Oleana-12(13),15(16)-diene-3[alpha],28-diyl di­acetate

The title compound, C₃₄H₅₂O₄, consists of five six-membered rings. Barring the two rings, with double bonds, all other rings are in chair conformations. Mean-plane and ring-puckering calculations indicate these two rings to be in distorted-chair conformations, with distortion towards the boat conformation. There are no strong hydrogen bonds and the structure is stabilized by van der Waals interactions only. The structure is compared with those reported for other triterpenes.

S1. Comment

The title compound, (I), has been isolated from the leaves of the plant Jacquinia Ruscifolia which is found in Mexico. Air-dried crushed leaves of the plant was extracted with petroleum ether (333–353 K), chloroform and methanol successively. The methanol extract in turn was refluxed with 6% methanolic hydrochloric acid (250 ml) for 6 h. The solvent was removed under reduced pressure, water being added during distillation to keep the acid concentration constant. The resulting mixture was extracted with a large volume of ether. The ethereal solution in turn was extracted with a saturated solution of sodium bicarbonate. The neutral fraction was washed thoroughly with water, dried and chromatographed over silica gel repeatedly. Benzene–ether (1:1) eluate afforded a white solid, crystallized from methanol. The diol was then acetylated by heating it with pyridine and acetic anhydride over water bath for 2 h. Usual work up, followed by crystallization from methanol resulted in oleana-12 (13),15 (16)-diene-3α,28 diol diacetate (Dutta, 1972; Rao & Bose, 1962).

Several studies have been made on this class of triterpenes. The structure elucidation by X-ray method of several triterpenes such as Acide acetoxy-3β e oleanane-12 (13)oique-28α (Roques et al., 1978), triterpene gymnemagenin (Hoge & Nordman, 1974), 18-α(H)-oleanane (Fowell et al., 1978) and (+)oleanolic acid (van Schalkwyk & Kruger, 1974) has also been done. By convention the stereochemistry of this class of compounds is 3β-OAc,8β-Me,10β-Me,14α-Me,17β-COOMe. In the case of the present compound, we have obtained opposite chirality. However the crystallographic study does not provide an unambiguous determination of the absolute configuration. In our previous work on Oleana-13 (18),15 (16)-diene-3beta, 28 diol diacetate (Bhattacharyya et al., 1999), we reported the conventional structure.

In the case of the present compound, except for the two rings with double bonds, all other rings are in chair conformation. The acetate group at C3 is almost planar with a tortion angle C32—C31—O1—C3 = 175°. The atom O1, attached to the atom C3 is lying below the least-squares plane defined by the atoms C2, C3, C5 and C10 of the ring A. The torsion angle is C2—C3—O1—C31 = −113.9 (3)°. The acetate group at C17, is almost planar, with mean deviation from the least-squares plane defined by the constituent atoms is 0.0274 Å, and C34 atom has the maximum out of plane deviation of 0.0337 Å This acetate group is equatorial to ring E (torsion angle, O3—C28—C17—C16 = −180°) and twisted from the plane of the ring D [torsion angle O3—C28—C17—C22 = −60.4 (3)°]. The mean Csp³—Csp³ bond length is 1.533 (3) Å with C8—C14 different with a value of 1.600 Å. As in the previous compound (Bhattacharyya et al., 1999), this is attributed to the steric effects as these two bonded Csp³ atoms have no attached H atoms.

Mean-plane calculations show similar behavior for the rings C and D containing double bonds. C9, C11, C13, C14 atoms of ring C define a least-squares plane, whose mean deviation from planarity is only 0.006 Å. The atom C8 is 0.7604 Å below this plane and C12 is 0.0262 Å above the plane. However the puckering parameter, ϕ = 178.2 (3)° which indicates distortion is towards boat. Similarly for the ring D, atoms C13, C14, C16, C17 define a least squares plane with mean deviation of 0.0006°. The atom C15 is 0.0205 Å below this plane, where as atom C18 is 0.6199° above the plane. Hence this ring is also a distorted chair and the distortion is towards boat as its puckering parameter ϕ is 59.6 (4)°. The puckering parameters of all the six-membered rings A, B, C, D and E have been calculated using the method of Cremer & Pople (1975), using the program PARST (Nardelli, 1983). The puckering parameters are given in Table 4. There are no hydrogen bonds and the structure is stabilized by van der Waals interaction.

S2. Experimental

The crystals of the title compound were obtained from a solution of the compound in methanol by slow evaporation at room temperature.

S3. Refinement

All the H atoms were included at geometrically calculated positions. For the methyl groups attached to sp³ centres (i.e. for C23, C24, C25, C26, C27, C29 and C30), H atoms are placed in a unique staggered conformation For methyl groups on sp² centres, i.e. for C32 and C34 atoms, H atoms were located from a circular Fourier synthesis. They were then allowed to ride on their parent atom with U_iso = xU_eq (parent), where x = 1.5 for methyl H atoms and x = 1.2 for all other atoms.

Computing details

Data collection: Local Program (Belletti, 1993); cell refinement: Local Program (Belletti, 1993); data reduction: Local Program (Belletti, 1993); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); software used to prepare material for publication: SHELXL93 (Sheldrick, 1993).

Oleana-12 (13), 15 (16)-diene-3α, 28 diol diacetate

Crystal data

C34H52O4	Dx = 1.150 Mg m^−3
Mr = 524.76	Melting point: 210° K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
a = 16.645 (2) Å	Cell parameters from 49 reflections
b = 25.768 (2) Å	θ = 12.3–40.8°
c = 7.066 (3) Å	µ = 0.57 mm^−1
V = 3030.7 (14) Å^3	T = 293 K
Z = 4	Needle, colourless
F(000) = 1152	0.4 × 0.3 × 0.1 mm

Data collection

Siemens AED diffractometer	2929 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	θmax = 70.0°, θmin = 3.2°
Graphite monochromator	h = −19→20
ω–θ scans	k = −30→31
Absorption correction: ψ scan (North et al., 1968)	l = −8→1
Tmin = 0.94, Tmax = 0.97	2 standard reflections every 100 reflections
3292 measured reflections	intensity decay: none
3292 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: geom & circular Difference Map
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.046	Calculated w = 1/[σ^2(Fo^2) + (0.1016P)^2 + 0.1981P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.137	(Δ/σ)max = −0.014
S = 1.12	Δρmax = 0.19 e Å^−3
3292 reflections	Δρmin = −0.21 e Å^−3
347 parameters	Extinction correction: SHELXL93, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0057 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.39 (36)

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 on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs 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
C1	0.16372 (14)	0.07638 (10)	−0.0721 (3)	0.0446 (5)
H11	0.18568	0.10420	−0.1488	0.053*
H12	0.19215	0.04476	−0.1046	0.053*
C2	0.07486 (14)	0.06966 (10)	−0.1204 (4)	0.0504 (6)
H21	0.06878	0.06353	−0.2551	0.060*
H22	0.05329	0.03993	−0.0532	0.060*
C3	0.02932 (14)	0.11820 (10)	−0.0643 (4)	0.0486 (6)
H3	0.05098	0.14757	−0.1362	0.058*
C4	0.03352 (14)	0.13127 (9)	0.1469 (4)	0.0454 (5)
C5	0.12459 (13)	0.13529 (8)	0.1948 (3)	0.0396 (5)
H5	0.14409	0.16433	0.1179	0.048*
C6	0.14221 (14)	0.15139 (10)	0.3992 (4)	0.0472 (5)
H61	0.10515	0.17847	0.4376	0.057*
H62	0.13470	0.12189	0.4827	0.057*
C7	0.22851 (14)	0.17117 (9)	0.4155 (4)	0.0477 (6)
H71	0.23915	0.17978	0.5468	0.057*
H72	0.23342	0.20285	0.3423	0.057*
C8	0.29297 (13)	0.13240 (8)	0.3473 (3)	0.0374 (4)
C9	0.26807 (12)	0.10835 (8)	0.1552 (3)	0.0356 (4)
H9	0.27223	0.13693	0.0643	0.043*
C10	0.17872 (12)	0.08877 (8)	0.1376 (3)	0.0362 (4)
C11	0.33042 (13)	0.06834 (9)	0.0886 (4)	0.0439 (5)
H111	0.31665	0.03480	0.1418	0.053*
H112	0.32714	0.06539	−0.0480	0.053*
C12	0.41553 (13)	0.08103 (8)	0.1419 (3)	0.0409 (5)
H121	0.45551	0.05875	0.0988	0.049*
C13	0.43847 (12)	0.12148 (8)	0.2455 (3)	0.0378 (4)
C14	0.37722 (13)	0.16097 (8)	0.3153 (3)	0.0407 (5)
C15	0.40621 (15)	0.18537 (9)	0.4970 (4)	0.0496 (6)
H15	0.37249	0.20940	0.5548	0.059*
C16	0.47562 (15)	0.17545 (9)	0.5811 (4)	0.0498 (6)
H16	0.48767	0.19394	0.6905	0.060*
C17	0.53690 (14)	0.13625 (9)	0.5125 (3)	0.0436 (5)
C18	0.52674 (13)	0.12937 (9)	0.2951 (3)	0.0409 (5)
H18	0.55565	0.09780	0.2585	0.049*
C19	0.56375 (14)	0.17482 (9)	0.1847 (4)	0.0481 (5)
H191	0.56014	0.16726	0.0505	0.058*
H192	0.53200	0.20570	0.2087	0.058*
C20	0.6517 (2)	0.18660 (10)	0.2335 (4)	0.0514 (6)
C21	0.6547 (2)	0.19803 (10)	0.4456 (4)	0.0545 (6)
H211	0.7098	0.20509	0.4820	0.065*
H212	0.6232	0.22889	0.4717	0.065*
C22	0.62281 (15)	0.15345 (10)	0.5638 (4)	0.0505 (6)
H221	0.62380	0.16361	0.6959	0.061*
H222	0.65858	0.12399	0.5493	0.061*
C23	−0.0054 (2)	0.18526 (11)	0.1746 (5)	0.0614 (7)
H231	0.0230	0.21048	0.1002	0.092*
H232	−0.0029	0.19479	0.3058	0.092*
H233	−0.0606	0.18400	0.1348	0.092*
C24	−0.01325 (14)	0.09234 (11)	0.2672 (4)	0.0548 (6)
H241	−0.00918	0.10182	0.3982	0.082*
H242	0.00873	0.05825	0.2493	0.082*
H243	−0.06867	0.09249	0.2296	0.082*
C25	0.16186 (14)	0.03893 (8)	0.2519 (4)	0.0447 (5)
H251	0.17077	0.04552	0.3840	0.067*
H252	0.19720	0.01181	0.2101	0.067*
H253	0.10712	0.02844	0.2328	0.067*
C26	0.30340 (14)	0.09098 (10)	0.5022 (3)	0.0465 (5)
H261	0.34330	0.06630	0.4632	0.070*
H262	0.25321	0.07347	0.5224	0.070*
H263	0.32019	0.10732	0.6177	0.070*
C27	0.36958 (15)	0.20543 (9)	0.1656 (4)	0.0536 (6)
H271	0.35119	0.19122	0.0477	0.080*
H272	0.42105	0.22149	0.1475	0.080*
H273	0.33182	0.23085	0.2097	0.080*
C28	0.51880 (15)	0.08502 (10)	0.6170 (4)	0.0533 (6)
H281	0.52275	0.09050	0.7525	0.064*
H282	0.46443	0.07396	0.5885	0.064*
C29	0.7068 (2)	0.14118 (13)	0.1812 (6)	0.0678 (8)
H291	0.7037	0.13493	0.0475	0.102*
H292	0.6901	0.11065	0.2483	0.102*
H293	0.7612	0.14951	0.2150	0.102*
C30	0.6779 (2)	0.23517 (14)	0.1248 (6)	0.0810 (10)
H301	0.6761	0.22828	−0.0087	0.121*
H302	0.7316	0.24435	0.1607	0.121*
H303	0.6422	0.26332	0.1541	0.121*
C31	−0.0834 (2)	0.1411 (2)	−0.2569 (4)	0.0677 (8)
C32	−0.1671 (2)	0.1253 (3)	−0.3093 (7)	0.115 (2)
H321	−0.1980 (8)	0.1198 (16)	−0.1964 (7)	0.173*
H322	−0.1653 (3)	0.0937 (10)	−0.382 (5)	0.173*
H323	−0.1916 (9)	0.1522 (8)	−0.384 (5)	0.173*
C33	0.6281 (2)	0.02702 (12)	0.6849 (6)	0.0684 (8)
C34	0.6841 (2)	−0.00991 (14)	0.5992 (8)	0.0949 (13)
H341	0.7266 (11)	0.00869 (14)	0.537 (4)	0.142*
H342	0.6561 (5)	−0.0308 (9)	0.508 (4)	0.142*
H343	0.7063 (15)	−0.0318 (9)	0.6958 (10)	0.142*
O1	−0.05451 (11)	0.11039 (9)	−0.1199 (3)	0.0639 (5)
O2	−0.0470 (2)	0.17556 (11)	−0.3291 (4)	0.0874 (8)
O3	0.57489 (11)	0.04500 (7)	0.5600 (3)	0.0588 (5)
O4	0.6297 (2)	0.04027 (14)	0.8470 (5)	0.1138 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0374 (10)	0.0525 (12)	0.0438 (11)	−0.0002 (9)	−0.0012 (9)	−0.0056 (10)
C2	0.0403 (11)	0.0622 (14)	0.0487 (12)	−0.0029 (10)	−0.0058 (10)	−0.0025 (12)
C3	0.0346 (10)	0.0580 (13)	0.0532 (13)	−0.0029 (10)	−0.0054 (10)	0.0103 (11)
C4	0.0356 (10)	0.0441 (11)	0.0565 (13)	0.0041 (9)	−0.0003 (10)	0.0048 (10)
C5	0.0373 (10)	0.0360 (10)	0.0455 (11)	0.0017 (8)	0.0024 (9)	0.0028 (9)
C6	0.0397 (11)	0.0471 (12)	0.0549 (13)	0.0061 (9)	0.0043 (10)	−0.0097 (11)
C7	0.0412 (11)	0.0448 (11)	0.0571 (13)	0.0048 (9)	−0.0001 (10)	−0.0171 (11)
C8	0.0368 (10)	0.0337 (9)	0.0415 (10)	0.0032 (8)	−0.0027 (9)	−0.0043 (9)
C9	0.0352 (10)	0.0321 (9)	0.0394 (10)	0.0006 (8)	−0.0019 (8)	−0.0007 (8)
C10	0.0348 (9)	0.0336 (9)	0.0401 (10)	−0.0005 (8)	0.0010 (8)	0.0007 (9)
C11	0.0375 (10)	0.0444 (11)	0.0500 (12)	0.0025 (9)	−0.0015 (10)	−0.0135 (10)
C12	0.0360 (10)	0.0420 (10)	0.0448 (11)	0.0037 (8)	0.0013 (9)	−0.0050 (9)
C13	0.0371 (10)	0.0370 (10)	0.0392 (10)	0.0001 (8)	−0.0023 (9)	0.0023 (9)
C14	0.0384 (10)	0.0359 (10)	0.0479 (12)	0.0003 (8)	−0.0038 (9)	−0.0019 (9)
C15	0.0459 (12)	0.0419 (11)	0.0608 (15)	0.0060 (9)	−0.0066 (11)	−0.0139 (11)
C16	0.0483 (12)	0.0494 (12)	0.0519 (13)	0.0033 (10)	−0.0078 (11)	−0.0097 (11)
C17	0.0395 (10)	0.0437 (11)	0.0475 (11)	0.0012 (9)	−0.0074 (10)	0.0001 (10)
C18	0.0362 (10)	0.0403 (10)	0.0463 (11)	0.0006 (9)	−0.0042 (9)	−0.0011 (9)
C19	0.0425 (12)	0.0527 (12)	0.0491 (12)	−0.0051 (10)	−0.0047 (10)	0.0074 (11)
C20	0.0418 (12)	0.0497 (12)	0.0627 (15)	−0.0071 (10)	−0.0054 (11)	0.0067 (12)
C21	0.0488 (12)	0.0465 (12)	0.068 (2)	−0.0070 (10)	−0.0156 (13)	−0.0037 (12)
C22	0.0451 (12)	0.0561 (13)	0.0504 (13)	−0.0018 (11)	−0.0130 (11)	−0.0001 (11)
C23	0.0458 (13)	0.0549 (14)	0.084 (2)	0.0145 (11)	−0.0010 (14)	0.0017 (15)
C24	0.0385 (12)	0.066 (2)	0.0599 (15)	−0.0055 (11)	0.0027 (11)	0.0058 (13)
C25	0.0444 (11)	0.0359 (10)	0.0538 (12)	−0.0021 (9)	0.0018 (10)	0.0041 (10)
C26	0.0451 (12)	0.0520 (12)	0.0424 (11)	−0.0002 (10)	−0.0001 (10)	0.0029 (11)
C27	0.0446 (11)	0.0382 (11)	0.078 (2)	−0.0014 (9)	−0.0097 (12)	0.0121 (12)
C28	0.0476 (13)	0.0549 (13)	0.0574 (14)	0.0059 (11)	0.0004 (12)	0.0126 (12)
C29	0.0445 (13)	0.079 (2)	0.079 (2)	0.0013 (13)	0.0013 (14)	−0.010 (2)
C30	0.066 (2)	0.081 (2)	0.096 (2)	−0.028 (2)	−0.011 (2)	0.032 (2)
C31	0.0509 (14)	0.100 (2)	0.0524 (14)	0.026 (2)	−0.0039 (13)	0.001 (2)
C32	0.050 (2)	0.205 (5)	0.091 (3)	0.020 (3)	−0.021 (2)	0.018 (3)
C33	0.059 (2)	0.0553 (15)	0.091 (2)	0.0022 (12)	−0.018 (2)	0.012 (2)
C34	0.067 (2)	0.068 (2)	0.150 (4)	0.011 (2)	−0.003 (3)	0.013 (2)
O1	0.0374 (8)	0.0877 (13)	0.0666 (11)	−0.0035 (9)	−0.0113 (9)	0.0181 (11)
O2	0.089 (2)	0.094 (2)	0.079 (2)	0.0228 (15)	−0.0081 (14)	0.0277 (14)
O3	0.0589 (10)	0.0490 (9)	0.0685 (12)	0.0062 (8)	−0.0060 (9)	0.0057 (9)
O4	0.124 (2)	0.125 (2)	0.093 (2)	0.049 (2)	−0.046 (2)	−0.004 (2)

Geometric parameters (Å, º)

C1—C2	1.528 (3)	C19—C20	1.535 (3)
C1—C10	1.536 (3)	C19—H191	0.97
C1—H11	0.97	C19—H192	0.97
C1—H12	0.97	C20—C21	1.528 (4)
C2—C3	1.515 (4)	C20—C30	1.532 (4)
C2—H21	0.97	C20—C29	1.532 (4)
C2—H22	0.97	C21—C22	1.516 (4)
C3—O1	1.463 (3)	C21—H211	0.97
C3—C4	1.532 (4)	C21—H212	0.97
C3—H3	0.98	C22—H221	0.97
C4—C24	1.528 (4)	C22—H222	0.97
C4—C23	1.547 (3)	C23—H231	0.96
C4—C5	1.557 (3)	C23—H232	0.96
C5—C6	1.531 (4)	C23—H233	0.96
C5—C10	1.553 (3)	C24—H241	0.96
C5—H5	0.98	C24—H242	0.96
C6—C7	1.529 (3)	C24—H243	0.96
C6—H61	0.97	C25—H251	0.96
C6—H62	0.97	C25—H252	0.96
C7—C8	1.543 (3)	C25—H253	0.96
C7—H71	0.97	C26—H261	0.96
C7—H72	0.97	C26—H262	0.96
C8—C26	1.539 (3)	C26—H263	0.96
C8—C9	1.548 (3)	C27—H271	0.96
C8—C14	1.600 (3)	C27—H272	0.96
C9—C11	1.537 (3)	C27—H273	0.96
C9—C10	1.576 (3)	C28—O3	1.448 (3)
C9—H9	0.98	C28—H281	0.97
C10—C25	1.543 (3)	C28—H282	0.97
C11—C12	1.502 (3)	C29—H291	0.96
C11—H111	0.97	C29—H292	0.96
C11—H112	0.97	C29—H293	0.96
C12—C13	1.330 (3)	C30—H301	0.96
C12—H121	0.93	C30—H302	0.96
C13—C14	1.522 (3)	C30—H303	0.96
C13—C18	1.524 (3)	C31—O2	1.189 (4)
C14—C15	1.509 (3)	C31—O1	1.340 (4)
C14—C27	1.564 (3)	C31—C32	1.499 (5)
C15—C16	1.324 (4)	C32—H321	0.96
C15—H15	0.93	C32—H322	0.96
C16—C17	1.515 (3)	C32—H323	0.96
C16—H16	0.93	C33—O4	1.195 (5)
C17—C22	1.540 (3)	C33—O3	1.333 (4)
C17—C28	1.542 (3)	C33—C34	1.463 (5)
C17—C18	1.556 (3)	C34—H341	0.96
C18—C19	1.536 (3)	C34—H342	0.96
C18—H18	0.98	C34—H343	0.96
C2—C1—C10	113.4 (2)	C19—C18—H18	107.57 (13)
C2—C1—H11	108.90 (14)	C17—C18—H18	107.57 (13)
C10—C1—H11	108.90 (12)	C20—C19—C18	114.8 (2)
C2—C1—H12	108.90 (14)	C20—C19—H191	108.57 (14)
C10—C1—H12	108.90 (12)	C18—C19—H191	108.57 (13)
H11—C1—H12	107.7	C20—C19—H192	108.57 (14)
C3—C2—C1	109.4 (2)	C18—C19—H192	108.57 (13)
C3—C2—H21	109.80 (14)	H191—C19—H192	107.5
C1—C2—H21	109.80 (13)	C21—C20—C30	109.0 (3)
C3—C2—H22	109.80 (14)	C21—C20—C29	111.4 (3)
C1—C2—H22	109.80 (14)	C30—C20—C29	109.5 (3)
H21—C2—H22	108.2	C21—C20—C19	106.8 (2)
O1—C3—C2	107.0 (2)	C30—C20—C19	108.7 (2)
O1—C3—C4	109.6 (2)	C29—C20—C19	111.5 (2)
C2—C3—C4	114.4 (2)	C22—C21—C20	112.5 (2)
O1—C3—H3	108.55 (13)	C22—C21—H211	109.09 (13)
C2—C3—H3	108.55 (14)	C20—C21—H211	109.09 (15)
C4—C3—H3	108.55 (13)	C22—C21—H212	109.09 (15)
C24—C4—C3	112.0 (2)	C20—C21—H212	109.1 (2)
C24—C4—C23	107.9 (2)	H211—C21—H212	107.8
C3—C4—C23	107.6 (2)	C21—C22—C17	114.4 (2)
C24—C4—C5	114.8 (2)	C21—C22—H221	108.65 (14)
C3—C4—C5	105.7 (2)	C17—C22—H221	108.65 (13)
C23—C4—C5	108.7 (2)	C21—C22—H222	108.65 (15)
C6—C5—C10	110.1 (2)	C17—C22—H222	108.65 (13)
C6—C5—C4	114.2 (2)	H221—C22—H222	107.6
C10—C5—C4	117.2 (2)	C4—C23—H231	109.47 (15)
C6—C5—H5	104.65 (12)	C4—C23—H232	109.5 (2)
C10—C5—H5	104.65 (11)	H231—C23—H232	109.5
C4—C5—H5	104.65 (12)	C4—C23—H233	109.47 (14)
C7—C6—C5	110.0 (2)	H231—C23—H233	109.5
C7—C6—H61	109.67 (12)	H232—C23—H233	109.5
C5—C6—H61	109.67 (12)	C4—C24—H241	109.5 (2)
C7—C6—H62	109.67 (14)	C4—C24—H242	109.47 (14)
C5—C6—H62	109.67 (12)	H241—C24—H242	109.5
H61—C6—H62	108.2	C4—C24—H243	109.47 (13)
C6—C7—C8	114.4 (2)	H241—C24—H243	109.5
C6—C7—H71	108.65 (14)	H242—C24—H243	109.5
C8—C7—H71	108.65 (13)	C10—C25—H251	109.47 (12)
C6—C7—H72	108.65 (14)	C10—C25—H252	109.47 (12)
C8—C7—H72	108.65 (13)	H251—C25—H252	109.5
H71—C7—H72	107.6	C10—C25—H253	109.47 (12)
C26—C8—C7	107.8 (2)	H251—C25—H253	109.5
C26—C8—C9	112.1 (2)	H252—C25—H253	109.5
C7—C8—C9	110.3 (2)	C8—C26—H261	109.47 (12)
C26—C8—C14	108.7 (2)	C8—C26—H262	109.47 (12)
C7—C8—C14	110.8 (2)	H261—C26—H262	109.5
C9—C8—C14	107.1 (2)	C8—C26—H263	109.47 (12)
C11—C9—C8	110.9 (2)	H261—C26—H263	109.5
C11—C9—C10	113.5 (2)	H262—C26—H263	109.5
C8—C9—C10	116.7 (2)	C14—C27—H271	109.47 (13)
C11—C9—H9	104.80 (12)	C14—C27—H272	109.47 (12)
C8—C9—H9	104.80 (11)	H271—C27—H272	109.5
C10—C9—H9	104.80 (11)	C14—C27—H273	109.47 (14)
C1—C10—C25	107.6 (2)	H271—C27—H273	109.5
C1—C10—C5	108.5 (2)	H272—C27—H273	109.5
C25—C10—C5	113.6 (2)	O3—C28—C17	110.5 (2)
C1—C10—C9	107.2 (2)	O3—C28—H281	109.55 (14)
C25—C10—C9	113.4 (2)	C17—C28—H281	109.55 (14)
C5—C10—C9	106.3 (2)	O3—C28—H282	109.55 (13)
C12—C11—C9	114.5 (2)	C17—C28—H282	109.55 (13)
C12—C11—H111	108.65 (13)	H281—C28—H282	108.1
C9—C11—H111	108.64 (12)	C20—C29—H291	109.5 (2)
C12—C11—H112	108.64 (13)	C20—C29—H292	109.5 (2)
C9—C11—H112	108.64 (12)	H291—C29—H292	109.5
H111—C11—H112	107.6	C20—C29—H293	109.47 (15)
C13—C12—C11	125.4 (2)	H291—C29—H293	109.5
C13—C12—H121	117.29 (13)	H292—C29—H293	109.5
C11—C12—H121	117.29 (11)	C20—C30—H301	109.5 (2)
C12—C13—C14	120.6 (2)	C20—C30—H302	109.5 (2)
C12—C13—C18	120.5 (2)	H301—C30—H302	109.5
C14—C13—C18	118.8 (2)	C20—C30—H303	109.5 (2)
C15—C14—C13	109.9 (2)	H301—C30—H303	109.5
C15—C14—C27	107.2 (2)	H302—C30—H303	109.5
C13—C14—C27	109.0 (2)	O2—C31—O1	124.7 (3)
C15—C14—C8	110.6 (2)	O2—C31—C32	124.8 (4)
C13—C14—C8	109.0 (2)	O1—C31—C32	110.5 (4)
C27—C14—C8	111.2 (2)	C31—C32—H321	109.5 (2)
C16—C15—C14	125.5 (2)	C31—C32—H322	109.5 (3)
C16—C15—H15	117.3 (2)	H321—C32—H322	109.5
C14—C15—H15	117.26 (12)	C31—C32—H323	109.5 (3)
C15—C16—C17	124.9 (2)	H321—C32—H323	109.5
C15—C16—H16	117.5 (2)	H322—C32—H323	109.5
C17—C16—H16	117.53 (13)	O4—C33—O3	123.4 (3)
C16—C17—C22	111.0 (2)	O4—C33—C34	124.6 (4)
C16—C17—C28	106.6 (2)	O3—C33—C34	112.0 (4)
C22—C17—C28	108.4 (2)	C33—C34—H341	109.5 (2)
C16—C17—C18	108.6 (2)	C33—C34—H342	109.5 (2)
C22—C17—C18	111.5 (2)	H341—C34—H342	109.5
C28—C17—C18	110.7 (2)	C33—C34—H343	109.5 (3)
C13—C18—C19	111.8 (2)	H341—C34—H343	109.5
C13—C18—C17	110.3 (2)	H342—C34—H343	109.5
C19—C18—C17	111.8 (2)	C31—O1—C3	117.0 (2)
C13—C18—H18	107.57 (12)	C33—O3—C28	119.4 (3)
C10—C1—C2—C3	56.8 (3)	C12—C13—C14—C8	30.6 (3)
C1—C2—C3—O1	178.0 (2)	C18—C13—C14—C8	−149.9 (2)
C1—C2—C3—C4	−60.4 (3)	C26—C8—C14—C15	−58.3 (2)
O1—C3—C4—C24	50.8 (3)	C7—C8—C14—C15	59.9 (2)
C2—C3—C4—C24	−69.4 (3)	C9—C8—C14—C15	−179.7 (2)
O1—C3—C4—C23	−67.5 (3)	C26—C8—C14—C13	62.5 (2)
C2—C3—C4—C23	172.2 (2)	C7—C8—C14—C13	−179.2 (2)
O1—C3—C4—C5	176.4 (2)	C9—C8—C14—C13	−58.8 (2)
C2—C3—C4—C5	56.2 (3)	C26—C8—C14—C27	−177.4 (2)
C24—C4—C5—C6	−59.5 (3)	C7—C8—C14—C27	−59.1 (3)
C3—C4—C5—C6	176.6 (2)	C9—C8—C14—C27	61.3 (2)
C23—C4—C5—C6	61.4 (3)	C13—C14—C15—C16	2.1 (4)
C24—C4—C5—C10	71.4 (3)	C27—C14—C15—C16	−116.2 (3)
C3—C4—C5—C10	−52.6 (3)	C8—C14—C15—C16	122.4 (3)
C23—C4—C5—C10	−167.8 (2)	C14—C15—C16—C17	−2.3 (4)
C10—C5—C6—C7	64.1 (2)	C15—C16—C17—C22	148.8 (3)
C4—C5—C6—C7	−161.6 (2)	C15—C16—C17—C28	−93.3 (3)
C5—C6—C7—C8	−56.0 (3)	C15—C16—C17—C18	26.0 (3)
C6—C7—C8—C26	−76.8 (3)	C12—C13—C18—C19	107.8 (3)
C6—C7—C8—C9	45.9 (3)	C14—C13—C18—C19	−71.7 (3)
C6—C7—C8—C14	164.4 (2)	C12—C13—C18—C17	−127.2 (2)
C26—C8—C9—C11	−58.1 (2)	C14—C13—C18—C17	53.4 (3)
C7—C8—C9—C11	−178.2 (2)	C16—C17—C18—C13	−47.8 (3)
C14—C8—C9—C11	61.1 (2)	C22—C17—C18—C13	−170.3 (2)
C26—C8—C9—C10	74.0 (2)	C28—C17—C18—C13	68.9 (2)
C7—C8—C9—C10	−46.1 (2)	C16—C17—C18—C19	77.3 (2)
C14—C8—C9—C10	−166.9 (2)	C22—C17—C18—C19	−45.3 (3)
C2—C1—C10—C25	71.8 (3)	C28—C17—C18—C19	−166.0 (2)
C2—C1—C10—C5	−51.5 (2)	C13—C18—C19—C20	177.5 (2)
C2—C1—C10—C9	−165.9 (2)	C17—C18—C19—C20	53.3 (3)
C6—C5—C10—C1	−175.9 (2)	C18—C19—C20—C21	−58.1 (3)
C4—C5—C10—C1	51.4 (2)	C18—C19—C20—C30	−175.5 (3)
C6—C5—C10—C25	64.5 (2)	C18—C19—C20—C29	63.8 (3)
C4—C5—C10—C25	−68.2 (3)	C30—C20—C21—C22	175.0 (2)
C6—C5—C10—C9	−60.9 (2)	C29—C20—C21—C22	−64.1 (3)
C4—C5—C10—C9	166.4 (2)	C19—C20—C21—C22	57.8 (3)
C11—C9—C10—C1	−59.6 (2)	C20—C21—C22—C17	−55.6 (3)
C8—C9—C10—C1	169.6 (2)	C16—C17—C22—C21	−73.5 (3)
C11—C9—C10—C25	59.0 (2)	C28—C17—C22—C21	169.7 (2)
C8—C9—C10—C25	−71.8 (2)	C18—C17—C22—C21	47.6 (3)
C11—C9—C10—C5	−175.5 (2)	C16—C17—C28—O3	−180.0 (2)
C8—C9—C10—C5	53.7 (2)	C22—C17—C28—O3	−60.4 (3)
C8—C9—C11—C12	−33.8 (3)	C18—C17—C28—O3	62.1 (3)
C10—C9—C11—C12	−167.5 (2)	O2—C31—O1—C3	−3.7 (5)
C9—C11—C12—C13	3.2 (4)	C32—C31—O1—C3	175.0 (3)
C11—C12—C13—C14	−2.3 (4)	C2—C3—O1—C31	−113.9 (3)
C11—C12—C13—C18	178.2 (2)	C4—C3—O1—C31	121.4 (3)
C12—C13—C14—C15	151.9 (2)	O4—C33—O3—C28	4.0 (5)
C18—C13—C14—C15	−28.6 (3)	C34—C33—O3—C28	−175.2 (2)
C12—C13—C14—C27	−90.9 (2)	C17—C28—O3—C33	112.5 (3)
C18—C13—C14—C27	88.6 (2)