Triterpenoide. XIX. 3β-Hydroxy-11-oxo-18α-olean-12-en-28-säure-methyl­ester und 3,11-Dioxo-18α-olean-12-en-28-säure-methyl­ester

The X-ray crystal structure analyses of 3β-hydroxy-11-oxo-18α-olean-12-en-28-oic acid methyl ester ethanol solvate, C₃₁H₄₈O₄·C₂H₆O, (I), and 3,11-dioxo-18α-olean-12-en-28-oic acid methyl ester, C₃₁H₄₆O₄, (II), are described. These two compounds differ only in the structure of ring A. In (I), ring A has a chair conformation, while in (II), it has a twisted boat conformation. In both compounds, ring C has a slightly distorted sofa conformation, rings B, D and E are in chair conformations, and rings D and E are trans-fused. The asymmetric unit of (I) contains one mol­ecule of ethanol linked by hydrogen bonds with two different mol­ecules of (I).

S1. Comment

Die Synthese der 3β-Hydroxy-11-oxo-18α-olean-12-en-28 - säure-methylester, (I), und 3,11-Dioxo-18α-olean-12-en-28 - säure-methylester (II), wurde von Zaprutko (1995) beschrieben. In dieser Mitteilung wird über die Kristallstrukturen dieser Verbindungen berichtet. \scheme

Beide untersuchten Verbindungen (Abb. 1 und Abb. 2) unterscheiden sich nur durch die Konformation des Ringes A. Die Oxydation der C3-Hydroxylgruppe in (I) zur Ketogruppe bewirkte eine Umwandlung der Sesselform [Verbindung (I)] in die Drehbootform [Verbindung (II)]. Die Ringe C mit der Doppelbindung C12═ C13 [(I) 1,345 (2), (II) 1,342 (2) Å] und C11═O2 α,β ungesättigten Carbonylgruppe [(I) 1,221 (2), (II) 1,223 (2) Å] liegen in beiden Verbindungen in einer nur gering deformierter Sofaform vor [die Cremer & Pople (1975) Parameter für (I): Q = 0.544 (2) Å, θ = 53.7 (2)° und ϕ = 356.2 (2)°; für (II): Q = 0.536 (2) Å, θ = 52.0 (2)° und ϕ = 357.2 (2)°]. Im Vergleich zu den schon von uns untersuchten 2-Oxo- und 3-Oxo-18β-olean-12-en-28 - säure-methylestern (Gzella, 1999c) lä\&st sich bei der Einführung der Ketogruppe in den ungesättigten C Ring der untersuchten 18α-Oleanolsäurederivate (I) und (II) eine Deformierungsverringerung der Sofaform beobachten. Einen Einflu\&s auf die Konformation des Ringes C hat wahrscheinlich auch die trans-Verknüpfung der Ringe D/E [Interplanarwinkel für (I) und (II) 2.52 (11) und 2,57 (10)°].

In beiden Verbindungen sind die Atome C28, C31, O3 und O4 der C17 Estergruppe koplanar. Aus den Torsionswinkeln C18—C17—C28—O3 [(I) 0,7(3) und (II) -1,7(3)°] geht hervor, da\&s die Carbonylgruppe eine synperiplanare Stellung zur C17—C18 Bindung einnimmt. Bei den meisten bis dahin untersuchten 18β-Oleanolsäurederivaten (Gzella, 1999a,b,c; Gzella et al., 1986, 1995, 1997, 1998, 1999; Zaprutko et al., 1990) weist die erwähnte Carbonylgruppe eine Mittellage zwischen synperiplanarer und synklinarer Stellung auf. Ausnahmen bilden zumeist Oleanolsäurederivaten, in denen die C17-Estergruppe an der Bildung einer Wasserstoffbrückenbindung beteiligt ist (Gzella, 1999c; Gzella et al., 1995, 1998). Die Carbonylgruppe nimmt in diesen Fällen eine Mittellage zwischen antiklinarer und antiperiplanarer Stellung ein.

Ähnlich wie es auch bei allen anderen untersuchten Oleanolsäurederivaten der Fall war [Gzella, 1999a,c; Gzella et al., 1986, 1987, 1995) werden auch bei (I) und (II) unabhängig von der Verknüpfungsart der Ringe D und E sterische Absto\&sungen zwischen den axialen Methylgruppen C24, C25 und C26 beobachtet. Davon zeugen die stark deformierten Bindungswinkel C4—C5—C10 und C8—C9—C10 [(I) 116,97 (14) und 117,96 (13), und (II) 114,09 (14) und 118,18 (12)°] und nichtbindenden Atomabstände C24···C25 und C25···C26 [(I) 3,201 (3) und 3,196 (3), und (II) 3,308 (4) und 3,276 (3) Å]. Im nicht deformierten 1,3-Dimethylcykloheksan (beide Methylgruppen in axialer Stellung) betragen die Kohlenstoffatom-Abstände der Methylgruppen 2,52 Å (Spirlet et al., 1980).

Die C3-Hydroxylgruppe in (I) ist β-orientiert.

In der unabhängigen Einheit von (I) befindet sich ein Kristallethanolmolekül. Letzteres beteiligt sich an der Bildung von zwei Wasserstoffbrückenbindungen O5—H5A···O1 und O1ⁱ—H1Aⁱ···O5 [Symmetriebezeichnungen: (i) 1 - x, 1/2 + y, 3 - z; Tabelle 1]. Die oben erwähnten Wasserstoffbrücken binden die Moleküle im Kristallgitter in zickzackförmige Ketten, die in der Richtung [010] anwachsen (Abb. 3). In (I) und (II) wurden nicht-konventionelle C—H···O Wasserstoffbrückenbindungen aufgefunden (Tabelle 1 und 2).

S2. Refinement

Alle H-Atome wurden in (I) und (II) aus Differenz-Fourier-Synthesen ermittelt. Die O1H– und O5H-Atome in (I) wurden frei verfeinert. Die H-Atome der Methylgruppen wurden als starre Gruppen betrachtet. Die übrigen H-Atome in (I) und (II) wurden mit Hilfe des Reitermodells verfeinert; für alle CH-Atome U(H) = 1,2U_äq(c). Bei der Bestimmung der absoluten Konfiguration von (I) bzw. (II) wurden 2236 bzw. 1927 Friedel-Reflexenpaare ausgewertet. Der Ursprung für Verbindung (I) wurde nach der Methode von Flack & Schwarzenbach (1988) festgelegt. Bei der Verbindung (I) weisen die erhöhten Auslenkungsparameter der C31, C32 und C33 Atome [U_äq = 0,1325 (17), 0,160 (2) und 0,190 (3) Ų] in der Estergruppe und im Ethanol-Molekül möglicherweize auf Fehlordnung der erwähnten Atome hin.

Computing details

For both compounds, data collection: KM-4 Software (Kuma Diffraction, 1991); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEPII (Johnson, 1976) und PLUTO (Motherwell & Clegg, 1978) for (I); ORTEPII (Johnson, 1976) for (II). For both compounds, software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Abbildung 1. Molekülstruktur von (I) (Wahrscheinlichkeitsniveau der Ellipsoide 50%)
	Fig. 2. Abbildung 2. Molekülstruktur von (II) (Wahrscheinlichkeitsniveau der Ellipsoide 50%)
	Fig. 3. Abbildung 3. Kristallstruktur von (I) (Die Wasserstoffbrückenbindungen sind durch gestrichelte Linien gekennzeichnet; H-Atome der Klarheit wegen weggelassen)

(I) 3β-Hydroxy-11-oxo-18α-olean-12-en-28-oic acid methyl ester

Crystal data

C31H48O4·C2H6O	F(000) = 584
Mr = 530.76	Dx = 1.177 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
a = 13.425 (3) Å	Cell parameters from 49 reflections
b = 7.4226 (12) Å	θ = 14.8–29.3°
c = 15.0382 (17) Å	µ = 0.60 mm^−1
β = 91.881 (13)°	T = 293 K
V = 1497.7 (4) Å^3	Prism, colourless
Z = 2	0.55 × 0.45 × 0.22 mm

Data collection

Kuma Diffraction KM-4 diffractometer	5073 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 70.1°, θmin = 2.9°
ω/2θ scans	h = −16→16
Absorption correction: ψ-scan (North et al., 1968)	k = −9→9
Tmin = 0.799, Tmax = 0.876	l = 0→18
5417 measured reflections	2 standard reflections every 100 reflections
5319 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.124	Calculated w = 1/[σ^2(Fo^2) + (0.0747P)^2 + 0.2129P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.004
5319 reflections	Δρmax = 0.19 e Å^−3
360 parameters	Δρmin = −0.24 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.1 (2)

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	0.44277 (14)	0.1631 (3)	1.39863 (10)	0.0742 (5)
H1A	0.432 (2)	0.252 (5)	1.4224 (18)	0.070 (8)*
O2	0.19150 (14)	0.4970 (2)	1.04841 (11)	0.0728 (5)
O3	0.24435 (13)	0.2394 (3)	0.71818 (12)	0.0802 (5)
O4	0.24445 (16)	−0.0058 (3)	0.63608 (15)	0.0985 (7)
O5	0.58223 (17)	−0.0263 (3)	1.50069 (15)	0.0930 (7)
H5A	0.539 (2)	0.004 (5)	1.466 (2)	0.094 (10)*
C1	0.27410 (15)	0.3172 (3)	1.20729 (12)	0.0544 (5)
H11	0.2523	0.4373	1.1903	0.065*
H12	0.2154	0.2473	1.2206	0.065*
C2	0.34156 (18)	0.3298 (3)	1.29087 (13)	0.0634 (5)
H21	0.3974	0.4084	1.2793	0.076*
H22	0.3045	0.3828	1.3386	0.076*
C3	0.38046 (16)	0.1476 (3)	1.31998 (13)	0.0562 (5)
H31	0.3229	0.0737	1.3349	0.067*
C4	0.43663 (14)	0.0471 (3)	1.24759 (13)	0.0495 (4)
C5	0.36745 (12)	0.0449 (2)	1.16184 (11)	0.0421 (4)
H51	0.3082	−0.0216	1.1794	0.051*
C6	0.40871 (13)	−0.0659 (3)	1.08636 (13)	0.0495 (4)
H61	0.4377	−0.1763	1.1100	0.059*
H62	0.4608	0.0016	1.0580	0.059*
C7	0.32658 (14)	−0.1113 (2)	1.01793 (13)	0.0474 (4)
H71	0.2766	−0.1845	1.0460	0.057*
H72	0.3546	−0.1822	0.9707	0.057*
C8	0.27607 (12)	0.0569 (2)	0.97723 (11)	0.0394 (3)
C9	0.24646 (12)	0.1870 (2)	1.05320 (11)	0.0389 (3)
H91	0.1939	0.1226	1.0838	0.047*
C10	0.32633 (12)	0.2294 (2)	1.12822 (11)	0.0417 (4)
C11	0.19367 (14)	0.3504 (2)	1.01177 (12)	0.0466 (4)
C12	0.14036 (14)	0.3277 (2)	0.92663 (11)	0.0450 (4)
H121	0.1101	0.4290	0.9013	0.054*
C13	0.13158 (12)	0.1714 (2)	0.88181 (11)	0.0412 (4)
C14	0.17895 (12)	0.0019 (2)	0.92179 (11)	0.0412 (3)
C15	0.20475 (15)	−0.1395 (3)	0.85063 (13)	0.0521 (4)
H151	0.2688	−0.1088	0.8267	0.063*
H152	0.2117	−0.2561	0.8793	0.063*
C16	0.12872 (16)	−0.1558 (3)	0.77401 (14)	0.0555 (5)
H161	0.0671	−0.2042	0.7960	0.067*
H162	0.1533	−0.2394	0.7303	0.067*
C17	0.10764 (14)	0.0264 (3)	0.72932 (12)	0.0498 (4)
C18	0.06434 (13)	0.1547 (3)	0.79922 (11)	0.0461 (4)
H181	0.0040	0.0948	0.8192	0.055*
C19	0.02840 (15)	0.3335 (3)	0.75911 (12)	0.0520 (4)
H191	−0.0046	0.4018	0.8046	0.062*
H192	0.0859	0.4023	0.7415	0.062*
C20	−0.04286 (15)	0.3136 (3)	0.67887 (13)	0.0556 (5)
C21	0.00160 (18)	0.1850 (3)	0.61120 (14)	0.0641 (5)
H211	−0.0471	0.1643	0.5632	0.077*
H212	0.0594	0.2415	0.5859	0.077*
C22	0.03236 (18)	0.0056 (3)	0.65121 (15)	0.0647 (5)
H221	0.0615	−0.0683	0.6056	0.078*
H222	−0.0263	−0.0561	0.6716	0.078*
C23	0.4525 (2)	−0.1479 (3)	1.27914 (16)	0.0689 (6)
H231	0.4981	−0.2074	1.2410	0.083*
H232	0.3899	−0.2104	1.2771	0.083*
H233	0.4795	−0.1478	1.3390	0.083*
C24	0.54005 (15)	0.1286 (4)	1.23413 (15)	0.0651 (6)
H241	0.5659	0.0847	1.1795	0.078*
H242	0.5841	0.0947	1.2829	0.078*
H243	0.5348	0.2575	1.2317	0.078*
C25	0.40647 (15)	0.3605 (3)	1.09604 (13)	0.0543 (4)
H251	0.4589	0.2935	1.0694	0.065*
H252	0.4333	0.4280	1.1457	0.065*
H253	0.3772	0.4416	1.0529	0.065*
C26	0.35078 (13)	0.1497 (3)	0.91583 (12)	0.0499 (4)
H261	0.3274	0.2686	0.9011	0.060*
H262	0.3565	0.0805	0.8623	0.060*
H263	0.4148	0.1576	0.9460	0.060*
C27	0.09767 (14)	−0.0843 (3)	0.97969 (13)	0.0510 (4)
H271	0.1255	−0.1854	1.0117	0.061*
H272	0.0429	−0.1241	0.9420	0.061*
H273	0.0744	0.0033	1.0211	0.061*
C28	0.20531 (16)	0.1030 (3)	0.69509 (13)	0.0588 (5)
C29	−0.14421 (17)	0.2457 (4)	0.70774 (19)	0.0768 (7)
H291	−0.1899	0.2435	0.6573	0.092*
H292	−0.1693	0.3246	0.7524	0.092*
H293	−0.1372	0.1263	0.7317	0.092*
C30	−0.0580 (2)	0.4982 (4)	0.63541 (16)	0.0716 (6)
H301	−0.1041	0.4874	0.5855	0.086*
H302	0.0046	0.5424	0.6155	0.086*
H303	−0.0842	0.5806	0.6779	0.086*
C31	0.3393 (3)	0.0524 (6)	0.6014 (3)	0.1325 (17)
H311	0.3398	0.0293	0.5386	0.159*
H312	0.3927	−0.0127	0.6308	0.159*
H313	0.3480	0.1791	0.6120	0.159*
C32	0.6599 (5)	0.0986 (7)	1.4993 (4)	0.160 (2)
H321	0.6739	0.1386	1.5598	0.192*
H322	0.6368	0.2026	1.4654	0.192*
C33	0.7529 (4)	0.0379 (12)	1.4624 (4)	0.190 (3)
H331	0.8017	0.1322	1.4679	0.228*
H332	0.7419	0.0081	1.4007	0.228*
H333	0.7765	−0.0666	1.4943	0.228*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0897 (12)	0.0769 (12)	0.0551 (8)	0.0272 (10)	−0.0131 (7)	−0.0039 (8)
O2	0.1044 (13)	0.0360 (7)	0.0761 (9)	0.0203 (8)	−0.0268 (8)	−0.0113 (7)
O3	0.0748 (10)	0.0806 (12)	0.0871 (11)	−0.0259 (9)	0.0313 (9)	−0.0176 (9)
O4	0.0981 (13)	0.0827 (12)	0.1184 (15)	−0.0038 (11)	0.0586 (12)	−0.0269 (12)
O5	0.0925 (13)	0.0805 (13)	0.1034 (14)	−0.0060 (11)	−0.0355 (11)	0.0303 (11)
C1	0.0595 (11)	0.0522 (11)	0.0515 (9)	0.0178 (9)	0.0035 (8)	−0.0036 (8)
C2	0.0765 (14)	0.0609 (12)	0.0524 (10)	0.0225 (11)	−0.0030 (9)	−0.0091 (9)
C3	0.0591 (11)	0.0602 (11)	0.0492 (9)	0.0081 (10)	0.0010 (8)	0.0036 (9)
C4	0.0447 (9)	0.0476 (10)	0.0561 (10)	0.0078 (8)	0.0017 (7)	0.0024 (8)
C5	0.0380 (8)	0.0365 (8)	0.0522 (9)	0.0022 (7)	0.0069 (6)	0.0026 (7)
C6	0.0440 (9)	0.0439 (9)	0.0608 (10)	0.0121 (8)	0.0040 (8)	−0.0023 (8)
C7	0.0460 (9)	0.0343 (9)	0.0619 (10)	0.0085 (7)	0.0031 (7)	−0.0048 (7)
C8	0.0360 (7)	0.0322 (8)	0.0505 (8)	0.0002 (6)	0.0092 (6)	−0.0015 (6)
C9	0.0391 (8)	0.0301 (8)	0.0481 (8)	0.0028 (6)	0.0093 (6)	0.0030 (6)
C10	0.0426 (8)	0.0352 (8)	0.0476 (8)	0.0021 (7)	0.0067 (7)	0.0012 (6)
C11	0.0529 (10)	0.0325 (8)	0.0544 (9)	0.0044 (7)	0.0021 (7)	0.0000 (7)
C12	0.0495 (9)	0.0331 (8)	0.0524 (9)	0.0063 (7)	0.0029 (7)	0.0041 (7)
C13	0.0380 (8)	0.0373 (8)	0.0488 (8)	0.0004 (7)	0.0096 (6)	0.0039 (7)
C14	0.0391 (8)	0.0322 (8)	0.0526 (8)	−0.0003 (7)	0.0074 (6)	−0.0005 (7)
C15	0.0536 (10)	0.0356 (9)	0.0671 (11)	0.0034 (8)	0.0014 (8)	−0.0085 (8)
C16	0.0579 (11)	0.0403 (10)	0.0682 (11)	−0.0020 (9)	0.0005 (9)	−0.0104 (8)
C17	0.0506 (10)	0.0441 (10)	0.0549 (9)	−0.0002 (8)	0.0032 (7)	−0.0069 (8)
C18	0.0464 (9)	0.0406 (9)	0.0516 (9)	−0.0018 (8)	0.0053 (7)	−0.0002 (7)
C19	0.0574 (11)	0.0441 (10)	0.0545 (9)	0.0022 (8)	0.0008 (8)	0.0017 (8)
C20	0.0546 (10)	0.0551 (11)	0.0570 (10)	0.0027 (9)	0.0009 (8)	0.0020 (9)
C21	0.0667 (13)	0.0675 (14)	0.0577 (11)	0.0016 (11)	−0.0050 (9)	−0.0052 (10)
C22	0.0692 (13)	0.0583 (12)	0.0661 (12)	0.0013 (11)	−0.0055 (10)	−0.0151 (10)
C23	0.0791 (15)	0.0569 (13)	0.0697 (12)	0.0197 (12)	−0.0112 (11)	0.0072 (10)
C24	0.0444 (10)	0.0794 (16)	0.0711 (12)	0.0021 (10)	−0.0028 (9)	−0.0027 (11)
C25	0.0571 (11)	0.0452 (10)	0.0605 (10)	−0.0143 (9)	−0.0009 (8)	0.0046 (8)
C26	0.0411 (9)	0.0527 (10)	0.0565 (9)	−0.0053 (8)	0.0126 (7)	−0.0018 (8)
C27	0.0443 (9)	0.0432 (9)	0.0659 (11)	−0.0082 (8)	0.0058 (8)	0.0092 (8)
C28	0.0597 (11)	0.0610 (12)	0.0562 (10)	0.0031 (10)	0.0114 (9)	−0.0042 (9)
C29	0.0523 (12)	0.0866 (17)	0.0914 (16)	−0.0026 (12)	0.0013 (11)	0.0055 (14)
C30	0.0819 (15)	0.0661 (14)	0.0660 (12)	0.0060 (12)	−0.0105 (11)	0.0106 (11)
C31	0.112 (3)	0.119 (3)	0.173 (4)	−0.005 (2)	0.093 (3)	−0.028 (3)
C32	0.191 (5)	0.105 (3)	0.178 (4)	−0.041 (3)	−0.098 (4)	0.053 (3)
C33	0.118 (4)	0.265 (9)	0.188 (5)	−0.049 (5)	0.027 (4)	−0.084 (6)

Geometric parameters (Å, º)

O1—C3	1.431 (3)	C9—C11	1.527 (2)
O1—H1A	0.76 (3)	C9—C10	1.563 (2)
O2—C11	1.221 (2)	C10—C25	1.540 (2)
O3—C28	1.186 (3)	C11—C12	1.456 (2)
O4—C28	1.321 (3)	C12—C13	1.345 (2)
O4—C31	1.458 (4)	C13—C18	1.516 (2)
O5—C32	1.396 (5)	C13—C14	1.525 (2)
O5—H5A	0.79 (3)	C14—C15	1.546 (2)
C1—C2	1.528 (3)	C14—C27	1.556 (2)
C1—C10	1.544 (2)	C15—C16	1.519 (3)
C2—C3	1.510 (3)	C16—C17	1.532 (3)
C3—C4	1.538 (3)	C17—C22	1.532 (3)
C4—C24	1.534 (3)	C17—C28	1.534 (3)
C4—C23	1.536 (3)	C17—C18	1.546 (2)
C4—C5	1.564 (2)	C18—C19	1.529 (3)
C5—C6	1.521 (2)	C19—C20	1.522 (3)
C5—C10	1.555 (2)	C20—C29	1.527 (3)
C6—C7	1.521 (3)	C20—C30	1.529 (3)
C7—C8	1.538 (2)	C20—C21	1.531 (3)
C8—C26	1.547 (2)	C21—C22	1.513 (4)
C8—C9	1.557 (2)	C32—C33	1.454 (8)
C8—C14	1.578 (2)
C28—O4—C31	115.5 (2)	C13—C12—C11	124.95 (15)
C2—C1—C10	112.80 (16)	C12—C13—C18	121.40 (16)
C3—C2—C1	111.95 (18)	C12—C13—C14	119.07 (15)
O1—C3—C2	110.81 (19)	C18—C13—C14	119.00 (15)
O1—C3—C4	109.70 (17)	C13—C14—C15	112.79 (14)
C2—C3—C4	113.73 (16)	C13—C14—C27	105.61 (13)
C24—C4—C23	107.19 (18)	C15—C14—C27	106.58 (15)
C24—C4—C3	111.65 (18)	C13—C14—C8	108.74 (13)
C23—C4—C3	107.76 (17)	C15—C14—C8	109.95 (13)
C24—C4—C5	114.25 (15)	C27—C14—C8	113.16 (14)
C23—C4—C5	108.51 (16)	C16—C15—C14	114.75 (15)
C3—C4—C5	107.28 (14)	C15—C16—C17	111.87 (15)
C6—C5—C10	111.57 (14)	C22—C17—C16	110.79 (16)
C6—C5—C4	113.58 (14)	C22—C17—C28	109.27 (17)
C10—C5—C4	116.97 (14)	C16—C17—C28	109.07 (16)
C5—C6—C7	110.56 (14)	C22—C17—C18	109.28 (16)
C6—C7—C8	112.91 (15)	C16—C17—C18	108.27 (15)
C7—C8—C26	108.24 (14)	C28—C17—C18	110.16 (15)
C7—C8—C9	109.35 (13)	C13—C18—C19	115.07 (15)
C26—C8—C9	110.35 (13)	C13—C18—C17	112.35 (15)
C7—C8—C14	110.23 (13)	C19—C18—C17	112.77 (15)
C26—C8—C14	109.91 (14)	C20—C19—C18	114.22 (16)
C9—C8—C14	108.76 (12)	C19—C20—C29	110.44 (17)
C11—C9—C8	108.62 (13)	C19—C20—C30	108.86 (18)
C11—C9—C10	115.64 (14)	C29—C20—C30	108.0 (2)
C8—C9—C10	117.96 (13)	C19—C20—C21	109.81 (17)
C25—C10—C1	108.36 (16)	C29—C20—C21	110.7 (2)
C25—C10—C5	114.48 (14)	C30—C20—C21	108.91 (18)
C1—C10—C5	106.65 (14)	C22—C21—C20	113.06 (18)
C25—C10—C9	111.73 (13)	C21—C22—C17	112.37 (18)
C1—C10—C9	108.83 (14)	O3—C28—O4	122.4 (2)
C5—C10—C9	106.55 (13)	O3—C28—C17	126.32 (18)
O2—C11—C12	118.80 (16)	O4—C28—C17	111.23 (19)
O2—C11—C9	122.78 (16)	O5—C32—C33	116.8 (5)
C12—C11—C9	118.37 (15)
C10—C1—C2—C3	−57.4 (2)	C18—C13—C14—C15	33.9 (2)
C1—C2—C3—O1	−179.60 (17)	C12—C13—C14—C27	89.67 (19)
C1—C2—C3—C4	56.3 (3)	C18—C13—C14—C27	−82.13 (17)
O1—C3—C4—C24	−50.7 (2)	C12—C13—C14—C8	−32.07 (19)
C2—C3—C4—C24	74.0 (2)	C18—C13—C14—C8	156.13 (13)
O1—C3—C4—C23	66.7 (2)	C7—C8—C14—C13	−179.46 (13)
C2—C3—C4—C23	−168.54 (19)	C26—C8—C14—C13	−60.23 (16)
O1—C3—C4—C5	−176.60 (17)	C9—C8—C14—C13	60.68 (15)
C2—C3—C4—C5	−51.9 (2)	C7—C8—C14—C15	−55.51 (17)
C24—C4—C5—C6	61.2 (2)	C26—C8—C14—C15	63.71 (18)
C23—C4—C5—C6	−58.3 (2)	C9—C8—C14—C15	−175.38 (14)
C3—C4—C5—C6	−174.51 (16)	C7—C8—C14—C27	63.53 (18)
C24—C4—C5—C10	−71.1 (2)	C26—C8—C14—C27	−177.24 (15)
C23—C4—C5—C10	169.43 (16)	C9—C8—C14—C27	−56.34 (18)
C3—C4—C5—C10	53.26 (19)	C13—C14—C15—C16	−38.3 (2)
C10—C5—C6—C7	−63.01 (19)	C27—C14—C15—C16	77.14 (19)
C4—C5—C6—C7	162.20 (15)	C8—C14—C15—C16	−159.86 (15)
C5—C6—C7—C8	58.9 (2)	C14—C15—C16—C17	54.1 (2)
C6—C7—C8—C26	70.88 (18)	C15—C16—C17—C22	178.88 (16)
C6—C7—C8—C9	−49.37 (18)	C15—C16—C17—C28	58.6 (2)
C6—C7—C8—C14	−168.88 (14)	C15—C16—C17—C18	−61.3 (2)
C7—C8—C9—C11	−178.30 (14)	C12—C13—C18—C19	13.9 (2)
C26—C8—C9—C11	62.75 (18)	C14—C13—C18—C19	−174.46 (14)
C14—C8—C9—C11	−57.89 (17)	C12—C13—C18—C17	144.82 (16)
C7—C8—C9—C10	47.60 (17)	C14—C13—C18—C17	−43.6 (2)
C26—C8—C9—C10	−71.35 (18)	C22—C17—C18—C13	175.84 (16)
C14—C8—C9—C10	168.02 (13)	C16—C17—C18—C13	55.08 (19)
C2—C1—C10—C25	−69.7 (2)	C28—C17—C18—C13	−64.1 (2)
C2—C1—C10—C5	54.0 (2)	C22—C17—C18—C19	−52.1 (2)
C2—C1—C10—C9	168.61 (16)	C16—C17—C18—C19	−172.89 (15)
C6—C5—C10—C25	−67.73 (19)	C28—C17—C18—C19	67.9 (2)
C4—C5—C10—C25	65.41 (19)	C13—C18—C19—C20	−177.27 (15)
C6—C5—C10—C1	172.44 (15)	C17—C18—C19—C20	52.0 (2)
C4—C5—C10—C1	−54.42 (19)	C18—C19—C20—C29	71.6 (2)
C6—C5—C10—C9	56.31 (17)	C18—C19—C20—C30	−169.91 (18)
C4—C5—C10—C9	−170.55 (13)	C18—C19—C20—C21	−50.8 (2)
C11—C9—C10—C25	−55.83 (18)	C19—C20—C21—C22	53.2 (2)
C8—C9—C10—C25	75.15 (18)	C29—C20—C21—C22	−69.0 (2)
C11—C9—C10—C1	63.79 (18)	C30—C20—C21—C22	172.31 (19)
C8—C9—C10—C1	−165.23 (14)	C20—C21—C22—C17	−57.3 (3)
C11—C9—C10—C5	178.44 (13)	C16—C17—C22—C21	174.17 (18)
C8—C9—C10—C5	−50.57 (17)	C28—C17—C22—C21	−65.6 (2)
C8—C9—C11—O2	−154.91 (19)	C18—C17—C22—C21	55.0 (2)
C10—C9—C11—O2	−19.6 (3)	C31—O4—C28—O3	0.3 (4)
C8—C9—C11—C12	27.7 (2)	C31—O4—C28—C17	−178.2 (3)
C10—C9—C11—C12	162.94 (15)	C22—C17—C28—O3	120.8 (3)
O2—C11—C12—C13	−175.8 (2)	C16—C17—C28—O3	−118.0 (3)
C9—C11—C12—C13	1.7 (3)	C18—C17—C28—O3	0.7 (3)
C11—C12—C13—C18	172.46 (16)	C22—C17—C28—O4	−60.8 (2)
C11—C12—C13—C14	0.9 (3)	C16—C17—C28—O4	60.4 (2)
C12—C13—C14—C15	−154.31 (16)	C18—C17—C28—O4	179.13 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O5^i	0.76 (3)	2.03 (3)	2.785 (3)	172 (3)
O5—H5A···O1	0.79 (3)	2.01 (4)	2.766 (3)	160 (4)
C1—H11···O2	0.97	2.30	2.923 (2)	121
C19—H192···O3	0.97	2.48	3.064 (3)	118
C25—H253···O2	0.96	2.52	3.120 (3)	120
C27—H271···O2^ii	0.96	2.57	3.496 (2)	162

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

(II) 3,11-Dioxo-18α-olean-12-en-28-oic acid methyl ester

Crystal data

C31H46O4	Dx = 1.193 Mg m^−3
Mr = 482.68	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P212121	Cell parameters from 42 reflections
a = 6.6304 (12) Å	θ = 14.8–29.4°
b = 12.886 (2) Å	µ = 0.60 mm^−1
c = 31.442 (5) Å	T = 293 K
V = 2686.4 (8) Å^3	Prism, colourless
Z = 4	0.55 × 0.25 × 0.23 mm
F(000) = 1056

Data collection

Kuma Diffraction KM-4 diffractometer	Rint = 0.015
Radiation source: fine-focus sealed tube	θmax = 70.2°, θmin = 2.8°
Graphite monochromator	h = −8→8
ω/2θ scans	k = 0→15
5157 measured reflections	l = 0→38
4878 independent reflections	2 standard reflections every 100 reflections
4389 reflections with I > 2σ(I)	intensity decay: 3.6%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.036	Calculated w = 1/[σ^2(Fo^2) + (0.0628P)^2 + 0.326P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.105	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.21 e Å^−3
4878 reflections	Δρmin = −0.14 e Å^−3
325 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00075 (17)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.1 (2)

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	0.8013 (3)	0.41491 (13)	0.41236 (5)	0.0859 (5)
O2	0.9677 (3)	0.56163 (13)	0.23755 (4)	0.0712 (4)
O3	0.9649 (2)	0.28951 (12)	0.10493 (5)	0.0637 (4)
O4	0.7588 (2)	0.18856 (11)	0.06742 (5)	0.0678 (4)
C1	0.7352 (4)	0.52677 (13)	0.31456 (6)	0.0581 (5)
H1A	0.8693	0.5568	0.3150	0.070*
H1B	0.6496	0.5727	0.2981	0.070*
C2	0.6556 (4)	0.52283 (14)	0.35989 (6)	0.0617 (5)
H2A	0.7173	0.5781	0.3763	0.074*
H2B	0.5111	0.5346	0.3596	0.074*
C3	0.6980 (4)	0.42182 (15)	0.38078 (5)	0.0575 (5)
C4	0.6021 (3)	0.32854 (14)	0.35944 (5)	0.0539 (5)
C5	0.5777 (3)	0.35027 (12)	0.31074 (5)	0.0441 (4)
H5A	0.4529	0.3905	0.3081	0.053*
C6	0.5429 (4)	0.25242 (13)	0.28490 (6)	0.0555 (5)
H6A	0.4389	0.2108	0.2983	0.067*
H6B	0.6660	0.2117	0.2842	0.067*
C7	0.4792 (3)	0.27923 (14)	0.23975 (5)	0.0529 (4)
H7A	0.3539	0.3180	0.2407	0.063*
H7B	0.4541	0.2155	0.2242	0.063*
C8	0.6375 (2)	0.34312 (11)	0.21582 (5)	0.0377 (3)
C9	0.6942 (2)	0.43867 (11)	0.24354 (5)	0.0372 (3)
H9A	0.5706	0.4804	0.2442	0.045*
C10	0.7456 (3)	0.42010 (11)	0.29164 (5)	0.0414 (4)
C11	0.8444 (3)	0.50624 (13)	0.21962 (5)	0.0448 (4)
C12	0.8350 (3)	0.50674 (12)	0.17321 (5)	0.0429 (4)
H12A	0.9258	0.5491	0.1588	0.052*
C13	0.7055 (2)	0.45080 (11)	0.14976 (5)	0.0377 (3)
C14	0.5468 (2)	0.38370 (11)	0.17223 (5)	0.0367 (3)
C15	0.4765 (2)	0.29150 (12)	0.14452 (5)	0.0435 (4)
H15A	0.5736	0.2356	0.1474	0.052*
H15B	0.3486	0.2666	0.1555	0.052*
C16	0.4514 (3)	0.31633 (14)	0.09755 (5)	0.0454 (4)
H16A	0.3443	0.3668	0.0940	0.054*
H16B	0.4135	0.2539	0.0823	0.054*
C17	0.6474 (3)	0.35957 (12)	0.07893 (5)	0.0425 (4)
C18	0.6951 (3)	0.46250 (12)	0.10185 (5)	0.0414 (3)
H18A	0.5774	0.5067	0.0967	0.050*
C19	0.8726 (3)	0.52106 (14)	0.08212 (5)	0.0511 (4)
H19A	0.9957	0.4831	0.0881	0.061*
H19B	0.8836	0.5884	0.0957	0.061*
C20	0.8553 (3)	0.53716 (15)	0.03368 (5)	0.0541 (4)
C21	0.8078 (3)	0.43358 (16)	0.01237 (6)	0.0551 (4)
H21A	0.7855	0.4453	−0.0177	0.066*
H21B	0.9236	0.3881	0.0152	0.066*
C22	0.6245 (3)	0.37993 (15)	0.03087 (5)	0.0520 (4)
H22A	0.6038	0.3144	0.0163	0.062*
H22B	0.5063	0.4227	0.0261	0.062*
C23	0.3904 (4)	0.3183 (2)	0.37950 (7)	0.0851 (8)
H23A	0.3202	0.2613	0.3666	0.102*
H23B	0.3160	0.3812	0.3749	0.102*
H23C	0.4035	0.3060	0.4095	0.102*
C24	0.7237 (5)	0.23041 (16)	0.37015 (7)	0.0837 (8)
H24A	0.6522	0.1703	0.3602	0.100*
H24B	0.7416	0.2257	0.4004	0.100*
H24C	0.8531	0.2339	0.3566	0.100*
C25	0.9578 (3)	0.37532 (18)	0.29871 (6)	0.0610 (5)
H25A	1.0527	0.4117	0.2811	0.073*
H25B	0.9583	0.3030	0.2914	0.073*
H25C	0.9949	0.3833	0.3280	0.073*
C26	0.8248 (3)	0.27475 (13)	0.20723 (6)	0.0518 (4)
H26A	0.9268	0.3155	0.1934	0.062*
H26B	0.7877	0.2177	0.1893	0.062*
H26C	0.8762	0.2487	0.2337	0.062*
C27	0.3604 (3)	0.45414 (14)	0.17798 (6)	0.0469 (4)
H27A	0.2578	0.4171	0.1933	0.056*
H27B	0.3096	0.4741	0.1506	0.056*
H27C	0.3980	0.5151	0.1937	0.056*
C28	0.8107 (3)	0.27883 (14)	0.08543 (5)	0.0469 (4)
C29	0.6951 (4)	0.61799 (17)	0.02306 (6)	0.0720 (6)
H29A	0.7307	0.6830	0.0359	0.086*
H29B	0.5669	0.5955	0.0338	0.086*
H29C	0.6870	0.6264	−0.0072	0.086*
C30	1.0597 (4)	0.5766 (2)	0.01722 (7)	0.0774 (7)
H30A	1.0949	0.6395	0.0318	0.093*
H30B	1.0505	0.5898	−0.0128	0.093*
H30C	1.1613	0.5250	0.0224	0.093*
C31	0.8940 (4)	0.10278 (18)	0.07455 (9)	0.0818 (7)
H31A	0.8469	0.0431	0.0592	0.098*
H31B	0.8986	0.0871	0.1044	0.098*
H31C	1.0267	0.1210	0.0648	0.098*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.1324 (15)	0.0761 (10)	0.0491 (8)	−0.0144 (10)	−0.0317 (9)	0.0082 (7)
O2	0.0839 (10)	0.0821 (10)	0.0478 (7)	−0.0471 (9)	−0.0049 (7)	−0.0051 (6)
O3	0.0453 (7)	0.0741 (9)	0.0718 (9)	0.0084 (7)	−0.0109 (7)	−0.0030 (7)
O4	0.0708 (9)	0.0542 (7)	0.0785 (9)	0.0097 (7)	−0.0096 (7)	−0.0162 (7)
C1	0.0952 (15)	0.0383 (8)	0.0409 (8)	−0.0063 (9)	−0.0068 (9)	−0.0012 (7)
C2	0.0939 (16)	0.0456 (9)	0.0457 (9)	0.0053 (10)	−0.0019 (10)	−0.0054 (7)
C3	0.0823 (14)	0.0544 (10)	0.0359 (8)	−0.0017 (10)	−0.0008 (9)	0.0019 (7)
C4	0.0754 (13)	0.0465 (9)	0.0396 (8)	−0.0040 (9)	−0.0047 (8)	0.0077 (7)
C5	0.0564 (10)	0.0378 (7)	0.0381 (8)	−0.0011 (7)	−0.0026 (7)	0.0049 (6)
C6	0.0794 (13)	0.0405 (8)	0.0466 (9)	−0.0150 (9)	−0.0019 (9)	0.0056 (7)
C7	0.0684 (12)	0.0456 (9)	0.0446 (9)	−0.0224 (9)	−0.0031 (9)	0.0011 (7)
C8	0.0426 (8)	0.0322 (7)	0.0383 (7)	−0.0021 (6)	−0.0031 (7)	−0.0009 (6)
C9	0.0404 (8)	0.0336 (7)	0.0377 (7)	−0.0016 (6)	−0.0024 (6)	−0.0012 (6)
C10	0.0493 (9)	0.0367 (7)	0.0383 (8)	−0.0016 (7)	−0.0053 (7)	−0.0001 (6)
C11	0.0498 (9)	0.0435 (8)	0.0411 (8)	−0.0113 (7)	−0.0033 (7)	−0.0022 (6)
C12	0.0437 (9)	0.0447 (8)	0.0404 (8)	−0.0117 (7)	0.0014 (7)	0.0026 (6)
C13	0.0376 (7)	0.0364 (7)	0.0389 (7)	−0.0007 (6)	−0.0002 (7)	0.0002 (6)
C14	0.0346 (7)	0.0365 (7)	0.0392 (8)	−0.0030 (6)	−0.0010 (6)	−0.0007 (6)
C15	0.0411 (8)	0.0437 (8)	0.0455 (8)	−0.0093 (7)	−0.0022 (7)	−0.0024 (7)
C16	0.0386 (8)	0.0520 (9)	0.0456 (9)	−0.0072 (7)	−0.0062 (7)	−0.0058 (7)
C17	0.0412 (8)	0.0481 (9)	0.0382 (8)	−0.0038 (7)	−0.0054 (7)	−0.0024 (6)
C18	0.0415 (8)	0.0450 (8)	0.0376 (7)	−0.0027 (7)	−0.0018 (7)	0.0013 (6)
C19	0.0541 (10)	0.0581 (10)	0.0412 (9)	−0.0141 (8)	−0.0004 (8)	0.0022 (7)
C20	0.0627 (11)	0.0628 (11)	0.0369 (8)	−0.0080 (9)	0.0026 (8)	0.0041 (7)
C21	0.0606 (11)	0.0651 (11)	0.0395 (8)	0.0010 (9)	0.0018 (8)	−0.0013 (8)
C22	0.0550 (10)	0.0598 (10)	0.0411 (8)	−0.0024 (9)	−0.0085 (8)	−0.0021 (8)
C23	0.0986 (18)	0.1059 (18)	0.0508 (11)	−0.0312 (16)	0.0061 (12)	0.0158 (12)
C24	0.143 (2)	0.0498 (10)	0.0583 (12)	0.0101 (14)	−0.0243 (14)	0.0149 (9)
C25	0.0535 (11)	0.0773 (13)	0.0521 (10)	0.0043 (10)	−0.0137 (9)	0.0007 (9)
C26	0.0616 (11)	0.0441 (8)	0.0496 (9)	0.0147 (8)	−0.0072 (8)	−0.0023 (7)
C27	0.0399 (8)	0.0525 (9)	0.0484 (9)	0.0047 (7)	−0.0010 (7)	0.0015 (7)
C28	0.0451 (9)	0.0539 (9)	0.0416 (8)	−0.0006 (8)	0.0019 (8)	−0.0019 (7)
C29	0.1019 (18)	0.0662 (12)	0.0478 (10)	0.0120 (13)	0.0020 (12)	0.0079 (9)
C30	0.0833 (16)	0.0939 (16)	0.0551 (11)	−0.0257 (14)	0.0154 (12)	0.0035 (11)
C31	0.1003 (19)	0.0620 (12)	0.0831 (15)	0.0249 (13)	0.0101 (14)	−0.0048 (11)

Geometric parameters (Å, º)

O1—C3	1.209 (3)	C9—C10	1.569 (2)
O2—C11	1.223 (2)	C10—C25	1.537 (3)
O3—C28	1.200 (2)	C11—C12	1.461 (2)
O4—C28	1.339 (2)	C12—C13	1.342 (2)
O4—C31	1.441 (3)	C13—C18	1.516 (2)
C1—C2	1.521 (3)	C13—C14	1.534 (2)
C1—C10	1.554 (2)	C14—C27	1.544 (2)
C2—C3	1.485 (3)	C14—C15	1.545 (2)
C3—C4	1.516 (3)	C15—C16	1.520 (2)
C4—C24	1.537 (3)	C16—C17	1.530 (2)
C4—C23	1.544 (3)	C17—C28	1.515 (2)
C4—C5	1.565 (2)	C17—C22	1.541 (2)
C5—C6	1.518 (2)	C17—C18	1.542 (2)
C5—C10	1.552 (2)	C18—C19	1.529 (2)
C6—C7	1.521 (3)	C19—C20	1.541 (2)
C7—C8	1.531 (2)	C20—C29	1.524 (3)
C8—C26	1.547 (2)	C20—C21	1.526 (3)
C8—C9	1.5547 (19)	C20—C30	1.537 (3)
C8—C14	1.585 (2)	C21—C22	1.514 (3)
C9—C11	1.522 (2)
C28—O4—C31	116.15 (17)	C12—C11—C9	117.93 (13)
C2—C1—C10	114.88 (14)	C13—C12—C11	125.02 (14)
C3—C2—C1	112.22 (16)	C12—C13—C18	121.45 (14)
O1—C3—C2	122.34 (19)	C12—C13—C14	119.25 (14)
O1—C3—C4	122.84 (17)	C18—C13—C14	118.87 (13)
C2—C3—C4	114.82 (16)	C13—C14—C27	105.75 (12)
C3—C4—C24	109.59 (18)	C13—C14—C15	112.37 (12)
C3—C4—C23	105.55 (18)	C27—C14—C15	106.04 (13)
C24—C4—C23	108.5 (2)	C13—C14—C8	108.92 (12)
C3—C4—C5	109.54 (14)	C27—C14—C8	113.34 (12)
C24—C4—C5	114.57 (16)	C15—C14—C8	110.38 (12)
C23—C4—C5	108.73 (16)	C16—C15—C14	114.77 (13)
C6—C5—C10	112.55 (14)	C15—C16—C17	110.82 (13)
C6—C5—C4	113.01 (13)	C28—C17—C16	107.76 (13)
C10—C5—C4	114.09 (14)	C28—C17—C22	108.64 (14)
C5—C6—C7	110.68 (13)	C16—C17—C22	110.69 (14)
C6—C7—C8	112.96 (15)	C28—C17—C18	112.38 (13)
C7—C8—C26	109.27 (14)	C16—C17—C18	107.97 (13)
C7—C8—C9	108.43 (13)	C22—C17—C18	109.39 (13)
C26—C8—C9	110.78 (13)	C13—C18—C19	114.67 (13)
C7—C8—C14	110.02 (13)	C13—C18—C17	112.85 (13)
C26—C8—C14	109.96 (12)	C19—C18—C17	113.12 (14)
C9—C8—C14	108.37 (11)	C18—C19—C20	114.21 (15)
C11—C9—C8	109.53 (12)	C29—C20—C21	110.96 (17)
C11—C9—C10	114.92 (13)	C29—C20—C30	108.33 (18)
C8—C9—C10	118.18 (12)	C21—C20—C30	108.85 (18)
C25—C10—C5	112.51 (14)	C29—C20—C19	111.12 (16)
C25—C10—C1	107.81 (15)	C21—C20—C19	109.36 (15)
C5—C10—C1	107.54 (14)	C30—C20—C19	108.15 (17)
C25—C10—C9	113.33 (14)	C22—C21—C20	113.33 (16)
C5—C10—C9	107.78 (13)	C21—C22—C17	112.04 (15)
C1—C10—C9	107.61 (12)	O3—C28—O4	122.33 (17)
O2—C11—C12	119.11 (15)	O3—C28—C17	126.78 (16)
O2—C11—C9	122.93 (14)	O4—C28—C17	110.84 (14)
C10—C1—C2—C3	28.5 (3)	C18—C13—C14—C27	−82.53 (16)
C1—C2—C3—O1	118.5 (2)	C12—C13—C14—C15	−154.78 (15)
C1—C2—C3—C4	−61.5 (3)	C18—C13—C14—C15	32.71 (19)
O1—C3—C4—C24	−24.7 (3)	C12—C13—C14—C8	−32.16 (19)
C2—C3—C4—C24	155.3 (2)	C18—C13—C14—C8	155.34 (13)
O1—C3—C4—C23	91.9 (3)	C7—C8—C14—C13	177.85 (13)
C2—C3—C4—C23	−88.1 (2)	C26—C8—C14—C13	−61.76 (15)
O1—C3—C4—C5	−151.2 (2)	C9—C8—C14—C13	59.46 (15)
C2—C3—C4—C5	28.8 (3)	C7—C8—C14—C27	60.44 (16)
C3—C4—C5—C6	162.76 (18)	C26—C8—C14—C27	−179.16 (14)
C24—C4—C5—C6	39.2 (3)	C9—C8—C14—C27	−57.95 (16)
C23—C4—C5—C6	−82.4 (2)	C7—C8—C14—C15	−58.33 (17)
C3—C4—C5—C10	32.5 (2)	C26—C8—C14—C15	62.06 (16)
C24—C4—C5—C10	−91.1 (2)	C9—C8—C14—C15	−176.72 (13)
C23—C4—C5—C10	147.38 (17)	C13—C14—C15—C16	−39.22 (19)
C10—C5—C6—C7	−60.2 (2)	C27—C14—C15—C16	75.84 (17)
C4—C5—C6—C7	168.73 (17)	C8—C14—C15—C16	−161.02 (13)
C5—C6—C7—C8	60.4 (2)	C14—C15—C16—C17	56.42 (19)
C6—C7—C8—C26	68.51 (19)	C15—C16—C17—C28	58.72 (17)
C6—C7—C8—C9	−52.32 (19)	C15—C16—C17—C22	177.40 (14)
C6—C7—C8—C14	−170.68 (14)	C15—C16—C17—C18	−62.89 (17)
C7—C8—C9—C11	−177.45 (14)	C12—C13—C18—C19	14.0 (2)
C26—C8—C9—C11	62.66 (16)	C14—C13—C18—C19	−173.71 (14)
C14—C8—C9—C11	−58.05 (16)	C12—C13—C18—C17	145.44 (16)
C7—C8—C9—C10	48.35 (19)	C14—C13—C18—C17	−42.23 (19)
C26—C8—C9—C10	−71.55 (17)	C28—C17—C18—C13	−63.31 (18)
C14—C8—C9—C10	167.74 (13)	C16—C17—C18—C13	55.40 (17)
C6—C5—C10—C25	−73.51 (19)	C22—C17—C18—C13	175.93 (14)
C4—C5—C10—C25	56.97 (19)	C28—C17—C18—C19	68.94 (17)
C6—C5—C10—C1	167.91 (15)	C16—C17—C18—C19	−172.35 (14)
C4—C5—C10—C1	−61.60 (18)	C22—C17—C18—C19	−51.82 (19)
C6—C5—C10—C9	52.16 (18)	C13—C18—C19—C20	−177.16 (15)
C4—C5—C10—C9	−177.36 (13)	C17—C18—C19—C20	51.5 (2)
C2—C1—C10—C25	−92.7 (2)	C18—C19—C20—C29	72.4 (2)
C2—C1—C10—C5	28.9 (2)	C18—C19—C20—C21	−50.4 (2)
C2—C1—C10—C9	144.73 (17)	C18—C19—C20—C30	−168.83 (18)
C11—C9—C10—C25	−54.82 (18)	C29—C20—C21—C22	−69.2 (2)
C8—C9—C10—C25	77.02 (18)	C30—C20—C21—C22	171.67 (17)
C11—C9—C10—C5	179.99 (13)	C19—C20—C21—C22	53.7 (2)
C8—C9—C10—C5	−48.16 (18)	C20—C21—C22—C17	−58.0 (2)
C11—C9—C10—C1	64.28 (18)	C28—C17—C22—C21	−68.07 (19)
C8—C9—C10—C1	−163.88 (15)	C16—C17—C22—C21	173.79 (15)
C8—C9—C11—O2	−152.33 (18)	C18—C17—C22—C21	54.9 (2)
C10—C9—C11—O2	−16.5 (2)	C31—O4—C28—O3	3.0 (3)
C8—C9—C11—C12	29.7 (2)	C31—O4—C28—C17	−174.83 (17)
C10—C9—C11—C12	165.51 (14)	C16—C17—C28—O3	−120.50 (19)
O2—C11—C12—C13	−179.13 (18)	C22—C17—C28—O3	119.5 (2)
C9—C11—C12—C13	−1.1 (3)	C18—C17—C28—O3	−1.7 (2)
C11—C12—C13—C18	175.06 (16)	C16—C17—C28—O4	57.26 (18)
C11—C12—C13—C14	2.8 (3)	C22—C17—C28—O4	−62.72 (19)
C12—C13—C14—C27	89.97 (17)	C18—C17—C28—O4	176.10 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19A···O3	0.97	2.56	3.129 (2)	118
C25—H25A···O2	0.96	2.43	3.077 (3)	124
C29—H29C···O1^i	0.96	2.58	3.506 (2)	161

Symmetry code: (i) −x+3/2, −y+1, z−1/2.