2′,3′-Dehydrosalannol

The title compound, methyl (2aS,3R,5R,5aS,6S,6aS,8R,9aS,10aR,10bR,10cS)-8-(3-furyl)-2a,4,5,5a,6,6a,8,9,9a,10a,10b,10c-dodeca­hydro-3-hydroxy-2a,5a,6a,7-tetra­methyl-5-(3-methylbut-2-enoyl­oxy)-2H,3H-cyclo­penta­[4′,5′]­furo­[2′,3′:6,5]benzo[cd]­isobenzo­furan-6-acetate, C₃₂H₄₂O₈, was isolated from uncrushed green leaves of Azadirachta indica A. Juss (neem) and has been found to possess antifeedant activity against Spodptera litura. The conformations of the functional groups are similar to those of 3-des­acetyl­salannin, which was isolated from neem kernels. The mol­ecules are linked into chains by intermolecular O—H...O hydrogen bonds.

S1. Comment

Azadirachta indica A. Juss, an indigenous tree of the Indian subcontinent, has attracted the attention of many chemists and biologists all over the world during the past two decades, due to the plethora of biological activities found in the compounds extracted therefrom, in particular insect-antifeedant and growth-inhibition activities (Singh, 1993; Eppler, 1995; Locke, 1995; Schmutterer, 1995). The title compound, (I), was isolated from the hexane extract of uncrushed green neem leaves and purified by preparative high-performance liquid chromatography techniques.

The antifeedant activity of (I) against Spodptera litura (Suresh et al., 2002) is similar to that of 3-desacetylsalannin (DAS) (Kabaleeswaran et al., 1999), which was isolated from neem kernels. The difference between the structure of (I) and that of DAS is that in (I), a 3-methylbutenoyl (O-senecioxy ester) group has replaced the 2-methylbutenoyl (O-tigloyl) group at C1 in DAS. Due to this difference in the chemical structure, there is a conformational variation in the orientation of this functional group in these structures, and this is evident in the different values for the C1—O1—C31—C32 dihedral angle [-177.6 (3)° in (I) and -171.9 (2)° in DAS]. Other functional groups, such as the –CH₂COOCH₃ group at C9 [C10—C9—C11—C12 - 149.1 (4)° in (I) and -149.6 (2)° in DAS] and the furan ring (E) at C17 [C16—C17—C20—C22 64.5 (6)° in (I) and 63.8 (5)° in DAS], show similar conformations. \sch

Rings A and B in (I) are in chair conformations, as is evident from the ring puckering amplitudes (Cremer & Pople, 1975); Q_T = 0.522 (5) Å, θ = 5.8 (5)° and ϕ₂ = -178 (5)°, and Q_T = 0.552 (4) Å, θ = 7.0 (5)° and ϕ₂= -29 (4)°, respectively. Ring F is in a half-chair conformation [q₂ = 0.454 (4) Å and ϕ₂ = 93.6 (5)°], with atoms C4 and C5 deviating from the least-squares plane defined by atoms C6, O6 and C28 by 0.450 (5) and -0.295 (4) Å, respectively. Ring I also adopts a half-chair conformation [q₂ = 0.405 (4) Å and ϕ₂= 241.1 (6)°], with atoms C7 and C8 deviating from the plane defined by atoms O7, C14 and C15 by -0.214 (4) and 0.459 (4) Å, respectively, while ring D' is in an envelope conformation [q₂ = 0.319 (5) Å and ϕ₂ = 103.8 (8)°], with atom C16 at the apex of the envelope. Ring E adopts a planar conformation (Nardelli, 1995). The ring junctions A/B, A/F and B/F are trans-fused. The B/I junction is cis-fused, and I/D' is quasi-trans-fused due to the sp² hybridization of C13.

The molecules in the crystal lattice of (I) are stabilized by an O—H···O hydrogen bond between atoms O3 and O6(-x, y + 1/2, 1/2 - z). This hydrogen bond links the molecules into infinite one-dimensional chains which run parallel to the y axis, and can be denoted by the graph set motif C(6) (Berstein et al., 1995). A similar pattern of hydrogen bonds was also observed in the related structure of DAS (Kabaleeswaran et al., 1999).

S2. Experimental

Fresh uncrushed green leaves of Azadirachta indica A. Juss (neem) (5 kg) were soaked in hexane (25 l) for 24 h and the decanted n-hexane extract was concentrated to 1 l in vacuo. The hexane extract was then partitioned with 95% MeOH-water. The methanol layer was concentrated to dryness in vacuo, resulting in a residue (16 g) which was subjected to primary preparative high-performance liquid chromatography (HPLC) separation (Shimadzu ODS column, 2 × 25 cm, 215 nm) using MeOH:H₂O (70:30) as eluent at a flow rate of 4 ml min^-1 to yield eight peaks with retention times of 6.9, 11.9, 14.1, 18.3, 22.8, 32.2, 47.7 and 61.4 min. The peak with a retention time of 18.3 min (262 mg) was further subjected to semi-preparative HPLC on an RP18 column (E-Merck, ODS, 10 µm, 9.6 mm × 25 cm) using acetonitrile-water (55:45) as eluent at a flow rate of 8 ml min^-1. On evaporation of the solvent, this yielded the title compound as a white solid (80 mg) with a melting point of 457 K. This compound was identified as 2'3'-dehydrosalannol by comparison of its spectroscopic data (one- and two-dimensional NMR) with published data (Garg & Bhakuni, 1985) (positions 2' and 3' are numbered as C32 and C34, respectively, in Fig. 1). Good diffraction-quality crystals of (I) were obtained from a solution of acetonitrile and water (Ratio?) at 293 K.

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 an inconclusive value (Flack & Bernadinelli, 2000) of -0.3 (4). Therefore, the 133 Friedel equivalents were merged before the final refinement. The enantiomer employed in the refined model was chosen to agree with the accepted configuration of limonoids (Narayanan et al., 1964; Harris et al., 1968; Henderson et al., 1968). The methyl and hydroxy H atoms were constrained to an ideal geometry (C—H = 0.96 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).

Computing details

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 view of the molecular structure of (I) with 30% probability displacement ellipsoids and the atomic numbering scheme. H atoms have been omitted for clarity.

methyl (2aS,3R,5R,5aS,6S,6aS,8R,9aS,10aR,10bR,10cS)]- 8-(3-furyl)-2a,4,5,5a,6,6a,8,9,9a,10a,10b,10c-dodecahydro-3-hydroxy- 2a,5a,6a,7-tetramethyl-5-(3-methylbut-2-enoyloxy)-2H,3H- cyclopenta[4',5']furo[2',3':6,5]benzo[cd]isobenzofuran-6-acetate

Crystal data

C32H42O8	F(000) = 1192
Mr = 554.66	Dx = 1.245 Mg m^−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 7.220 (2) Å	θ = 15–30°
b = 12.728 (2) Å	µ = 0.72 mm^−1
c = 32.210 (6) Å	T = 293 K
V = 2960.0 (11) Å^3	Needle, colourless
Z = 4	0.33 × 0.23 × 0.13 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.028
Radiation source: fine-focus sealed tube	θmax = 75.1°, θmin = 2.7°
Graphite monochromator	h = −2→8
non–profiled ω/2θ scans	k = −4→15
3407 measured reflections	l = −10→40
3280 independent reflections	3 standard reflections every 60 min
2091 reflections with I > 2σ(I)	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)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.151	Calculated w = 1/[σ^2(Fo^2) + (0.0876P)^2 + 0.3127P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
3280 reflections	Δρmax = 0.21 e Å^−3
367 parameters	Δρmin = −0.20 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: 0.0025 (4)

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	0.1417 (4)	0.84934 (18)	0.16929 (8)	0.0529 (7)
O3	−0.0312 (4)	0.8124 (2)	0.25251 (10)	0.0631 (8)
H3	−0.0627	0.8694	0.2430	0.095*
O6	0.1722 (5)	0.5228 (2)	0.26136 (8)	0.0605 (8)
O7	0.0670 (4)	0.50150 (19)	0.17641 (7)	0.0492 (7)
O12	0.1783 (6)	0.7262 (3)	0.06896 (10)	0.0809 (11)
O21	−0.1623 (8)	0.4012 (5)	−0.02194 (13)	0.1267 (19)
O27	0.4531 (5)	0.6904 (3)	0.04168 (10)	0.0824 (11)
O31	0.2388 (6)	0.9958 (3)	0.13869 (15)	0.1210 (18)
C1	0.3137 (6)	0.8420 (3)	0.19281 (14)	0.0516 (10)
H1	0.4075	0.8863	0.1795	0.062*
C2	0.2763 (7)	0.8838 (3)	0.23677 (14)	0.0593 (11)
H2A	0.3951	0.8948	0.2502	0.071*
H2B	0.2180	0.9521	0.2341	0.071*
C3	0.1573 (7)	0.8179 (3)	0.26592 (14)	0.0573 (11)
H3A	0.1614	0.8490	0.2937	0.069*
C4	0.2348 (7)	0.7062 (3)	0.26795 (12)	0.0528 (10)
C5	0.2588 (6)	0.6687 (2)	0.22303 (11)	0.0444 (9)
H5	0.1345	0.6739	0.2110	0.053*
C6	0.2914 (7)	0.5536 (3)	0.22740 (12)	0.0503 (10)
H6	0.4203	0.5425	0.2358	0.060*
C7	0.2588 (6)	0.4965 (3)	0.18728 (12)	0.0470 (9)
H7	0.2964	0.4229	0.1903	0.056*
C8	0.3676 (6)	0.5478 (3)	0.15042 (13)	0.0469 (9)
C9	0.3433 (6)	0.6709 (2)	0.14995 (12)	0.0457 (9)
H9	0.2113	0.6826	0.1446	0.055*
C10	0.3821 (6)	0.7261 (3)	0.19251 (13)	0.0467 (9)
C11	0.4435 (7)	0.7217 (3)	0.11341 (13)	0.0591 (11)
H11A	0.4631	0.7954	0.1195	0.071*
H11B	0.5641	0.6890	0.1104	0.071*
C12	0.3424 (8)	0.7129 (3)	0.07354 (14)	0.0601 (11)
C13	0.2799 (6)	0.4369 (3)	0.08379 (12)	0.0539 (11)
C14	0.2521 (6)	0.4987 (3)	0.11677 (11)	0.0454 (9)
C15	0.0571 (6)	0.4919 (3)	0.13197 (11)	0.0450 (9)
H15	−0.0173	0.5490	0.1202	0.054*
C16	−0.0072 (7)	0.3866 (3)	0.11495 (13)	0.0579 (11)
H16A	−0.1394	0.3871	0.1095	0.069*
H16B	0.0212	0.3300	0.1341	0.069*
C17	0.1048 (6)	0.3753 (3)	0.07405 (13)	0.0584 (12)
H17	0.1384	0.3012	0.0706	0.070*
C18	0.4497 (8)	0.4180 (4)	0.05835 (16)	0.0759 (15)
H18A	0.5409	0.4704	0.0647	0.114*
H18B	0.4187	0.4218	0.0294	0.114*
H18C	0.4986	0.3496	0.0646	0.114*
C19	0.5894 (7)	0.7299 (4)	0.20337 (16)	0.0674 (13)
H19A	0.6112	0.7847	0.2232	0.101*
H19B	0.6599	0.7436	0.1787	0.101*
H19C	0.6266	0.6636	0.2150	0.101*
C20	−0.0003 (8)	0.4095 (4)	0.03642 (14)	0.0671 (13)
C21	−0.0621 (12)	0.3462 (6)	0.00635 (18)	0.104 (2)
H21	−0.0395	0.2744	0.0050	0.125*
C22	−0.0644 (8)	0.5111 (5)	0.02672 (16)	0.0810 (15)
H22	−0.0441	0.5720	0.0420	0.097*
C23	−0.1605 (9)	0.5033 (7)	−0.00885 (19)	0.0976 (19)
H23	−0.2174	0.5590	−0.0225	0.117*
C27	0.3650 (11)	0.6814 (6)	0.00128 (16)	0.107 (2)
H27A	0.4570	0.6662	−0.0194	0.160*
H27B	0.3043	0.7463	−0.0054	0.160*
H27C	0.2754	0.6257	0.0019	0.160*
C28	0.1052 (8)	0.6177 (3)	0.28159 (12)	0.0633 (13)
H28A	0.1083	0.6096	0.3115	0.076*
H28B	−0.0211	0.6326	0.2732	0.076*
C29	0.4066 (8)	0.7039 (4)	0.29547 (15)	0.0764 (15)
H29A	0.4552	0.6337	0.2964	0.115*
H29B	0.3741	0.7259	0.3230	0.115*
H29C	0.4985	0.7505	0.2843	0.115*
C30	0.5677 (6)	0.5095 (3)	0.15092 (16)	0.0641 (12)
H30A	0.5696	0.4340	0.1510	0.096*
H30B	0.6286	0.5353	0.1754	0.096*
H30C	0.6309	0.5349	0.1267	0.096*
C31	0.1212 (7)	0.9304 (3)	0.14339 (15)	0.0616 (12)
C32	−0.0604 (8)	0.9285 (3)	0.12375 (14)	0.0637 (13)
H32	−0.1290	0.8672	0.1271	0.076*
C33	−0.0525 (10)	1.1063 (4)	0.09314 (18)	0.0953 (19)
H33A	−0.1359	1.1482	0.0769	0.143*
H33B	0.0607	1.0960	0.0781	0.143*
H33C	−0.0265	1.1416	0.1188	0.143*
C34	−0.1382 (7)	1.0037 (3)	0.10186 (13)	0.0589 (11)
C35	−0.3265 (9)	0.9922 (5)	0.0841 (2)	0.106 (2)
H35A	−0.3634	0.9198	0.0853	0.160*
H35B	−0.3258	1.0153	0.0557	0.160*
H35C	−0.4122	1.0342	0.0997	0.160*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0574 (18)	0.0355 (11)	0.0657 (16)	−0.0065 (12)	−0.0105 (15)	0.0085 (12)
O3	0.066 (2)	0.0473 (15)	0.075 (2)	0.0018 (14)	−0.0058 (18)	−0.0090 (14)
O6	0.090 (2)	0.0413 (13)	0.0501 (15)	−0.0048 (15)	0.0047 (16)	0.0032 (11)
O7	0.0564 (18)	0.0425 (12)	0.0487 (14)	−0.0059 (13)	0.0080 (13)	−0.0049 (11)
O12	0.081 (3)	0.096 (3)	0.066 (2)	0.015 (2)	−0.006 (2)	0.0087 (19)
O21	0.139 (5)	0.162 (5)	0.080 (3)	−0.051 (4)	−0.014 (3)	−0.002 (3)
O27	0.080 (3)	0.103 (3)	0.0637 (19)	−0.007 (2)	0.018 (2)	0.0014 (19)
O31	0.084 (3)	0.092 (3)	0.187 (4)	−0.036 (2)	−0.036 (3)	0.087 (3)
C1	0.051 (3)	0.0351 (17)	0.069 (3)	−0.0100 (17)	−0.014 (2)	0.0005 (17)
C2	0.072 (3)	0.0323 (17)	0.074 (3)	−0.0087 (19)	−0.009 (3)	−0.0088 (18)
C3	0.066 (3)	0.0465 (19)	0.059 (2)	−0.007 (2)	−0.009 (2)	−0.0156 (19)
C4	0.066 (3)	0.046 (2)	0.047 (2)	−0.004 (2)	−0.010 (2)	−0.0001 (16)
C5	0.054 (2)	0.0316 (15)	0.0470 (19)	−0.0027 (17)	−0.0056 (19)	0.0002 (14)
C6	0.063 (3)	0.0353 (17)	0.052 (2)	0.0037 (18)	−0.006 (2)	0.0024 (16)
C7	0.053 (3)	0.0301 (15)	0.058 (2)	0.0035 (17)	−0.002 (2)	0.0033 (16)
C8	0.042 (2)	0.0376 (16)	0.061 (2)	0.0011 (16)	0.003 (2)	−0.0009 (17)
C9	0.047 (2)	0.0371 (16)	0.053 (2)	−0.0064 (16)	0.004 (2)	0.0030 (16)
C10	0.043 (2)	0.0356 (16)	0.062 (2)	−0.0066 (16)	−0.007 (2)	−0.0003 (17)
C11	0.061 (3)	0.052 (2)	0.065 (3)	−0.007 (2)	0.006 (2)	0.0067 (19)
C12	0.073 (3)	0.051 (2)	0.056 (2)	−0.003 (2)	0.010 (3)	0.008 (2)
C13	0.060 (3)	0.046 (2)	0.056 (2)	0.0007 (19)	0.016 (2)	−0.0061 (17)
C14	0.046 (2)	0.0382 (16)	0.052 (2)	0.0015 (18)	0.0080 (19)	−0.0008 (16)
C15	0.051 (2)	0.0394 (17)	0.0445 (19)	−0.0035 (18)	0.0111 (18)	−0.0063 (16)
C16	0.063 (3)	0.050 (2)	0.060 (2)	−0.010 (2)	0.012 (2)	−0.0103 (19)
C17	0.068 (3)	0.047 (2)	0.060 (2)	−0.009 (2)	0.020 (2)	−0.0172 (19)
C18	0.071 (3)	0.077 (3)	0.079 (3)	0.000 (3)	0.029 (3)	−0.020 (3)
C19	0.057 (3)	0.064 (3)	0.081 (3)	−0.006 (2)	−0.014 (3)	−0.004 (2)
C20	0.073 (3)	0.072 (3)	0.056 (3)	−0.020 (2)	0.013 (2)	−0.012 (2)
C21	0.147 (6)	0.098 (4)	0.067 (3)	−0.042 (5)	−0.008 (4)	−0.011 (3)
C22	0.073 (4)	0.097 (4)	0.073 (3)	0.001 (3)	0.005 (3)	−0.001 (3)
C23	0.079 (4)	0.130 (6)	0.083 (4)	−0.004 (4)	0.003 (3)	0.023 (4)
C27	0.125 (6)	0.140 (6)	0.056 (3)	−0.022 (5)	0.013 (4)	−0.009 (3)
C28	0.097 (4)	0.048 (2)	0.045 (2)	−0.005 (2)	0.005 (3)	−0.0010 (17)
C29	0.094 (4)	0.067 (3)	0.068 (3)	−0.003 (3)	−0.025 (3)	−0.003 (2)
C30	0.048 (3)	0.061 (2)	0.084 (3)	0.013 (2)	0.004 (3)	−0.004 (3)
C31	0.072 (3)	0.0393 (18)	0.074 (3)	−0.002 (2)	−0.006 (3)	0.0131 (19)
C32	0.075 (3)	0.0413 (19)	0.075 (3)	−0.011 (2)	−0.008 (3)	0.016 (2)
C33	0.116 (5)	0.061 (3)	0.109 (4)	−0.012 (3)	−0.017 (4)	0.036 (3)
C34	0.075 (3)	0.050 (2)	0.051 (2)	−0.003 (2)	0.003 (2)	0.0097 (18)
C35	0.091 (4)	0.098 (4)	0.130 (5)	−0.008 (4)	−0.034 (4)	0.049 (4)

Geometric parameters (Å, º)

O1—C31	1.335 (5)	C13—C17	1.521 (6)
O1—C1	1.458 (5)	C14—C15	1.493 (6)
O3—C3	1.430 (6)	C15—C16	1.520 (5)
O3—H3	0.8200	C15—H15	0.9800
O6—C6	1.446 (5)	C16—C17	1.553 (6)
O6—C28	1.455 (5)	C16—H16A	0.9700
O7—C7	1.430 (5)	C16—H16B	0.9700
O7—C15	1.439 (4)	C17—C20	1.494 (7)
O12—C12	1.206 (6)	C17—H17	0.9800
O21—C21	1.358 (8)	C18—H18A	0.9600
O21—C23	1.366 (9)	C18—H18B	0.9600
O27—C12	1.332 (5)	C18—H18C	0.9600
O27—C27	1.453 (7)	C19—H19A	0.9600
O31—C31	1.199 (5)	C19—H19B	0.9600
C1—C2	1.537 (6)	C19—H19C	0.9600
C1—C10	1.555 (5)	C20—C21	1.336 (7)
C1—H1	0.9800	C20—C22	1.409 (7)
C2—C3	1.524 (6)	C21—H21	0.9300
C2—H2A	0.9700	C22—C23	1.343 (8)
C2—H2B	0.9700	C22—H22	0.9300
C3—C4	1.529 (6)	C23—H23	0.9300
C3—H3A	0.9800	C27—H27A	0.9600
C4—C29	1.525 (6)	C27—H27B	0.9600
C4—C28	1.529 (6)	C27—H27C	0.9600
C4—C5	1.533 (5)	C28—H28A	0.9700
C5—C6	1.490 (4)	C28—H28B	0.9700
C5—C10	1.514 (5)	C29—H29A	0.9600
C5—H5	0.9800	C29—H29B	0.9600
C6—C7	1.501 (5)	C29—H29C	0.9600
C6—H6	0.9800	C30—H30A	0.9600
C7—C8	1.566 (5)	C30—H30B	0.9600
C7—H7	0.9800	C30—H30C	0.9600
C8—C14	1.504 (6)	C31—C32	1.456 (7)
C8—C30	1.525 (6)	C32—C34	1.315 (6)
C8—C9	1.577 (5)	C32—H32	0.9300
C9—C11	1.525 (5)	C33—C34	1.472 (7)
C9—C10	1.566 (5)	C33—H33A	0.9600
C9—H9	0.9800	C33—H33B	0.9600
C10—C19	1.538 (6)	C33—H33C	0.9600
C11—C12	1.481 (6)	C34—C35	1.483 (7)
C11—H11A	0.9700	C35—H35A	0.9600
C11—H11B	0.9700	C35—H35B	0.9600
C13—C14	1.337 (5)	C35—H35C	0.9600
C13—C18	1.494 (6)
C31—O1—C1	118.0 (3)	O7—C15—H15	110.3
C3—O3—H3	109.5	C14—C15—H15	110.3
C6—O6—C28	108.1 (3)	C16—C15—H15	110.3
C7—O7—C15	106.7 (3)	C15—C16—C17	103.2 (3)
C21—O21—C23	106.1 (5)	C15—C16—H16A	111.1
C12—O27—C27	116.4 (5)	C17—C16—H16A	111.1
O1—C1—C2	107.9 (3)	C15—C16—H16B	111.1
O1—C1—C10	109.2 (3)	C17—C16—H16B	111.1
C2—C1—C10	113.0 (3)	H16A—C16—H16B	109.1
O1—C1—H1	108.9	C20—C17—C13	116.1 (4)
C2—C1—H1	108.9	C20—C17—C16	113.4 (4)
C10—C1—H1	108.9	C13—C17—C16	102.1 (3)
C3—C2—C1	118.5 (3)	C20—C17—H17	108.3
C3—C2—H2A	107.7	C13—C17—H17	108.3
C1—C2—H2A	107.7	C16—C17—H17	108.3
C3—C2—H2B	107.7	C13—C18—H18A	109.5
C1—C2—H2B	107.7	C13—C18—H18B	109.5
H2A—C2—H2B	107.1	H18A—C18—H18B	109.5
O3—C3—C2	112.2 (4)	C13—C18—H18C	109.5
O3—C3—C4	108.4 (3)	H18A—C18—H18C	109.5
C2—C3—C4	109.4 (4)	H18B—C18—H18C	109.5
O3—C3—H3A	109.0	C10—C19—H19A	109.5
C2—C3—H3A	109.0	C10—C19—H19B	109.5
C4—C3—H3A	109.0	H19A—C19—H19B	109.5
C29—C4—C28	108.4 (4)	C10—C19—H19C	109.5
C29—C4—C3	109.9 (3)	H19A—C19—H19C	109.5
C28—C4—C3	118.3 (4)	H19B—C19—H19C	109.5
C29—C4—C5	116.8 (4)	C21—C20—C22	106.4 (6)
C28—C4—C5	96.4 (3)	C21—C20—C17	125.6 (5)
C3—C4—C5	106.9 (3)	C22—C20—C17	127.9 (4)
C6—C5—C10	116.3 (4)	C20—C21—O21	110.7 (6)
C6—C5—C4	103.6 (3)	C20—C21—H21	124.6
C10—C5—C4	121.9 (3)	O21—C21—H21	124.6
C6—C5—H5	104.4	C23—C22—C20	106.9 (6)
C10—C5—H5	104.4	C23—C22—H22	126.5
C4—C5—H5	104.4	C20—C22—H22	126.5
O6—C6—C5	104.1 (3)	C22—C23—O21	109.8 (6)
O6—C6—C7	115.3 (3)	C22—C23—H23	125.1
C5—C6—C7	111.7 (3)	O21—C23—H23	125.1
O6—C6—H6	108.5	O27—C27—H27A	109.5
C5—C6—H6	108.5	O27—C27—H27B	109.5
C7—C6—H6	108.5	H27A—C27—H27B	109.5
O7—C7—C6	109.9 (3)	O27—C27—H27C	109.5
O7—C7—C8	106.3 (3)	H27A—C27—H27C	109.5
C6—C7—C8	111.9 (3)	H27B—C27—H27C	109.5
O7—C7—H7	109.6	O6—C28—C4	106.2 (4)
C6—C7—H7	109.6	O6—C28—H28A	110.5
C8—C7—H7	109.6	C4—C28—H28A	110.5
C14—C8—C30	113.6 (3)	O6—C28—H28B	110.5
C14—C8—C7	95.5 (3)	C4—C28—H28B	110.5
C30—C8—C7	109.5 (3)	H28A—C28—H28B	108.7
C14—C8—C9	110.2 (3)	C4—C29—H29A	109.5
C30—C8—C9	115.0 (3)	C4—C29—H29B	109.5
C7—C8—C9	111.5 (3)	H29A—C29—H29B	109.5
C11—C9—C10	113.6 (3)	C4—C29—H29C	109.5
C11—C9—C8	112.1 (3)	H29A—C29—H29C	109.5
C10—C9—C8	114.7 (3)	H29B—C29—H29C	109.5
C11—C9—H9	105.1	C8—C30—H30A	109.5
C10—C9—H9	105.1	C8—C30—H30B	109.5
C8—C9—H9	105.1	H30A—C30—H30B	109.5
C5—C10—C19	116.1 (4)	C8—C30—H30C	109.5
C5—C10—C1	105.5 (3)	H30A—C30—H30C	109.5
C19—C10—C1	106.2 (3)	H30B—C30—H30C	109.5
C5—C10—C9	104.3 (3)	O31—C31—O1	122.5 (4)
C19—C10—C9	112.8 (4)	O31—C31—C32	126.5 (4)
C1—C10—C9	112.0 (3)	O1—C31—C32	111.0 (4)
C12—C11—C9	113.8 (4)	C34—C32—C31	127.3 (4)
C12—C11—H11A	108.8	C34—C32—H32	116.4
C9—C11—H11A	108.8	C31—C32—H32	116.4
C12—C11—H11B	108.8	C34—C33—H33A	109.5
C9—C11—H11B	108.8	C34—C33—H33B	109.5
H11A—C11—H11B	107.7	H33A—C33—H33B	109.5
O12—C12—O27	121.7 (5)	C34—C33—H33C	109.5
O12—C12—C11	125.4 (5)	H33A—C33—H33C	109.5
O27—C12—C11	112.9 (5)	H33B—C33—H33C	109.5
C14—C13—C18	130.9 (4)	C32—C34—C33	124.7 (5)
C14—C13—C17	110.0 (4)	C32—C34—C35	121.8 (4)
C18—C13—C17	119.1 (3)	C33—C34—C35	113.5 (5)
C13—C14—C15	111.6 (4)	C34—C35—H35A	109.5
C13—C14—C8	137.2 (4)	C34—C35—H35B	109.5
C15—C14—C8	108.1 (3)	H35A—C35—H35B	109.5
O7—C15—C14	105.9 (3)	C34—C35—H35C	109.5
O7—C15—C16	116.7 (3)	H35A—C35—H35C	109.5
C14—C15—C16	102.8 (3)	H35B—C35—H35C	109.5
C31—O1—C1—C2	99.9 (4)	C11—C9—C10—C19	−57.5 (5)
C31—O1—C1—C10	−137.0 (4)	C8—C9—C10—C19	73.2 (4)
O1—C1—C2—C3	71.1 (4)	C11—C9—C10—C1	62.2 (5)
C10—C1—C2—C3	−49.6 (5)	C8—C9—C10—C1	−167.1 (3)
C1—C2—C3—O3	−67.8 (5)	C10—C9—C11—C12	−149.1 (4)
C1—C2—C3—C4	52.5 (5)	C8—C9—C11—C12	78.9 (5)
O3—C3—C4—C29	−160.6 (4)	C27—O27—C12—O12	−0.8 (7)
C2—C3—C4—C29	76.8 (4)	C27—O27—C12—C11	−179.4 (5)
O3—C3—C4—C28	−35.4 (5)	C9—C11—C12—O12	43.0 (6)
C2—C3—C4—C28	−158.0 (4)	C9—C11—C12—O27	−138.5 (4)
O3—C3—C4—C5	71.7 (4)	C18—C13—C14—C15	−180.0 (5)
C2—C3—C4—C5	−50.8 (5)	C17—C13—C14—C15	−3.0 (5)
C29—C4—C5—C6	69.2 (5)	C18—C13—C14—C8	−23.1 (8)
C28—C4—C5—C6	−45.2 (4)	C17—C13—C14—C8	153.9 (4)
C3—C4—C5—C6	−167.3 (4)	C30—C8—C14—C13	−8.4 (6)
C29—C4—C5—C10	−64.2 (5)	C7—C8—C14—C13	−122.4 (5)
C28—C4—C5—C10	−178.6 (4)	C9—C8—C14—C13	122.3 (5)
C3—C4—C5—C10	59.3 (5)	C30—C8—C14—C15	149.0 (3)
C28—O6—C6—C5	−11.8 (4)	C7—C8—C14—C15	35.0 (3)
C28—O6—C6—C7	−134.5 (4)	C9—C8—C14—C15	−80.3 (4)
C10—C5—C6—O6	173.5 (3)	C7—O7—C15—C14	−9.0 (4)
C4—C5—C6—O6	36.9 (4)	C7—O7—C15—C16	104.6 (4)
C10—C5—C6—C7	−61.5 (5)	C13—C14—C15—O7	145.0 (3)
C4—C5—C6—C7	161.9 (4)	C8—C14—C15—O7	−18.7 (4)
C15—O7—C7—C6	153.8 (3)	C13—C14—C15—C16	22.1 (4)
C15—O7—C7—C8	32.5 (4)	C8—C14—C15—C16	−141.6 (3)
O6—C6—C7—O7	51.9 (4)	O7—C15—C16—C17	−146.3 (4)
C5—C6—C7—O7	−66.7 (4)	C14—C15—C16—C17	−30.9 (4)
O6—C6—C7—C8	169.8 (3)	C14—C13—C17—C20	107.0 (4)
C5—C6—C7—C8	51.2 (5)	C18—C13—C17—C20	−75.6 (5)
O7—C7—C8—C14	−40.9 (3)	C14—C13—C17—C16	−16.9 (5)
C6—C7—C8—C14	−160.9 (3)	C18—C13—C17—C16	160.5 (4)
O7—C7—C8—C30	−158.3 (3)	C15—C16—C17—C20	−96.5 (4)
C6—C7—C8—C30	81.7 (4)	C15—C16—C17—C13	29.2 (4)
O7—C7—C8—C9	73.3 (4)	C13—C17—C20—C21	131.3 (6)
C6—C7—C8—C9	−46.7 (5)	C16—C17—C20—C21	−110.9 (6)
C14—C8—C9—C11	−73.5 (4)	C13—C17—C20—C22	−53.3 (7)
C30—C8—C9—C11	56.4 (5)	C16—C17—C20—C22	64.5 (6)
C7—C8—C9—C11	−178.2 (3)	C22—C20—C21—O21	−0.2 (8)
C14—C8—C9—C10	155.0 (3)	C17—C20—C21—O21	176.1 (5)
C30—C8—C9—C10	−75.1 (5)	C23—O21—C21—C20	0.6 (8)
C7—C8—C9—C10	50.3 (5)	C21—C20—C22—C23	−0.3 (7)
C6—C5—C10—C19	−65.1 (5)	C17—C20—C22—C23	−176.4 (5)
C4—C5—C10—C19	63.0 (5)	C20—C22—C23—O21	0.7 (7)
C6—C5—C10—C1	177.7 (3)	C21—O21—C23—C22	−0.8 (7)
C4—C5—C10—C1	−54.2 (5)	C6—O6—C28—C4	−17.8 (4)
C6—C5—C10—C9	59.6 (4)	C29—C4—C28—O6	−82.8 (4)
C4—C5—C10—C9	−172.3 (4)	C3—C4—C28—O6	151.3 (3)
O1—C1—C10—C5	−76.0 (4)	C5—C4—C28—O6	38.2 (4)
C2—C1—C10—C5	44.0 (4)	C1—O1—C31—O31	0.7 (7)
O1—C1—C10—C19	160.3 (3)	C1—O1—C31—C32	−177.6 (3)
C2—C1—C10—C19	−79.7 (4)	O31—C31—C32—C34	−9.7 (9)
O1—C1—C10—C9	36.8 (4)	O1—C31—C32—C34	168.5 (5)
C2—C1—C10—C9	156.8 (3)	C31—C32—C34—C33	0.0 (8)
C11—C9—C10—C5	175.8 (3)	C31—C32—C34—C35	−179.0 (5)
C8—C9—C10—C5	−53.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O6^i	0.82	2.11	2.900 (4)	161

Symmetry code: (i) −x, y+1/2, −z+1/2.