The isomeric compounds nimbolide and isonimbolide

Nimbolide [systematic name: (4α,5α,6α,7α,15β,17α)-7,15:21,23-diepoxy-6-hydroxy-4,8-dimethyl-1-oxo-18,24-dinor-11,12-secochola-2,13,20,22-tetraene-4,11-dicarboxylic acid γ-lactone methyl ester], C₂₇H₃₀O₇, was isolated from the leaves of Azadirachta indica, and its isomer, isonimbolide [systematic name: (4α,5α,6α,7α,15α)-7,15:21,23-diepoxy-6-hydroxy-4,8-dimethyl-1-oxo-18,24-dinor-11,12-secochola-2,16,20,22-tetra­ene-4,11-dicarboxylic acid γ-lactone methyl ester], was prepared from a novel rearrangement reaction of nimbolide, using boron trifluoride etherate and tetra­butyl­ammonium bromide. The reaction conditions are probably responsible for the ether cleavage, double-bond rearrangement and reformation of the ether linkage. As a result, there are conformational changes in two cyclo­pentane rings and the side-chain –CH₂COOMe group. In isonimbolide, an (24) hydrogen-bond motif is observed.

S1. Comment

The neem (Azadirachta indica) and its constituents have been shown to possess bioinsecticidal activity at different levels (Chawla et al., 1996; Govindachari et al., 1992; Govindachari, Narasimhan et al., 1996; Govindachari & Geetha Gopalakrishnan, 1998). More than 300 limonoids have been isolated and many of them belong to the class of tetranortriterpenoids, the crystal structures of many of which have been established (Govindachari et al., 1994; Govindachari, Geetha Gopalakrishnan et al., 1996; Kabaleeswaran et al., 1994, 1997, 1999; Malathi et al., 2003). It has also been shown that the bioinsecticidal activity can be enhanced by photo-oxidation and microwave-induced oxidation (Suresh et al., 2002; Gopalakrishnan et al., 2001; Geetha Gopalakrishnan et al., 2000). The present paper reports the structures of two compounds, namely nimbolide, (I), a tetranortriterpenoid, isolated from the leaves of Azadirachta indica, and a novel rearranged product, isonimbolide, (II). The rearranged product was synthesized with a view to enhancing the activity of the native compound through the reaction of nimbolide with a Lewis acid, BF₃·OEt₂, in the presence of tetrabutylammonium bromide.

The chemical modification brought about the cleavage of the ether linkage between atoms C7 and C15. Due to stability constraints, there is a rearrangement of the double bond, from C13═C14 in nimbolide to C16═C17 in isonimbolide, along with ring closure between C7 and C13, resulting in the re-formation of the ether linkage. Hence, chemically, nimbolide and its isomer differ in the ether linkage, which is between C7 and C15 in nimbolide, and C7 and C13 in isonimbolide (scheme and Fig. 1). Nimbolide and isonimbolide thus differ primarily in the orientation of the –CH₂COOMe group attached to C9. The orientation of this group can be defined by the torsion angle C8—C9—C11—C12, which is 91.1 (5)° in nimbolide and 132.5 (6)° in isonimbolide. The orientation of the carbomethoxy group (C9—C11—C12–027) is -ac [−148.8 (5)°] and sp [−29.0 (9)°] (Klyne & Prelog, 1960) in nimbolide and isonimbolide, respectively. These differences in the side-chain conformation arise due to the change in the orientation of ring I and the methyl group attached to C13 between nimbolide and isonimbolide. The migration of the double bond in ring I of isonimbolide accompanies a difference in the fusion of rings I/D, which is quasi-trans in nimbolide and trans in isonimbolide.

The ring junctions A/B, A/F, B/F and B/D in both structures are trans, trans, trans and cis, respectively. In isonimbolide, atom C13 is sp³ hybridized and the C18 methyl attached to this atom is in an α conformation. There are considerable variations in the torsion angles involving the atoms of rings D and I, which indicates that the reaction centre would have been atom O7, which is a potential centre for the coordination of the Lewis acid. In both structures, the rings A, B and F have sofa, chair and half-chair conformations, respectively (Cremer & Pople, 1975), and the methyl atoms C19, C29 and C30 are in β conformations. In nimbolide, the furan ring at C17 shows rotational disorder about the C17—C20 bond. This rotational flexibility has resulted in disorder of all the atoms of the furan ring except C20, and these atoms show split positions viz. C21A, O21A, C22A and C23A, and C21B, O21B, C22B and C23B. However, the furan ring of isonimbolide shows no disorder (Fig. 1 b). The orientation of this furan ring, described by the torsion angle C16—C17—C20—C22, are −101.2 (14) and −55.3 (13)° for the congeners A and B, respectively, in nimbolide, and −12.1 (10)° in isonimbolide. The angles between the least-squares planes of ring A and the furan ring E are 123.0 (7) and 95.6 (9)° for disorder components A and B, respectively, in nimbolide, and 151.4 (2)° in isonimbolide.

No significant hydrogen-bonding interactions are seen in nimbolide, but an interesting hydrogen-bonding pattern is present in isonimbolide, for which three hydrogen-bonded chain motifs (Bernstein et al., 1995) are observed (Table 1). The first, C3···O12(3/2 − x, −y, 1/2 + z), produces a C(9) chain parallel to the z axis. The second chain, a C(6) motif mediated by C6···O1(1 − x, 1/2 + y, 1/2 − z), runs parallel to the y axis. The third, linked by C16···O28(3/2 − x, 1 − y, z − 1/2), forms a C(9) chain along the z axis. These combine to generate a ring with an R₄⁴(24) motif (Fig. 2).

S2. Experimental

Nimbolide, (I), was isolated from the the fresh uncrushed leaves of Azadirachta indica following the procedure described by Govindachari et al. (1999). To prepare isonimbolide, (II), nimbolide (200 mg) was dissolved in chloroform (analytical reagent, 200 ml) at 258 K. To this, tetrabutyl ammonium bromide (145 mg) and boron triflouride etherate (0.3 ml) were added. The reaction mixture was allowed to reach room temperature and was stirred for 6 h. On completion of the reaction (monitored by thin-layer chromatography), it was quenched with solid sodium bicarbonate. The organic layer was filtered and concentrated under reduced pressure to yield the crude isonimbolide. Flash column chromatography of the product over silica gel using hexane ethyl acetate as eluent furnished pure isonimbolide. The final yield was 52%.

S3. Refinement

In the absence of suitable anomalous scatters, Friedel equivalents could not be used to determine the absolute structure. Refinement of the Flack parameter (Flack, 1983) led to inconclusive values (Flack & Bernadinelli, 2000) for this parameter [−0.8 (7) for nimbolide and −1(3) for isonimbolide]. Therefore, the 103 and 34 Friedel equivalents of nimbolide and isonimbolide, respectively, were merged before the final refinements. The enantiomer employed in the refined model was chosen to agree with the accepted configuration of triterpenoids (Henderson et al., 1968; Narayanan et al., 1964; Harris et al., 1968). The methyl and hydroxyl H atoms were constrained to an ideal geometry (C—H = 0.96 Å and O—H = 0.82 Å), with U_iso(H) = 1.5U_eq(parent atom), but were allowed to rotate freely about the C—C and C—O bonds, respectively. All remaining H atoms were placed in geometrically idealized positions (C—H = 0.97–0.98 Å) and constrained to ride on their parent atom, with U_iso(H) = 1.2U_eq(C). All the disordered atoms were restrained using SAME, SADI and DFIX restraints. A SIMU restraint was used for the chemically equivalent disordered congeners.

Computing details

For both compounds, data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 and PARST97 (Nardelli, 1995).

Figures

	Fig. 1. (a) The molecular structure of nimbolide, (I), and (b) isonimbolide, (II), with the atom-numbering schemes. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted.
	Fig. 2. A view of the supramolecular structure of isonimbolide, showing the R4^4(24) motif. The suffixes *, $, # and & denote symmetry positions (1 − x, y + 1/2, 1/2 − z), (3/2 − x, 1 − y, z − 1/2), (x, y, z) and (x, y − 1, z), respectively.

(I) (4α,5α,6α,7α,15β,17α)-7,15:21,23-diepoxy-6 -hydroxy-4,8-dimethyl-1-oxo-18,24-dinor-11,12-secochola-2,13,20,22-tetraene- 4,11-dicarboxylic acid γ-lactone methyl ester

Crystal data

C27H30O7	Dx = 1.332 Mg m^−3
Mr = 466.51	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 12.115 (3) Å	θ = 15–30°
b = 12.225 (4) Å	µ = 0.79 mm^−1
c = 15.710 (3) Å	T = 293 K
V = 2326.8 (10) Å^3	Rod, colourless
Z = 4	0.40 × 0.25 × 0.15 mm
F(000) = 992

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.119
Radiation source: fine-focus sealed tube	θmax = 75.2°, θmin = 4.6°
Graphite monochromator	h = −15→15
non–profiled ω/2θ scans	k = −5→15
2806 measured reflections	l = −10→19
2695 independent reflections	3 standard reflections every 200 reflections
1958 reflections with I > 2σ(I)	intensity decay: 4%

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)] = 0.059	H-atom parameters constrained
wR(F^2) = 0.183	w = 1/[σ^2(Fo^2) + (0.1148P)^2 + 0.6918P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.015
2695 reflections	Δρmax = 0.41 e Å^−3
355 parameters	Δρmin = −0.29 e Å^−3
108 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0029 (6)

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	Occ. (<1)
O1	0.6613 (3)	0.3608 (4)	0.9991 (2)	0.0863 (13)
O6	0.9127 (3)	0.2687 (3)	0.6940 (2)	0.0615 (9)
O7	0.6887 (3)	0.2937 (2)	0.6557 (2)	0.0534 (8)
O12	0.4232 (3)	0.3780 (3)	0.8542 (3)	0.0766 (12)
O27	0.3838 (3)	0.5555 (3)	0.8562 (3)	0.0842 (13)
O28	0.9928 (4)	0.1214 (4)	0.7530 (4)	0.0926 (14)
C1	0.7359 (4)	0.3384 (4)	0.9499 (3)	0.0556 (12)
C2	0.8079 (5)	0.2456 (5)	0.9693 (4)	0.0775 (17)
H2	0.7932	0.2076	1.0193	0.093*
C3	0.8927 (5)	0.2098 (5)	0.9223 (4)	0.0775 (17)
H3	0.9316	0.1476	0.9384	0.093*
C4	0.9240 (4)	0.2706 (4)	0.8439 (3)	0.0569 (12)
C5	0.8214 (3)	0.3291 (4)	0.8117 (3)	0.0437 (9)
H5	0.7688	0.2695	0.8018	0.052*
C6	0.8519 (4)	0.3645 (4)	0.7247 (3)	0.0501 (10)
H6	0.9006	0.4284	0.7271	0.060*
C7	0.7492 (4)	0.3904 (4)	0.6733 (3)	0.0467 (10)
H7	0.7711	0.4244	0.6194	0.056*
C8	0.6717 (4)	0.4708 (3)	0.7228 (3)	0.0435 (9)
C9	0.6521 (3)	0.4323 (3)	0.8180 (3)	0.0408 (9)
H9	0.6138	0.3620	0.8131	0.049*
C10	0.7588 (3)	0.4066 (3)	0.8702 (3)	0.0453 (10)
C11	0.5697 (4)	0.5081 (4)	0.8637 (3)	0.0545 (11)
H11A	0.5893	0.5123	0.9234	0.065*
H11B	0.5760	0.5811	0.8399	0.065*
C12	0.4528 (4)	0.4711 (4)	0.8563 (3)	0.0520 (11)
C13	0.4936 (4)	0.4961 (4)	0.6254 (3)	0.0512 (11)
C14	0.5700 (4)	0.4428 (3)	0.6726 (3)	0.0435 (9)
C15	0.5739 (4)	0.3234 (3)	0.6518 (3)	0.0460 (10)
H15	0.5314	0.2815	0.6937	0.055*
C16	0.5182 (4)	0.3180 (4)	0.5647 (3)	0.0541 (11)
H16A	0.4784	0.2497	0.5575	0.065*
H16B	0.5718	0.3255	0.5192	0.065*
C17	0.4379 (4)	0.4171 (4)	0.5670 (3)	0.0543 (11)
H17	0.4339	0.4494	0.5100	0.065*
C18	0.4620 (5)	0.6132 (4)	0.6271 (4)	0.0724 (16)
H18A	0.4053	0.6263	0.5857	0.109*
H18B	0.5253	0.6574	0.6140	0.109*
H18C	0.4351	0.6319	0.6827	0.109*
C19	0.8220 (4)	0.5086 (4)	0.9002 (3)	0.0589 (12)
H19A	0.8543	0.5446	0.8519	0.088*
H19B	0.8792	0.4872	0.9391	0.088*
H19C	0.7720	0.5577	0.9283	0.088*
C20	0.3226 (4)	0.3867 (5)	0.5954 (3)	0.0637 (13)
C23A	0.1478 (17)	0.3371 (19)	0.6006 (10)	0.102 (5)	0.526 (11)
H23A	0.0762	0.3248	0.5815	0.122*	0.526 (11)
O21A	0.1807 (8)	0.3242 (11)	0.6807 (7)	0.093 (3)	0.526 (11)
C21A	0.2896 (10)	0.3499 (14)	0.6702 (9)	0.100 (4)	0.526 (11)
H21A	0.3394	0.3416	0.7148	0.120*	0.526 (11)
C22A	0.2295 (15)	0.3696 (18)	0.5522 (14)	0.133 (6)	0.526 (11)
H22A	0.2232	0.3796	0.4937	0.160*	0.526 (11)
C23B	0.1617 (18)	0.3047 (14)	0.6142 (12)	0.082 (4)	0.474 (11)
H23B	0.1102	0.2484	0.6166	0.098*	0.474 (11)
O21B	0.1629 (12)	0.3981 (15)	0.6599 (11)	0.130 (4)	0.474 (11)
C21B	0.2716 (13)	0.4394 (17)	0.6579 (12)	0.119 (6)	0.474 (11)
H21B	0.3015	0.4928	0.6933	0.143*	0.474 (11)
C22B	0.2502 (12)	0.3112 (12)	0.5652 (12)	0.089 (4)	0.474 (11)
H22B	0.2613	0.2696	0.5164	0.107*	0.474 (11)
C27A	0.2691 (19)	0.535 (3)	0.826 (5)	0.105 (12)	0.39 (7)
H27A	0.2285	0.6022	0.8252	0.158*	0.39 (7)
H27B	0.2335	0.4836	0.8630	0.158*	0.39 (7)
H27C	0.2716	0.5051	0.7691	0.158*	0.39 (7)
C27B	0.2683 (14)	0.526 (2)	0.874 (3)	0.101 (7)	0.61 (7)
H27D	0.2232	0.5907	0.8726	0.151*	0.61 (7)
H27E	0.2636	0.4935	0.9298	0.151*	0.61 (7)
H27F	0.2427	0.4749	0.8324	0.151*	0.61 (7)
C28	0.9466 (4)	0.2068 (4)	0.7628 (4)	0.0643 (14)
C29	1.0287 (4)	0.3406 (5)	0.8603 (4)	0.0705 (15)
H29A	1.0491	0.3782	0.8090	0.106*
H29B	1.0882	0.2939	0.8779	0.106*
H29C	1.0137	0.3931	0.9043	0.106*
C30	0.7140 (5)	0.5881 (4)	0.7115 (3)	0.0589 (13)
H30A	0.6690	0.6372	0.7443	0.088*
H30B	0.7103	0.6081	0.6525	0.088*
H30C	0.7890	0.5926	0.7307	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.073 (3)	0.123 (4)	0.063 (2)	0.012 (3)	0.017 (2)	0.022 (2)
O6	0.0392 (15)	0.072 (2)	0.074 (2)	0.0050 (17)	0.0022 (16)	−0.0179 (19)
O7	0.0451 (16)	0.0459 (15)	0.069 (2)	0.0018 (14)	−0.0057 (16)	−0.0127 (16)
O12	0.062 (2)	0.0531 (19)	0.115 (3)	−0.0067 (19)	0.016 (2)	0.013 (2)
O27	0.0481 (19)	0.0529 (19)	0.151 (4)	0.0083 (16)	0.011 (3)	0.001 (3)
O28	0.062 (2)	0.075 (3)	0.140 (4)	0.021 (2)	−0.001 (3)	−0.019 (3)
C1	0.048 (2)	0.069 (3)	0.050 (3)	−0.004 (2)	−0.005 (2)	0.005 (2)
C2	0.063 (3)	0.090 (4)	0.080 (4)	0.007 (3)	0.003 (3)	0.037 (3)
C3	0.060 (3)	0.076 (4)	0.096 (4)	0.007 (3)	−0.015 (3)	0.032 (3)
C4	0.039 (2)	0.060 (3)	0.071 (3)	0.007 (2)	−0.004 (2)	0.008 (2)
C5	0.0322 (19)	0.046 (2)	0.053 (2)	0.0010 (18)	−0.0033 (18)	0.0026 (19)
C6	0.039 (2)	0.049 (2)	0.063 (3)	0.0015 (19)	0.004 (2)	−0.007 (2)
C7	0.044 (2)	0.051 (2)	0.045 (2)	−0.001 (2)	0.0013 (19)	−0.0022 (19)
C8	0.042 (2)	0.039 (2)	0.049 (2)	−0.0022 (18)	−0.0015 (19)	−0.0011 (18)
C9	0.0343 (18)	0.0388 (18)	0.049 (2)	0.0008 (17)	−0.0047 (17)	−0.0063 (17)
C10	0.038 (2)	0.046 (2)	0.052 (2)	−0.0025 (19)	−0.0014 (19)	−0.002 (2)
C11	0.051 (2)	0.052 (2)	0.061 (3)	0.007 (2)	0.004 (2)	−0.010 (2)
C12	0.048 (2)	0.049 (2)	0.059 (3)	0.004 (2)	0.010 (2)	0.008 (2)
C13	0.051 (2)	0.047 (2)	0.055 (2)	0.001 (2)	−0.007 (2)	0.007 (2)
C14	0.042 (2)	0.0414 (19)	0.047 (2)	0.0003 (19)	−0.0052 (19)	0.0003 (18)
C15	0.044 (2)	0.041 (2)	0.053 (2)	0.0004 (19)	−0.004 (2)	0.0007 (19)
C16	0.058 (3)	0.054 (3)	0.050 (2)	−0.005 (2)	−0.002 (2)	−0.005 (2)
C17	0.051 (2)	0.063 (3)	0.048 (2)	−0.002 (2)	−0.008 (2)	0.007 (2)
C18	0.082 (4)	0.053 (3)	0.082 (4)	0.012 (3)	−0.022 (3)	0.011 (3)
C19	0.053 (3)	0.060 (3)	0.063 (3)	−0.008 (3)	−0.007 (2)	−0.009 (2)
C20	0.048 (3)	0.084 (4)	0.059 (3)	−0.001 (3)	−0.007 (2)	−0.013 (3)
C23A	0.061 (7)	0.147 (10)	0.098 (8)	−0.035 (8)	0.005 (6)	−0.026 (8)
O21A	0.073 (5)	0.113 (7)	0.094 (6)	−0.016 (6)	0.014 (5)	0.004 (6)
C21A	0.062 (6)	0.123 (10)	0.115 (8)	0.001 (7)	0.001 (7)	0.043 (8)
C22A	0.112 (10)	0.179 (13)	0.109 (9)	−0.015 (11)	−0.005 (9)	0.016 (11)
C23B	0.075 (8)	0.089 (8)	0.081 (8)	−0.012 (7)	0.017 (7)	0.008 (7)
O21B	0.096 (7)	0.145 (9)	0.151 (8)	−0.018 (8)	0.032 (7)	−0.026 (8)
C21B	0.077 (8)	0.137 (12)	0.143 (11)	−0.029 (10)	0.034 (9)	−0.051 (11)
C22B	0.078 (8)	0.068 (7)	0.120 (10)	−0.020 (7)	0.042 (7)	−0.032 (8)
C27A	0.033 (8)	0.066 (11)	0.22 (3)	0.018 (7)	0.027 (16)	0.01 (2)
C27B	0.041 (6)	0.101 (12)	0.16 (2)	0.002 (6)	0.035 (9)	−0.009 (14)
C28	0.032 (2)	0.064 (3)	0.097 (4)	0.011 (2)	−0.006 (3)	−0.011 (3)
C29	0.039 (2)	0.087 (4)	0.085 (4)	−0.001 (3)	−0.014 (3)	−0.002 (3)
C30	0.063 (3)	0.043 (2)	0.071 (3)	−0.010 (2)	−0.005 (3)	0.009 (2)

Geometric parameters (Å, º)

O1—C1	1.220 (6)	C15—H15	0.9800
O6—C28	1.382 (7)	C16—C17	1.555 (7)
O6—C6	1.464 (5)	C16—H16A	0.9700
O7—C7	1.418 (5)	C16—H16B	0.9700
O7—C15	1.439 (5)	C17—C20	1.513 (7)
O12—C12	1.193 (6)	C17—H17	0.9800
O27—C12	1.328 (6)	C18—H18A	0.9600
O27—C27B	1.473 (11)	C18—H18B	0.9600
O27—C27A	1.492 (16)	C18—H18C	0.9600
O28—C28	1.195 (6)	C19—H19A	0.9600
C1—C2	1.463 (8)	C19—H19B	0.9600
C1—C10	1.530 (7)	C19—H19C	0.9600
C2—C3	1.339 (8)	C20—C21A	1.320 (13)
C2—H2	0.9300	C20—C21B	1.328 (14)
C3—C4	1.488 (8)	C20—C22A	1.333 (16)
C3—H3	0.9300	C20—C22B	1.359 (13)
C4—C28	1.518 (8)	C23A—C22A	1.310 (16)
C4—C5	1.521 (6)	C23A—O21A	1.330 (13)
C4—C29	1.552 (7)	C23A—H23A	0.9300
C5—C6	1.480 (6)	O21A—C21A	1.367 (13)
C5—C10	1.522 (6)	C21A—H21A	0.9300
C5—H5	0.9800	C22A—H22A	0.9300
C6—C7	1.518 (6)	C23B—C22B	1.322 (16)
C6—H6	0.9800	C23B—O21B	1.349 (14)
C7—C8	1.565 (6)	C23B—H23B	0.9300
C7—H7	0.9800	O21B—C21B	1.411 (15)
C8—C14	1.502 (6)	C21B—H21B	0.9300
C8—C30	1.533 (6)	C22B—H22B	0.9300
C8—C9	1.587 (6)	C27A—H27A	0.9600
C9—C11	1.540 (6)	C27A—H27B	0.9600
C9—C10	1.562 (6)	C27A—H27C	0.9600
C9—H9	0.9800	C27B—H27D	0.9600
C10—C19	1.537 (6)	C27B—H27E	0.9600
C11—C12	1.492 (7)	C27B—H27F	0.9600
C11—H11A	0.9700	C29—H29A	0.9600
C11—H11B	0.9700	C29—H29B	0.9600
C13—C14	1.353 (6)	C29—H29C	0.9600
C13—C18	1.483 (6)	C30—H30A	0.9600
C13—C17	1.492 (7)	C30—H30B	0.9600
C14—C15	1.496 (6)	C30—H30C	0.9600
C15—C16	1.527 (6)
C28—O6—C6	109.2 (4)	C15—C16—H16A	111.2
C7—O7—C15	107.3 (3)	C17—C16—H16A	111.2
C12—O27—C27B	114.1 (13)	C15—C16—H16B	111.2
C12—O27—C27A	117.0 (13)	C17—C16—H16B	111.2
O1—C1—C2	118.9 (5)	H16A—C16—H16B	109.1
O1—C1—C10	122.0 (5)	C13—C17—C20	113.3 (4)
C2—C1—C10	119.0 (4)	C13—C17—C16	103.6 (4)
C3—C2—C1	126.6 (5)	C20—C17—C16	113.1 (4)
C3—C2—H2	116.7	C13—C17—H17	108.9
C1—C2—H2	116.7	C20—C17—H17	108.9
C2—C3—C4	119.3 (5)	C16—C17—H17	108.9
C2—C3—H3	120.4	C13—C18—H18A	109.5
C4—C3—H3	120.4	C13—C18—H18B	109.5
C3—C4—C28	118.9 (5)	H18A—C18—H18B	109.5
C3—C4—C5	107.6 (4)	C13—C18—H18C	109.5
C28—C4—C5	96.3 (4)	H18A—C18—H18C	109.5
C3—C4—C29	110.3 (5)	H18B—C18—H18C	109.5
C28—C4—C29	106.0 (4)	C10—C19—H19A	109.5
C5—C4—C29	117.7 (4)	C10—C19—H19B	109.5
C6—C5—C4	103.9 (4)	H19A—C19—H19B	109.5
C6—C5—C10	120.0 (4)	C10—C19—H19C	109.5
C4—C5—C10	119.9 (4)	H19A—C19—H19C	109.5
C6—C5—H5	103.5	H19B—C19—H19C	109.5
C4—C5—H5	103.5	C21A—C20—C22A	98.3 (12)
C10—C5—H5	103.5	C21B—C20—C22B	106.7 (10)
O6—C6—C5	101.3 (4)	C21A—C20—C17	128.7 (7)
O6—C6—C7	113.8 (4)	C21B—C20—C17	121.9 (8)
C5—C6—C7	110.3 (4)	C22A—C20—C17	132.1 (11)
O6—C6—H6	110.3	C22B—C20—C17	131.3 (8)
C5—C6—H6	110.3	C22A—C23A—O21A	111.1 (17)
C7—C6—H6	110.3	C22A—C23A—H23A	124.5
O7—C7—C6	110.7 (4)	O21A—C23A—H23A	124.5
O7—C7—C8	108.1 (3)	C23A—O21A—C21A	98.5 (13)
C6—C7—C8	111.0 (3)	C20—C21A—O21A	118.6 (12)
O7—C7—H7	109.0	C20—C21A—H21A	120.7
C6—C7—H7	109.0	O21A—C21A—H21A	120.7
C8—C7—H7	109.0	C23A—C22A—C20	113.0 (17)
C14—C8—C30	115.2 (4)	C23A—C22A—H22A	123.5
C14—C8—C7	95.0 (3)	C20—C22A—H22A	123.5
C30—C8—C7	109.3 (4)	C22B—C23B—O21B	104.5 (17)
C14—C8—C9	107.7 (3)	C22B—C23B—H23B	127.7
C30—C8—C9	115.9 (4)	O21B—C23B—H23B	127.7
C7—C8—C9	111.8 (3)	C23B—O21B—C21B	107.5 (16)
C11—C9—C10	114.4 (3)	C20—C21B—O21B	106.1 (12)
C11—C9—C8	111.0 (4)	C20—C21B—H21B	127.0
C10—C9—C8	115.5 (3)	O21B—C21B—H21B	127.0
C11—C9—H9	104.9	C23B—C22B—C20	111.1 (15)
C10—C9—H9	104.9	C23B—C22B—H22B	124.4
C8—C9—H9	104.9	C20—C22B—H22B	124.4
C5—C10—C1	104.2 (4)	O27—C27A—H27A	109.5
C5—C10—C19	116.2 (4)	O27—C27A—H27B	109.5
C1—C10—C19	106.4 (4)	H27A—C27A—H27B	109.5
C5—C10—C9	102.7 (3)	O27—C27A—H27C	109.5
C1—C10—C9	112.9 (4)	H27A—C27A—H27C	109.5
C19—C10—C9	114.2 (4)	H27B—C27A—H27C	109.5
C12—C11—C9	113.4 (4)	O27—C27B—H27D	109.5
C12—C11—H11A	108.9	O27—C27B—H27E	109.5
C9—C11—H11A	108.9	H27D—C27B—H27E	109.5
C12—C11—H11B	108.9	O27—C27B—H27F	109.5
C9—C11—H11B	108.9	H27D—C27B—H27F	109.5
H11A—C11—H11B	107.7	H27E—C27B—H27F	109.5
O12—C12—O27	123.5 (5)	O28—C28—O6	121.1 (6)
O12—C12—C11	125.2 (5)	O28—C28—C4	129.9 (6)
O27—C12—C11	111.2 (4)	O6—C28—C4	108.8 (4)
C14—C13—C18	129.2 (5)	C4—C29—H29A	109.5
C14—C13—C17	109.6 (4)	C4—C29—H29B	109.5
C18—C13—C17	121.3 (4)	H29A—C29—H29B	109.5
C13—C14—C15	111.8 (4)	C4—C29—H29C	109.5
C13—C14—C8	137.7 (4)	H29A—C29—H29C	109.5
C15—C14—C8	108.1 (4)	H29B—C29—H29C	109.5
O7—C15—C14	105.5 (4)	C8—C30—H30A	109.5
O7—C15—C16	117.0 (4)	C8—C30—H30B	109.5
C14—C15—C16	103.0 (4)	H30A—C30—H30B	109.5
O7—C15—H15	110.3	C8—C30—H30C	109.5
C14—C15—H15	110.3	H30A—C30—H30C	109.5
C16—C15—H15	110.3	H30B—C30—H30C	109.5
C15—C16—C17	102.8 (4)
O1—C1—C2—C3	179.8 (7)	C27B—O27—C12—C11	−163 (2)
C10—C1—C2—C3	−2.4 (9)	C27A—O27—C12—C11	164 (3)
C1—C2—C3—C4	3.2 (10)	C9—C11—C12—O12	34.1 (8)
C2—C3—C4—C28	−134.2 (6)	C9—C11—C12—O27	−148.8 (5)
C2—C3—C4—C5	−26.3 (8)	C18—C13—C14—C15	178.7 (5)
C2—C3—C4—C29	103.1 (6)	C17—C13—C14—C15	−0.3 (6)
C3—C4—C5—C6	−166.9 (4)	C18—C13—C14—C8	−21.8 (10)
C28—C4—C5—C6	−43.8 (4)	C17—C13—C14—C8	159.1 (5)
C29—C4—C5—C6	67.9 (5)	C30—C8—C14—C13	−9.9 (8)
C3—C4—C5—C10	55.6 (6)	C7—C8—C14—C13	−124.0 (6)
C28—C4—C5—C10	178.6 (4)	C9—C8—C14—C13	121.2 (6)
C29—C4—C5—C10	−69.6 (6)	C30—C8—C14—C15	150.0 (4)
C28—O6—C6—C5	−19.6 (4)	C7—C8—C14—C15	35.9 (4)
C28—O6—C6—C7	−138.0 (4)	C9—C8—C14—C15	−78.9 (4)
C4—C5—C6—O6	40.4 (4)	C7—O7—C15—C14	−2.8 (5)
C10—C5—C6—O6	177.9 (4)	C7—O7—C15—C16	110.9 (4)
C4—C5—C6—C7	161.4 (4)	C13—C14—C15—O7	142.2 (4)
C10—C5—C6—C7	−61.2 (5)	C8—C14—C15—O7	−23.4 (5)
C15—O7—C7—C6	148.7 (4)	C13—C14—C15—C16	19.1 (5)
C15—O7—C7—C8	27.0 (5)	C8—C14—C15—C16	−146.5 (4)
O6—C6—C7—O7	44.2 (5)	O7—C15—C16—C17	−143.7 (4)
C5—C6—C7—O7	−68.9 (5)	C14—C15—C16—C17	−28.6 (5)
O6—C6—C7—C8	164.2 (3)	C14—C13—C17—C20	104.7 (5)
C5—C6—C7—C8	51.1 (5)	C18—C13—C17—C20	−74.4 (6)
O7—C7—C8—C14	−38.3 (4)	C14—C13—C17—C16	−18.3 (5)
C6—C7—C8—C14	−159.9 (4)	C18—C13—C17—C16	162.6 (5)
O7—C7—C8—C30	−157.3 (4)	C15—C16—C17—C13	28.8 (5)
C6—C7—C8—C30	81.2 (5)	C15—C16—C17—C20	−94.3 (5)
O7—C7—C8—C9	73.1 (4)	C13—C17—C20—C21A	−52.4 (12)
C6—C7—C8—C9	−48.5 (5)	C16—C17—C20—C21A	65.2 (12)
C14—C8—C9—C11	−73.1 (4)	C13—C17—C20—C21B	10.3 (13)
C30—C8—C9—C11	57.7 (5)	C16—C17—C20—C21B	127.9 (13)
C7—C8—C9—C11	−176.2 (3)	C13—C17—C20—C22A	141.2 (14)
C14—C8—C9—C10	154.7 (3)	C16—C17—C20—C22A	−101.2 (14)
C30—C8—C9—C10	−74.6 (5)	C13—C17—C20—C22B	−172.9 (12)
C7—C8—C9—C10	51.5 (5)	C16—C17—C20—C22B	−55.3 (13)
C6—C5—C10—C1	176.0 (4)	C22A—C23A—O21A—C21A	−2 (2)
C4—C5—C10—C1	−53.2 (5)	C22A—C20—C21A—O21A	−8.1 (15)
C6—C5—C10—C19	−67.3 (5)	C17—C20—C21A—O21A	−177.9 (10)
C4—C5—C10—C19	63.4 (5)	C23A—O21A—C21A—C20	7 (2)
C6—C5—C10—C9	58.1 (5)	O21A—C23A—C22A—C20	−3 (3)
C4—C5—C10—C9	−171.1 (4)	C21A—C20—C22A—C23A	6.4 (17)
O1—C1—C10—C5	−157.9 (5)	C17—C20—C22A—C23A	175.7 (13)
C2—C1—C10—C5	24.3 (6)	C22B—C23B—O21B—C21B	−20 (2)
O1—C1—C10—C19	78.8 (6)	C22B—C20—C21B—O21B	−4.2 (16)
C2—C1—C10—C19	−99.0 (5)	C17—C20—C21B—O21B	173.3 (11)
O1—C1—C10—C9	−47.2 (6)	C23B—O21B—C21B—C20	15 (2)
C2—C1—C10—C9	135.0 (5)	O21B—C23B—C22B—C20	18 (2)
C11—C9—C10—C5	178.4 (4)	C21B—C20—C22B—C23B	−8.7 (16)
C8—C9—C10—C5	−51.0 (4)	C17—C20—C22B—C23B	174.1 (11)
C11—C9—C10—C1	66.8 (5)	C6—O6—C28—O28	176.0 (4)
C8—C9—C10—C1	−162.6 (4)	C6—O6—C28—C4	−8.9 (5)
C11—C9—C10—C19	−54.9 (5)	C3—C4—C28—O28	−39.2 (8)
C8—C9—C10—C19	75.8 (5)	C5—C4—C28—O28	−153.3 (5)
C10—C9—C11—C12	−136.0 (4)	C29—C4—C28—O28	85.6 (7)
C8—C9—C11—C12	91.1 (5)	C3—C4—C28—O6	146.3 (5)
C27B—O27—C12—O12	14 (2)	C5—C4—C28—O6	32.3 (4)
C27A—O27—C12—O12	−19 (3)	C29—C4—C28—O6	−88.9 (4)

(II) (4α,5α,6α,7α,15α)-7,15:21,23-diepoxy-6-hydroxy- 4,8-dimethyl-1-oxo-18,24-dinor-11,12-secochola-2,16,20,22-tetraene-4,11- dicarboxylic acid γ-lactone methyl ester

Crystal data

C27H30O7	Dx = 1.325 Mg m^−3
Mr = 466.51	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 9.026 (2) Å	θ = 5–12°
b = 14.009 (18) Å	µ = 0.10 mm^−1
c = 18.495 (5) Å	T = 293 K
V = 2339 (3) Å^3	Rod, colourless
Z = 4	0.40 × 0.25 × 0.20 mm
F(000) = 992

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.019
Radiation source: fine-focus sealed tube	θmax = 30.6°, θmin = 2.2°
Graphite monochromator	h = 0→12
non–profiled ω/2θ scans	k = 0→19
3895 measured reflections	l = 0→26
3864 independent reflections	3 standard reflections every 200 reflections
1434 reflections with I > 2σ(I)	intensity decay: 3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full with fixed elements per cycle	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.066	H-atom parameters constrained
wR(F^2) = 0.198	w = 1/[σ^2(Fo^2) + (0.0844P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.001
3864 reflections	Δρmax = 0.23 e Å^−3
308 parameters	Δρmin = −0.23 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.015 (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
C1	0.6506 (6)	0.0539 (4)	0.2753 (3)	0.0511 (14)
C2	0.6964 (7)	0.0524 (4)	0.3517 (3)	0.0575 (16)
H2	0.7372	−0.0040	0.3693	0.069*
C3	0.6839 (7)	0.1261 (4)	0.3983 (3)	0.0557 (15)
H3	0.7197	0.1208	0.4453	0.067*
C4	0.6124 (7)	0.2157 (4)	0.3736 (3)	0.0492 (14)
C5	0.6326 (6)	0.2219 (3)	0.2923 (2)	0.0392 (12)
H5	0.7405	0.2196	0.2866	0.047*
C6	0.5963 (7)	0.3239 (3)	0.2751 (2)	0.0436 (13)
H6	0.4887	0.3337	0.2747	0.052*
C7	0.6613 (6)	0.3497 (3)	0.2035 (3)	0.0454 (13)
H7	0.6256	0.4129	0.1889	0.054*
C8	0.6250 (6)	0.2757 (3)	0.1430 (2)	0.0431 (13)
C9	0.6489 (6)	0.1696 (3)	0.1678 (3)	0.0449 (13)
H9	0.7561	0.1633	0.1746	0.054*
C10	0.5795 (6)	0.1434 (4)	0.2431 (3)	0.0453 (13)
C11	0.6101 (7)	0.0986 (4)	0.1061 (3)	0.0616 (17)
H11A	0.5157	0.0691	0.1177	0.074*
H11B	0.5964	0.1350	0.0620	0.074*
C12	0.7183 (9)	0.0214 (5)	0.0912 (3)	0.069 (2)
C15	0.7206 (8)	0.3623 (4)	0.0217 (3)	0.0624 (17)
H13A	0.7745	0.3396	−0.0202	0.075*
H13B	0.6156	0.3631	0.0107	0.075*
C14	0.7524 (7)	0.2996 (4)	0.0881 (3)	0.0492 (14)
H14	0.7986	0.2399	0.0721	0.059*
C13	0.8669 (6)	0.3577 (4)	0.1334 (3)	0.0477 (13)
C17	0.8515 (6)	0.4584 (4)	0.1046 (3)	0.0483 (13)
C16	0.7733 (7)	0.4593 (4)	0.0440 (3)	0.0591 (16)
H17	0.7532	0.5146	0.0179	0.071*
C19	0.4102 (7)	0.1268 (5)	0.2428 (4)	0.0654 (17)
H19A	0.3618	0.1807	0.2211	0.098*
H19B	0.3759	0.1190	0.2915	0.098*
H19C	0.3880	0.0703	0.2154	0.098*
C20	0.9101 (6)	0.5411 (4)	0.1430 (3)	0.0521 (15)
C21	0.9596 (7)	0.5456 (4)	0.2124 (3)	0.0605 (16)
H21	0.9678	0.4930	0.2428	0.073*
C22	0.9188 (7)	0.6382 (4)	0.1174 (3)	0.0566 (15)
H22	0.8951	0.6597	0.0712	0.068*
C23	0.9674 (7)	0.6912 (4)	0.1725 (4)	0.0692 (18)
H23	0.9803	0.7570	0.1707	0.083*
C27	0.9682 (9)	−0.0301 (6)	0.0908 (4)	0.096 (2)
H27A	1.0638	−0.0068	0.1053	0.144*
H27B	0.9693	−0.0439	0.0400	0.144*
H27C	0.9454	−0.0872	0.1173	0.144*
C28	0.6828 (7)	0.3113 (4)	0.3930 (3)	0.0531 (15)
C29	0.4535 (7)	0.2206 (4)	0.4051 (3)	0.0668 (18)
H29A	0.4027	0.1618	0.3954	0.100*
H29B	0.4007	0.2725	0.3831	0.100*
H29C	0.4586	0.2306	0.4564	0.100*
C30	0.4696 (7)	0.2979 (5)	0.1143 (3)	0.0609 (16)
H30A	0.4441	0.2529	0.0772	0.091*
H30B	0.4679	0.3613	0.0946	0.091*
H30C	0.3993	0.2935	0.1531	0.091*
C18	1.0245 (7)	0.3206 (4)	0.1310 (3)	0.0647 (18)
H31A	1.0863	0.3596	0.1612	0.097*
H31B	1.0603	0.3229	0.0821	0.097*
H31C	1.0267	0.2559	0.1481	0.097*
O1	0.6672 (5)	−0.0196 (3)	0.2390 (2)	0.0720 (12)
O12	0.6786 (8)	−0.0550 (4)	0.0648 (3)	0.114 (2)
O7	0.8194 (4)	0.3509 (2)	0.20789 (16)	0.0462 (9)
O6	0.6638 (4)	0.3739 (2)	0.33638 (17)	0.0521 (10)
O21	0.9957 (5)	0.6362 (3)	0.2319 (2)	0.0701 (12)
O27	0.8561 (5)	0.0424 (3)	0.1059 (2)	0.0744 (13)
O28	0.7461 (6)	0.3362 (3)	0.44667 (19)	0.0703 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.050 (3)	0.031 (3)	0.072 (4)	−0.006 (3)	0.010 (3)	0.004 (3)
C2	0.059 (4)	0.038 (3)	0.075 (4)	0.003 (3)	0.008 (3)	0.015 (3)
C3	0.074 (4)	0.047 (3)	0.047 (3)	−0.006 (3)	0.005 (3)	0.010 (3)
C4	0.066 (4)	0.038 (3)	0.043 (3)	0.001 (3)	0.010 (3)	0.002 (2)
C5	0.047 (3)	0.024 (2)	0.047 (3)	0.000 (2)	0.008 (3)	0.001 (2)
C6	0.051 (3)	0.037 (3)	0.043 (3)	0.005 (2)	0.004 (3)	−0.006 (2)
C7	0.055 (4)	0.029 (3)	0.052 (3)	0.004 (3)	0.003 (3)	−0.001 (2)
C8	0.054 (3)	0.036 (3)	0.039 (3)	0.004 (3)	0.000 (3)	−0.002 (2)
C9	0.048 (3)	0.034 (3)	0.052 (3)	−0.007 (3)	0.006 (3)	−0.005 (2)
C10	0.050 (3)	0.037 (3)	0.048 (3)	0.000 (3)	0.006 (3)	0.000 (3)
C11	0.070 (4)	0.047 (3)	0.067 (4)	−0.004 (3)	0.001 (3)	−0.023 (3)
C12	0.095 (6)	0.051 (4)	0.061 (4)	0.000 (4)	0.007 (4)	−0.020 (3)
C15	0.089 (5)	0.055 (3)	0.043 (3)	0.001 (4)	−0.001 (3)	−0.004 (3)
C14	0.074 (4)	0.035 (3)	0.039 (3)	0.004 (3)	0.002 (3)	−0.006 (2)
C13	0.054 (4)	0.051 (3)	0.037 (3)	0.005 (3)	0.009 (3)	0.005 (2)
C17	0.064 (4)	0.045 (3)	0.036 (3)	−0.004 (3)	0.011 (3)	0.007 (2)
C16	0.077 (4)	0.050 (3)	0.050 (3)	0.000 (3)	0.006 (3)	0.013 (3)
C19	0.055 (4)	0.062 (4)	0.079 (4)	−0.006 (3)	0.000 (3)	−0.002 (4)
C20	0.055 (3)	0.044 (3)	0.057 (3)	−0.001 (3)	0.009 (3)	0.007 (3)
C21	0.080 (4)	0.038 (3)	0.064 (4)	−0.002 (3)	−0.004 (4)	0.003 (3)
C22	0.059 (4)	0.051 (3)	0.060 (3)	−0.005 (3)	−0.004 (3)	0.011 (3)
C23	0.068 (5)	0.043 (3)	0.096 (5)	−0.001 (3)	−0.015 (4)	0.015 (4)
C27	0.102 (6)	0.088 (5)	0.098 (5)	0.041 (5)	0.018 (5)	−0.007 (5)
C28	0.066 (4)	0.051 (3)	0.042 (3)	0.003 (3)	0.011 (3)	−0.005 (3)
C29	0.070 (4)	0.058 (4)	0.072 (4)	−0.001 (3)	0.023 (4)	0.009 (3)
C30	0.062 (4)	0.060 (4)	0.061 (4)	0.006 (3)	−0.014 (3)	−0.007 (3)
C18	0.069 (4)	0.057 (4)	0.069 (4)	0.001 (3)	0.013 (4)	0.004 (3)
O1	0.098 (3)	0.0340 (19)	0.084 (3)	0.000 (2)	0.001 (3)	−0.005 (2)
O12	0.149 (5)	0.068 (3)	0.124 (4)	−0.021 (4)	0.023 (4)	−0.048 (3)
O7	0.057 (2)	0.0403 (19)	0.0414 (19)	−0.0050 (19)	0.0057 (18)	0.0045 (16)
O6	0.077 (3)	0.0366 (18)	0.0422 (18)	−0.003 (2)	0.005 (2)	−0.0057 (16)
O21	0.082 (3)	0.046 (2)	0.082 (3)	−0.005 (2)	−0.012 (3)	−0.001 (2)
O27	0.070 (3)	0.062 (3)	0.092 (3)	0.007 (3)	0.003 (3)	−0.019 (2)
O28	0.106 (4)	0.061 (3)	0.044 (2)	−0.006 (3)	−0.004 (2)	−0.0069 (19)

Geometric parameters (Å, º)

C1—O1	1.239 (7)	C14—C13	1.559 (8)
C1—C2	1.472 (9)	C14—H14	0.9800
C1—C10	1.530 (8)	C13—O7	1.446 (6)
C2—C3	1.350 (8)	C13—C18	1.514 (8)
C2—H2	0.9300	C13—C17	1.515 (8)
C3—C4	1.483 (8)	C17—C16	1.324 (8)
C3—H3	0.9300	C17—C20	1.458 (8)
C4—C5	1.516 (7)	C16—H17	0.9300
C4—C28	1.524 (8)	C19—H19A	0.9600
C4—C29	1.550 (9)	C19—H19B	0.9600
C5—C6	1.501 (7)	C19—H19C	0.9600
C5—C10	1.506 (7)	C20—C21	1.359 (8)
C5—H5	0.9800	C20—C22	1.443 (8)
C6—O6	1.466 (6)	C21—O21	1.360 (7)
C6—C7	1.492 (7)	C21—H21	0.9300
C6—H6	0.9800	C22—C23	1.335 (9)
C7—O7	1.429 (7)	C22—H22	0.9300
C7—C8	1.559 (7)	C23—O21	1.366 (8)
C7—H7	0.9800	C23—H23	0.9300
C8—C30	1.532 (8)	C27—O27	1.460 (8)
C8—C9	1.571 (7)	C27—H27A	0.9600
C8—C14	1.570 (8)	C27—H27B	0.9600
C9—C11	1.554 (7)	C27—H27C	0.9600
C9—C10	1.569 (7)	C28—O28	1.198 (7)
C9—H9	0.9800	C28—O6	1.377 (6)
C10—C19	1.545 (8)	C29—H29A	0.9600
C11—C12	1.483 (9)	C29—H29B	0.9600
C11—H11A	0.9700	C29—H29C	0.9600
C11—H11B	0.9700	C30—H30A	0.9600
C12—O12	1.230 (8)	C30—H30B	0.9600
C12—O27	1.307 (8)	C30—H30C	0.9600
C15—C16	1.497 (8)	C18—H31A	0.9600
C15—C14	1.537 (8)	C18—H31B	0.9600
C15—H13A	0.9700	C18—H31C	0.9600
C15—H13B	0.9700
O1—C1—C2	118.4 (5)	C15—C14—C8	120.1 (5)
O1—C1—C10	121.4 (5)	C13—C14—C8	104.4 (4)
C2—C1—C10	120.2 (5)	C15—C14—H14	109.0
C3—C2—C1	125.4 (6)	C13—C14—H14	109.0
C3—C2—H2	117.3	C8—C14—H14	109.0
C1—C2—H2	117.3	O7—C13—C18	106.5 (5)
C2—C3—C4	119.1 (5)	O7—C13—C17	111.7 (4)
C2—C3—H3	120.4	C18—C13—C17	113.3 (5)
C4—C3—H3	120.4	O7—C13—C14	106.3 (4)
C3—C4—C5	107.6 (5)	C18—C13—C14	115.3 (5)
C3—C4—C28	119.3 (5)	C17—C13—C14	103.7 (4)
C5—C4—C28	97.6 (4)	C16—C17—C20	126.8 (5)
C3—C4—C29	108.9 (5)	C16—C17—C13	110.8 (5)
C5—C4—C29	118.8 (5)	C20—C17—C13	122.3 (5)
C28—C4—C29	105.0 (5)	C17—C16—C15	113.2 (5)
C6—C5—C4	103.8 (4)	C17—C16—H17	123.4
C6—C5—C10	119.8 (4)	C15—C16—H17	123.4
C4—C5—C10	121.3 (4)	C10—C19—H19A	109.5
C6—C5—H5	103.0	C10—C19—H19B	109.5
C4—C5—H5	103.0	H19A—C19—H19B	109.5
C10—C5—H5	103.0	C10—C19—H19C	109.5
O6—C6—C7	114.1 (4)	H19A—C19—H19C	109.5
O6—C6—C5	101.5 (4)	H19B—C19—H19C	109.5
C7—C6—C5	109.4 (4)	C21—C20—C22	104.4 (6)
O6—C6—H6	110.5	C21—C20—C17	128.0 (6)
C7—C6—H6	110.5	C22—C20—C17	127.4 (5)
C5—C6—H6	110.5	O21—C21—C20	111.9 (6)
O7—C7—C6	110.2 (5)	O21—C21—H21	124.1
O7—C7—C8	105.0 (4)	C20—C21—H21	124.1
C6—C7—C8	113.2 (4)	C23—C22—C20	106.9 (6)
O7—C7—H7	109.5	C23—C22—H22	126.5
C6—C7—H7	109.5	C20—C22—H22	126.5
C8—C7—H7	109.5	C22—C23—O21	111.2 (6)
C30—C8—C9	114.8 (5)	C22—C23—H23	124.4
C30—C8—C7	107.8 (5)	O21—C23—H23	124.4
C9—C8—C7	112.9 (4)	O27—C27—H27A	109.5
C30—C8—C14	113.8 (4)	O27—C27—H27B	109.5
C9—C8—C14	106.9 (4)	H27A—C27—H27B	109.5
C7—C8—C14	99.7 (4)	O27—C27—H27C	109.5
C11—C9—C8	111.1 (4)	H27A—C27—H27C	109.5
C11—C9—C10	114.3 (4)	H27B—C27—H27C	109.5
C8—C9—C10	115.2 (4)	O28—C28—O6	120.2 (5)
C11—C9—H9	105.0	O28—C28—C4	130.6 (5)
C8—C9—H9	105.0	O6—C28—C4	109.2 (5)
C10—C9—H9	105.0	C4—C29—H29A	109.5
C5—C10—C1	103.2 (4)	C4—C29—H29B	109.5
C5—C10—C19	115.3 (5)	H29A—C29—H29B	109.5
C1—C10—C19	107.0 (5)	C4—C29—H29C	109.5
C5—C10—C9	103.8 (4)	H29A—C29—H29C	109.5
C1—C10—C9	111.7 (4)	H29B—C29—H29C	109.5
C19—C10—C9	115.3 (5)	C8—C30—H30A	109.5
C12—C11—C9	117.1 (6)	C8—C30—H30B	109.5
C12—C11—H11A	108.0	H30A—C30—H30B	109.5
C9—C11—H11A	108.0	C8—C30—H30C	109.5
C12—C11—H11B	108.0	H30A—C30—H30C	109.5
C9—C11—H11B	108.0	H30B—C30—H30C	109.5
H11A—C11—H11B	107.3	C13—C18—H31A	109.5
O12—C12—O27	123.8 (7)	C13—C18—H31B	109.5
O12—C12—C11	121.1 (7)	H31A—C18—H31B	109.5
O27—C12—C11	115.1 (6)	C13—C18—H31C	109.5
C16—C15—C14	103.9 (5)	H31A—C18—H31C	109.5
C16—C15—H13A	111.0	H31B—C18—H31C	109.5
C14—C15—H13A	111.0	C7—O7—C13	104.1 (4)
C16—C15—H13B	111.0	C28—O6—C6	109.6 (4)
C14—C15—H13B	111.0	C21—O21—C23	105.5 (5)
H13A—C15—H13B	109.0	C12—O27—C27	117.7 (6)
C15—C14—C13	104.7 (4)
O1—C1—C2—C3	−179.2 (6)	C9—C11—C12—O27	−29.0 (9)
C10—C1—C2—C3	−1.3 (9)	C16—C15—C14—C13	−18.0 (6)
C1—C2—C3—C4	3.1 (10)	C16—C15—C14—C8	98.7 (6)
C2—C3—C4—C5	−26.4 (8)	C30—C8—C14—C15	14.5 (7)
C2—C3—C4—C28	−136.1 (6)	C9—C8—C14—C15	142.3 (5)
C2—C3—C4—C29	103.5 (6)	C7—C8—C14—C15	−100.0 (5)
C3—C4—C5—C6	−165.0 (5)	C30—C8—C14—C13	131.5 (5)
C28—C4—C5—C6	−40.9 (6)	C9—C8—C14—C13	−100.8 (5)
C29—C4—C5—C6	70.8 (6)	C7—C8—C14—C13	16.9 (5)
C3—C4—C5—C10	56.5 (7)	C15—C14—C13—O7	136.3 (5)
C28—C4—C5—C10	−179.4 (5)	C8—C14—C13—O7	9.3 (6)
C29—C4—C5—C10	−67.6 (7)	C15—C14—C13—C18	−105.9 (6)
C4—C5—C6—O6	39.2 (5)	C8—C14—C13—C18	127.1 (5)
C10—C5—C6—O6	178.5 (5)	C15—C14—C13—C17	18.5 (6)
C4—C5—C6—C7	160.0 (5)	C8—C14—C13—C17	−108.6 (4)
C10—C5—C6—C7	−60.7 (7)	O7—C13—C17—C16	−126.5 (5)
O6—C6—C7—O7	45.1 (6)	C18—C13—C17—C16	113.2 (6)
C5—C6—C7—O7	−67.8 (5)	C14—C13—C17—C16	−12.5 (6)
O6—C6—C7—C8	162.2 (4)	O7—C13—C17—C20	50.3 (7)
C5—C6—C7—C8	49.3 (6)	C18—C13—C17—C20	−70.0 (7)
O7—C7—C8—C30	−158.0 (5)	C14—C13—C17—C20	164.3 (5)
C6—C7—C8—C30	81.8 (6)	C20—C17—C16—C15	−175.7 (6)
O7—C7—C8—C9	74.2 (6)	C13—C17—C16—C15	0.9 (7)
C6—C7—C8—C9	−46.1 (7)	C14—C15—C16—C17	11.3 (7)
O7—C7—C8—C14	−38.9 (5)	C16—C17—C20—C21	163.2 (7)
C6—C7—C8—C14	−159.1 (5)	C13—C17—C20—C21	−13.0 (10)
C30—C8—C9—C11	55.3 (6)	C16—C17—C20—C22	−12.1 (10)
C7—C8—C9—C11	179.5 (5)	C13—C17—C20—C22	171.7 (6)
C14—C8—C9—C11	−71.9 (6)	C22—C20—C21—O21	0.9 (7)
C30—C8—C9—C10	−76.7 (6)	C17—C20—C21—O21	−175.2 (6)
C7—C8—C9—C10	47.5 (7)	C21—C20—C22—C23	−1.6 (7)
C14—C8—C9—C10	156.1 (4)	C17—C20—C22—C23	174.5 (6)
C6—C5—C10—C1	175.0 (5)	C20—C22—C23—O21	1.8 (8)
C4—C5—C10—C1	−52.9 (7)	C3—C4—C28—O28	−36.3 (9)
C6—C5—C10—C19	−68.7 (7)	C5—C4—C28—O28	−151.4 (7)
C4—C5—C10—C19	63.4 (7)	C29—C4—C28—O28	86.0 (8)
C6—C5—C10—C9	58.3 (6)	C3—C4—C28—O6	144.1 (5)
C4—C5—C10—C9	−169.6 (5)	C5—C4—C28—O6	29.0 (6)
O1—C1—C10—C5	−159.3 (5)	C29—C4—C28—O6	−93.6 (5)
C2—C1—C10—C5	22.9 (7)	C6—C7—O7—C13	169.1 (4)
O1—C1—C10—C19	78.7 (7)	C8—C7—O7—C13	46.9 (5)
C2—C1—C10—C19	−99.1 (6)	C18—C13—O7—C7	−158.0 (4)
O1—C1—C10—C9	−48.3 (7)	C17—C13—O7—C7	77.8 (5)
C2—C1—C10—C9	133.9 (5)	C14—C13—O7—C7	−34.6 (5)
C11—C9—C10—C5	−179.9 (5)	O28—C28—O6—C6	174.7 (6)
C8—C9—C10—C5	−49.4 (6)	C4—C28—O6—C6	−5.7 (6)
C11—C9—C10—C1	69.5 (6)	C7—C6—O6—C28	−138.3 (5)
C8—C9—C10—C1	−160.0 (5)	C5—C6—O6—C28	−20.7 (6)
C11—C9—C10—C19	−52.9 (7)	C20—C21—O21—C23	0.2 (7)
C8—C9—C10—C19	77.6 (6)	C22—C23—O21—C21	−1.3 (7)
C8—C9—C11—C12	132.5 (6)	O12—C12—O27—C27	−0.8 (10)
C10—C9—C11—C12	−95.0 (7)	C11—C12—O27—C27	−178.8 (6)
C9—C11—C12—O12	153.0 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O12^i	0.93	2.56	3.466 (8)	163
C6—H6···O1^ii	0.98	2.50	3.244 (7)	132
C16—H17···O28^iii	0.93	2.47	3.387 (8)	169

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