9	0.0221 (14)	0.0215 (14)	0.0213 (14)	0.0014 (11)	0.0029 (11)	−0.0039 (11)
C10	0.0194 (14)	0.0223 (14)	0.0225 (14)	−0.0005 (11)	0.0031 (12)	0.0042 (11)
C11	0.0231 (14)	0.0170 (14)	0.0175 (13)	−0.0005 (11)	0.0062 (11)	−0.0013 (10)
C12	0.0212 (14)	0.0192 (14)	0.0179 (13)	0.0003 (11)	0.0027 (11)	0.0004 (11)
C13	0.0237 (16)	0.0418 (19)	0.0486 (19)	−0.0081 (14)	0.0059 (14)	0.0150 (16)
C14	0.0380 (17)	0.0322 (17)	0.0306 (16)	0.0005 (14)	0.0192 (14)	−0.0004 (13)
C15	0.0323 (16)	0.0249 (15)	0.0275 (15)	−0.0031 (12)	0.0102 (13)	0.0048 (12)
C16	0.0240 (15)	0.0287 (16)	0.0203 (14)	0.0022 (13)	0.0013 (12)	−0.0015 (12)
C17	0.0216 (14)	0.0206 (14)	0.0160 (13)	0.0019 (11)	0.0016 (11)	−0.0014 (11)
C18	0.0214 (14)	0.0225 (15)	0.0185 (13)	0.0027 (12)	0.0011 (11)	−0.0018 (11)
C19	0.0195 (14)	0.0277 (15)	0.0154 (13)	0.0028 (12)	0.0005 (11)	−0.0006 (11)
C20	0.0236 (15)	0.0321 (16)	0.0219 (14)	0.0012 (12)	0.0043 (12)	0.0032 (12)
C21	0.0272 (16)	0.0394 (18)	0.0239 (14)	0.0046 (13)	0.0094 (13)	0.0055 (13)
C22	0.0264 (16)	0.0425 (19)	0.0245 (15)	0.0139 (14)	0.0052 (13)	0.0000 (13)
C23	0.0273 (15)	0.0283 (16)	0.0243 (15)	0.0085 (13)	−0.0009 (12)	−0.0028 (12)
C24	0.0225 (14)	0.0279 (16)	0.0173 (13)	0.0026 (12)	0.0018 (11)	−0.0003 (11)
C25	0.0167 (13)	0.0201 (14)	0.0266 (14)	0.0012 (11)	0.0072 (12)	−0.0017 (11)
C26	0.0188 (13)	0.0233 (14)	0.0222 (14)	0.0004 (11)	0.0044 (11)	−0.0039 (11)
C27	0.0233 (14)	0.0196 (14)	0.0198 (13)	0.0005 (11)	0.0053 (11)	0.0027 (11)
C28	0.0286 (16)	0.0366 (18)	0.0372 (17)	−0.0033 (13)	0.0147 (13)	0.0014 (14)
C29	0.0227 (14)	0.0224 (14)	0.0203 (13)	−0.0025 (11)	0.0047 (11)	0.0027 (11)
C30	0.0286 (16)	0.0258 (15)	0.0308 (15)	−0.0010 (12)	0.0058 (13)	−0.0018 (12)

Geometric parameters (Å, º)

O1—C9	1.376 (3)	C14—H14A	0.9600
O1—C1	1.385 (3)	C14—H14B	0.9600
O2—C1	1.209 (3)	C14—H14C	0.9600
O3—C3	1.343 (3)	C15—H15A	0.9600
O3—C10	1.486 (3)	C15—H15B	0.9600
O4—C24	1.377 (3)	C15—H15C	0.9600
O4—C16	1.384 (3)	C16—C17	1.438 (4)
O5—C16	1.209 (3)	C17—C18	1.358 (3)
O6—C18	1.348 (3)	C17—C27	1.509 (3)
O6—C25	1.469 (3)	C18—C19	1.461 (4)
C1—C2	1.449 (3)	C19—C24	1.402 (3)
C2—C3	1.362 (3)	C19—C20	1.415 (4)
C2—C12	1.509 (3)	C20—C21	1.388 (4)
C3—C4	1.458 (3)	C20—C28	1.509 (4)
C4—C9	1.401 (3)	C21—C22	1.384 (4)
C4—C5	1.411 (3)	C21—H21A	0.9300
C5—C6	1.382 (4)	C22—C23	1.362 (4)
C5—C13	1.514 (4)	C22—H22A	0.9300
C6—C7	1.382 (4)	C23—C24	1.387 (3)
C6—H6A	0.9300	C23—H23A	0.9300
C7—C8	1.375 (4)	C25—C30	1.517 (3)
C7—H7A	0.9300	C25—C26	1.524 (3)
C8—C9	1.372 (3)	C25—C29	1.545 (3)
C8—H8A	0.9300	C26—C27	1.526 (3)
C10—C15	1.516 (4)	C26—H26A	0.9700
C10—C11	1.518 (3)	C26—H26B	0.9700
C10—C14	1.530 (3)	C27—H27A	0.9800
C11—C12	1.540 (3)	C28—H28A	0.9600
C11—C27	1.563 (3)	C28—H28B	0.9600
C11—H11A	0.9800	C28—H28C	0.9600
C12—C29	1.520 (3)	C29—H29A	0.9700
C12—H12A	0.9800	C29—H29B	0.9700
C13—H13A	0.9600	C30—H30A	0.9600
C13—H13B	0.9600	C30—H30B	0.9600
C13—H13C	0.9600	C30—H30C	0.9600
C9—O1—C1	123.2 (2)	H15A—C15—H15C	109.5
C3—O3—C10	122.63 (19)	H15B—C15—H15C	109.5
C24—O4—C16	122.1 (2)	O5—C16—O4	116.1 (2)
C18—O6—C25	116.16 (19)	O5—C16—C17	126.1 (3)
O2—C1—O1	115.0 (2)	O4—C16—C17	117.8 (2)
O2—C1—C2	127.9 (2)	C18—C17—C16	120.1 (2)
O1—C1—C2	117.1 (2)	C18—C17—C27	121.9 (2)
C3—C2—C1	119.2 (2)	C16—C17—C27	117.9 (2)
C3—C2—C12	118.5 (2)	O6—C18—C17	123.2 (2)
C1—C2—C12	122.3 (2)	O6—C18—C19	114.6 (2)
O3—C3—C2	123.5 (2)	C17—C18—C19	122.2 (2)
O3—C3—C4	113.4 (2)	C24—C19—C20	118.0 (2)
C2—C3—C4	123.1 (2)	C24—C19—C18	115.3 (2)
C9—C4—C5	118.1 (2)	C20—C19—C18	126.7 (2)
C9—C4—C3	115.3 (2)	C21—C20—C19	118.1 (3)
C5—C4—C3	126.6 (2)	C21—C20—C28	117.7 (3)
C6—C5—C4	117.9 (2)	C19—C20—C28	124.1 (2)
C6—C5—C13	117.8 (2)	C22—C21—C20	122.0 (3)
C4—C5—C13	124.3 (2)	C22—C21—H21A	119.0
C7—C6—C5	122.4 (3)	C20—C21—H21A	119.0
C7—C6—H6A	118.8	C23—C22—C21	120.6 (3)
C5—C6—H6A	118.8	C23—C22—H22A	119.7
C8—C7—C6	120.3 (3)	C21—C22—H22A	119.7
C8—C7—H7A	119.9	C22—C23—C24	118.5 (3)
C6—C7—H7A	119.9	C22—C23—H23A	120.8
C9—C8—C7	118.1 (3)	C24—C23—H23A	120.8
C9—C8—H8A	121.0	O4—C24—C23	115.3 (2)
C7—C8—H8A	121.0	O4—C24—C19	122.2 (2)
C8—C9—O1	115.4 (2)	C23—C24—C19	122.5 (3)
C8—C9—C4	123.1 (3)	O6—C25—C30	103.93 (19)
O1—C9—C4	121.5 (2)	O6—C25—C26	107.21 (19)
O3—C10—C15	102.56 (19)	C30—C25—C26	113.1 (2)
O3—C10—C11	108.26 (18)	O6—C25—C29	108.41 (19)
C15—C10—C11	113.5 (2)	C30—C25—C29	111.7 (2)
O3—C10—C14	106.1 (2)	C26—C25—C29	112.0 (2)
C15—C10—C14	110.6 (2)	C25—C26—C27	106.8 (2)
C11—C10—C14	114.8 (2)	C25—C26—H26A	110.4
C10—C11—C12	110.9 (2)	C27—C26—H26A	110.4
C10—C11—C27	114.45 (19)	C25—C26—H26B	110.4
C12—C11—C27	110.99 (19)	C27—C26—H26B	110.4
C10—C11—H11A	106.7	H26A—C26—H26B	108.6
C12—C11—H11A	106.7	C17—C27—C26	107.2 (2)
C27—C11—H11A	106.7	C17—C27—C11	112.3 (2)
C2—C12—C29	117.5 (2)	C26—C27—C11	110.1 (2)
C2—C12—C11	106.84 (19)	C17—C27—H27A	109.0
C29—C12—C11	109.8 (2)	C26—C27—H27A	109.0
C2—C12—H12A	107.4	C11—C27—H27A	109.0
C29—C12—H12A	107.4	C20—C28—H28A	109.5
C11—C12—H12A	107.4	C20—C28—H28B	109.5
C5—C13—H13A	109.5	H28A—C28—H28B	109.5
C5—C13—H13B	109.5	C20—C28—H28C	109.5
H13A—C13—H13B	109.5	H28A—C28—H28C	109.5
C5—C13—H13C	109.5	H28B—C28—H28C	109.5
H13A—C13—H13C	109.5	C12—C29—C25	111.4 (2)
H13B—C13—H13C	109.5	C12—C29—H29A	109.3
C10—C14—H14A	109.5	C25—C29—H29A	109.3
C10—C14—H14B	109.5	C12—C29—H29B	109.3
H14A—C14—H14B	109.5	C25—C29—H29B	109.3
C10—C14—H14C	109.5	H29A—C29—H29B	108.0
H14A—C14—H14C	109.5	C25—C30—H30A	109.5
H14B—C14—H14C	109.5	C25—C30—H30B	109.5
C10—C15—H15A	109.5	H30A—C30—H30B	109.5
C10—C15—H15B	109.5	C25—C30—H30C	109.5
H15A—C15—H15B	109.5	H30A—C30—H30C	109.5
C10—C15—H15C	109.5	H30B—C30—H30C	109.5
C9—O1—C1—O2	−175.3 (2)	O5—C16—C17—C18	179.8 (2)
C9—O1—C1—C2	5.3 (3)	O4—C16—C17—C18	−2.2 (3)
O2—C1—C2—C3	173.8 (3)	O5—C16—C17—C27	2.0 (4)
O1—C1—C2—C3	−6.8 (4)	O4—C16—C17—C27	179.9 (2)
O2—C1—C2—C12	−5.1 (4)	C25—O6—C18—C17	−8.8 (3)
O1—C1—C2—C12	174.3 (2)	C25—O6—C18—C19	171.27 (19)
C10—O3—C3—C2	−10.4 (4)	C16—C17—C18—O6	176.6 (2)
C10—O3—C3—C4	169.5 (2)	C27—C17—C18—O6	−5.7 (4)
C1—C2—C3—O3	−178.2 (2)	C16—C17—C18—C19	−3.5 (4)
C12—C2—C3—O3	0.7 (4)	C27—C17—C18—C19	174.2 (2)
C1—C2—C3—C4	1.9 (4)	O6—C18—C19—C24	−174.3 (2)
C12—C2—C3—C4	−179.1 (2)	C17—C18—C19—C24	5.8 (3)
O3—C3—C4—C9	−175.3 (2)	O6—C18—C19—C20	7.9 (3)
C2—C3—C4—C9	4.5 (4)	C17—C18—C19—C20	−172.0 (2)
O3—C3—C4—C5	1.6 (4)	C24—C19—C20—C21	4.7 (3)
C2—C3—C4—C5	−178.5 (3)	C18—C19—C20—C21	−177.6 (2)
C9—C4—C5—C6	0.5 (4)	C24—C19—C20—C28	−174.3 (2)
C3—C4—C5—C6	−176.4 (2)	C18—C19—C20—C28	3.4 (4)
C9—C4—C5—C13	−178.7 (2)	C19—C20—C21—C22	−1.4 (4)
C3—C4—C5—C13	4.4 (4)	C28—C20—C21—C22	177.7 (2)
C4—C5—C6—C7	2.0 (4)	C20—C21—C22—C23	−1.9 (4)
C13—C5—C6—C7	−178.7 (3)	C21—C22—C23—C24	1.7 (4)
C5—C6—C7—C8	−2.3 (4)	C16—O4—C24—C23	177.3 (2)
C6—C7—C8—C9	−0.1 (4)	C16—O4—C24—C19	−3.3 (3)
C7—C8—C9—O1	−176.7 (2)	C22—C23—C24—O4	−178.8 (2)
C7—C8—C9—C4	2.7 (4)	C22—C23—C24—C19	1.8 (4)
C1—O1—C9—C8	−179.1 (2)	C20—C19—C24—O4	175.6 (2)
C1—O1—C9—C4	1.5 (4)	C18—C19—C24—O4	−2.4 (3)
C5—C4—C9—C8	−2.9 (4)	C20—C19—C24—C23	−5.0 (4)
C3—C4—C9—C8	174.3 (2)	C18—C19—C24—C23	177.0 (2)
C5—C4—C9—O1	176.5 (2)	C18—O6—C25—C30	165.99 (19)
C3—C4—C9—O1	−6.3 (3)	C18—O6—C25—C26	46.0 (3)
C3—O3—C10—C15	−137.4 (2)	C18—O6—C25—C29	−75.1 (2)
C3—O3—C10—C11	−17.2 (3)	O6—C25—C26—C27	−69.4 (2)
C3—O3—C10—C14	106.6 (2)	C30—C25—C26—C27	176.7 (2)
O3—C10—C11—C12	52.4 (3)	C29—C25—C26—C27	49.4 (3)
C15—C10—C11—C12	165.5 (2)	C18—C17—C27—C26	−18.7 (3)
C14—C10—C11—C12	−66.0 (3)	C16—C17—C27—C26	159.1 (2)
O3—C10—C11—C27	178.91 (19)	C18—C17—C27—C11	102.5 (3)
C15—C10—C11—C27	−68.0 (3)	C16—C17—C27—C11	−79.8 (3)
C14—C10—C11—C27	60.5 (3)	C25—C26—C27—C17	54.1 (2)
C3—C2—C12—C29	157.7 (2)	C25—C26—C27—C11	−68.3 (2)
C1—C2—C12—C29	−23.5 (3)	C10—C11—C27—C17	134.9 (2)
C3—C2—C12—C11	33.8 (3)	C12—C11—C27—C17	−98.6 (2)
C1—C2—C12—C11	−147.3 (2)	C10—C11—C27—C26	−105.6 (2)
C10—C11—C12—C2	−60.7 (2)	C12—C11—C27—C26	20.8 (3)
C27—C11—C12—C2	170.86 (19)	C2—C12—C29—C25	176.1 (2)
C10—C11—C12—C29	170.81 (19)	C11—C12—C29—C25	−61.6 (3)
C27—C11—C12—C29	42.4 (3)	O6—C25—C29—C12	131.7 (2)
C24—O4—C16—O5	−176.1 (2)	C30—C25—C29—C12	−114.4 (2)
C24—O4—C16—C17	5.7 (3)	C26—C25—C29—C12	13.6 (3)