The chemical structures of two withanolides, isolated from the leaves of Physalis angulata by column chromatography, were studied. The isolated compounds are (17S,20R,22R,24R,25S)-5β,6β:20,24-diepoxy-4β,25-dihydroxy-1-oxowith-2-en-26,22-olide and (20R,22R)-5α,14α,20-Trihydroxy-1-oxo-6α,7α-epoxywitha-2-enolide.
Keywords: Physalis angulata L., physangulide B, 14α-hydroxyixocarpanolide, molecular structure, hydrogen bonding, chloroform solvate, crystal structure
Abstract
The compounds (17S,20R,22R,24R,25S)-5β,6β:20,24-diepoxy-4β,25-dihydroxy-1-oxowith-2-en-26,22-olide and (20R,22R)-5α,14α,20-Trihydroxy-1-oxo-6α,7α-epoxywitha-2-enolide were isolated from a chloroform extract of the aerial parts of Physalis angulata L. (Solanaceae). Two products were isolated from the chromatographic separation extract. Compound I corresponds to physangulide B chloroform monosolvate, C28H38O7·CHCl3, while compound II is 14α-hydroxyixocarpanolide, C28H40O7. In the two molecular structures, the conformation of the steroid part (rings A, B, C, D) does not differ. In both crystals, molecules are linked by intermolecular O—H⋯O hydrogen bonds along the c-axis direction and form a two-dimensional network parallel to the ac plane. The absolute configuration was determined from X-ray diffraction data.
Chemical context
The genus Physalis belongs to the nightshade family of plants and is widely distributed in subtropical and tropical regions around the world. Some Physalis species are important in the diet because of their edible fruits. Phytochemical and pharmacological studies show that in plants of the genus Physalis, the main biological substances are withanolides (Huang et al., 2020 ▸). The fruits of Physalis angulata L. are edible, traditionally collected from wild populations, but the plant is now widely cultivated. In different countries of the world the fruits, roots and leaves of Physalis angulata L. are used in folk medicine as a treatment for various diseases (Salgado & Arana, 2013 ▸). The main secondary metabolites of Physalis angulata are withanolides, which are highly variable in chemical structure and exhibit interesting pharmacological activity (Ray & Gupta, 1994 ▸; Figueiredo et al., 2020 ▸; Sá et al., 2011 ▸; Pinto et al., 2016 ▸). The plant Physalis angulata is widespread in Uzbekistan and its reserves are sufficient for industrial use (Vasina et al., 1990 ▸).
To study the chemical structure of withanolides, leaves of Physalis angulata collected in the Tashkent region were used. Isolation of withanolides from the leaves of Physalis angulata and separation of components into individual substances was carried out by column chromatography. The isolated compounds were identified as physangulide B chloroform solvate (I) and 14α-hydroxyixocarpanolide (II).
Structural commentary
The asymmetric unit of I, a chloroform solvate of physangulide B, is shown in Fig. 1 ▸. The use of Cu Kα radiation allowed the determination of the absolute configuration of the physangulide B molecule. The Flack parameter refined to 0.014 (6). The chiral centres of the physangulide B molecule have the following chirality: 4S, 5R, 6R, 8S, 9S,10R, 13S, 14S, 17S, 20R, 22R, 24R and 25S. The stereochemistry of physangulide B [systematic name (17S,20R,22R,24R,25S)-5β,6β:20,24-diepoxy-4β,25-dihydroxy-1-oxowith-2-en-26,22-olide] does not differ from that found for the acetyl derivative and confirms the absolute configuration proposed earlier for physangulide B (Maldonado et al., 2015 ▸).
Figure 1.
Molecular structure of the chloroform solvate of physangulide B (compound I), including atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
The molecular structure of withanolide II is shown in Fig. 2 ▸. The Flack parameter refined to −0.1 (2) and allowed the absolute configuration of II to be confirmed. The chiral centres in the molecule have the following chirality: 5R, 6S, 7S, 8S, 9S, 10R, 13R, 14R, 17S, 20R, 22R, 24S, 25R. According to the experimental data, the isolated compound is 14α-hydroxyixocarpanolide [systematic name: (20R,22R)-5α,14α,20-trihydroxy-1-oxo-6α,7α-epoxywitha-2-enolide (Vasina et al., 1986 ▸; Ray & Gupta, 1994 ▸).
Figure 2.
Molecular structure of the 14α-hydroxyixocarpanolide (compound II), including atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
In both molecules, ring C adopts a chair conformation and ring D an envelope conformation with atom C13 as the flap. Ring A exhibits a half–chair conformation, but differs slightly in the arrangement of atoms. The C1–C4 fragment is planar with r.m.s deviations of 0.0045 Å for I and 0.034 Å for II. The deviations of atoms C5 and C10 atoms from this plane are −0.225 (7) and 0.291 (7) Å, respectively, for I and −0.478 (7) and 0.280 (7) Å for II.
In the molecule of I, atoms of ring B are located in one plane (with an r.m.s deviation of 0.0132 Å), except for C8 which deviates from the plane of the remaining atoms by 0.666 (4) Å. A similar envelope conformation for ring B is observed in II. Here, the C5–C9 atoms are located in one plane with an accuracy of 0.0643 Å, atom C10 being displaced from the plane through the remaining atoms by 0.696 (4) Å. This difference in the arrangement of atoms in planes is explained by the position of the epoxy bridge, which is located in the β-position for I and the α-position for II.
Supramolecular features
In both crystal structures, intermolecular hydrogen bonds of the O—H⋯O type are observed, which link the molecules along the c-axis direction. In compound I, O—H⋯O and C—H⋯O hydrogen bonds are observed between molecules of physangulide B (Table 1 ▸). O4—H4⋯O26 and O25—H25⋯O56 hydrogen bonds are involved in the formation of an infinite chain along the c-axis (Fig. 3 ▸). In addition, the chloroform molecule participates in a hydrogen bond with the oxygen atom O26 of the lactone fragment. A similar hydrogen bond with a solvate molecule (methanol) is observed in the structure of the acetyl derivative of physangulide B (FUQKAF; Maldonado et al., 2015 ▸).
Table 1. Hydrogen-bond geometry (Å, °) for (I) .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O4—H4⋯O26i | 0.79 (6) | 2.10 (6) | 2.819 (4) | 151 |
| O25—H25⋯O56ii | 0.74 (5) | 2.12 (5) | 2.856 (4) | 169 |
| C23—H23A⋯O26iii | 0.97 | 2.57 | 3.473 (4) | 154 |
| C1S—H1SA⋯O26 | 0.98 | 2.43 | 3.393 (6) | 168 |
Symmetry codes: (i) x, y, z+1; (ii) x, y, z-1; (iii) x+1, y, z.
Figure 3.
Hydrogen bonding in the crystal structure of I (the molecules are cross-linked along the c axis).
Similar intermolecular O—H⋯O and C—H⋯O hydrogen bonds are observed in the structure of II (Table 2 ▸). The formation of an infinite O20—H20⋯O5 hydrogen-bonded chain is shown in Fig. 4 ▸. Paired hydrogen bonds are observed between molecules, which extend along the c-axis direction.
Table 2. Hydrogen-bond geometry (Å, °) for (II) .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O20—H20⋯O5i | 0.76 (6) | 2.22 (6) | 2.973 (4) | 173 |
| C7—H7A⋯O26ii | 0.98 | 2.59 | 3.367 (5) | 136 |
Symmetry codes: (i) x, y, z+1; (ii) x-1, y, z-1.
Figure 4.
O20—H20⋯O5 hydrogen bonds in the crystal structure of compound II (the molecules are cross-linked along the c axis).
Database survey
A search for related structures (A, B, C, D, E rings are connected according to the order of the studied compounds) in the Cambridge Structural Database (CSD Version 5.42, update of November 2020; Groom et al., 2016 ▸) resulted in eleven hits. Of the structures found, the closest structure considering the connectivity and chirality of atoms is 17-(4-hydroxy-4,5,7-trimethyl-3-oxo-2,6-dioxabicyclo[3.2.1]oct-7-yl)-1-oxo-5,6-epoxyandrost-2-en-4-yl acetate methanol solvate (FUQKAF; Maldonado et al., 2015 ▸). Structures with the 5β,6β-epoxy-4β-hydroxy groups in the same location in the molecule as the title compounds are 4,16,20,24-tetrahydroxy-5,6:22,26-diepoxyergost-2-ene-1,26-dione methanol solvate (GANFOS, Maldonado et al., 2011 ▸), (17R,20R,22R,24S,25R)-4β,17α,20β-trihydroxy-5β,6β-epoxy-1-oxowitha-2-en-26,22-olide (Philadelphicalactone A, XIVYEG; Su et al., 2002 ▸) and (17R,20S,22R)-4β-hydroxy-1-oxo-5β,6β-epoxy-16α-acetoxywitha-2-enolide ethyl acetate clathrate (YISSOI; Alfonso et al., 1993 ▸).
Synthesis and crystallization
Isolation of individual substances from the leaves of Physalis angulata
Collected dried leaves (4 kg) of Physalis angulata L. were poured into cold water and heated to boiling. The hot mass was squeezed out through a canvas. The plant was again poured into cold water, heated, and the hot mass was squeezed out through the canvas again. The water extract was distilled until the volume decreased to 3 L. Chloroform (3 L) was poured into the received solution and substances were extracted. From the chloroform layer, insoluble and soluble substances (25 g) were isolated. To the isolated dry mass, 0.5 L of chloroform were added and the solution was filtered (the mass of the insoluble compounds was 5.8 g). From the filtrate after distillation, 19.2 g of compounds were isolated. The compounds isolated from the filtrate were loaded onto a column containing 0.5 kg of silica gel (Silica gel 60, 0.063-0.1 mm, Merck). The sums of substances were eluted with system 1 (chloroform:methanol 99:1) to produce fractions 1–5, and eluted with system 2 (chloroform:methanol 97:3) to produce fractions 5–9. The process was monitored by thin layer chromatography (Silica gel on TLC Al foils, fluorescent indicator 254 nm). Fractions 2–4 (6.8 g) and 6–8 (4.0 g) were shown by TLC to consist of individual substances.
The obtained fractions were purified by repeated chromatography. Rechromatography of fractions 2–4 containing physangulide B in system 3 (chloroform:methanol 10:1) gave 5.96 g of the individual product. The R F in system 3 was 0.58, visualized as a crimson spot. The yield was 0.15%, based on the weight of the air-dry raw material. Rechromatography of fractions 6–8 in system 1 yielded 3.6 g of 14α-hydroxyixocarpanolide, R F = 0.34 in system 2, visualized as a pink spot. The yield was 0.028%.
Physangulide B [(17 S ,20 R ,22 R ,24 R ,25 S )-5β,6β:20,24-diepoxy-4β,25-dihydroxy-1-oxowith-2-en-26,22-olide]
C28H40O7 (methanol), m.p. 553–555 K, [α]20 D = −56.0 (c = 0.21, CHCl3). UV spectrum, λCH3OHmax (logɛ 5600) 212 (4.00) nm. IR (FT–IR, νKBrmax, cm−1): 3411 (v br, O—H str), 2958 (m, Csycl—H str), 1706 (s, C=O str), 1676 (v s, C=O), 1457 (m), 1380 (m), 1272 (s), 1101 (s), 1085 (m), 1024 (m), 962 (m), 921 (w), 905 (w).
14α-hydroxyixocarpanolide (5α,14α,20R-trihydroxy-1-oxo-6α,7α-epoxywitha-2-enolide)
C28H40O7 (methanol), mp. 528–530 K, [α]20 D = + 29.1 ±2 (c = 1.18, CHCl3). UV spectrum, λC2H5OHmax: 225 nm (ɛ 10370). IR (FT–IR, νKBrmax, cm−1): 3584–3477 (v br, O—H str), 2949 (m, Csycl—H str), 1754 (v s, C=O str), 1458 (w), 1388 (m), 1261 (s), 1182 (m), 1094 (v), 1034 (m), 910 (m).
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The H atoms bonded to C atoms were placed geometrically (with C—H distances of 0.98 Å for CH, 0.97 Å for CH2, 0.96 Å for CH3 and 0.93 Å for Car) and included in the refinement in a riding-motion approximation with U iso(H) = 1.2U eq(C) [U iso = 1.5U eq(C) for methyl H atoms]. The hydrogen atoms on the O atoms were located in difference-Fourier maps and refined freely.
Table 3. Experimental details.
| (I) | (II) | |
|---|---|---|
| Crystal data | ||
| Chemical formula | C28H38O7·CHCl3 | C28H40O7 |
| M r | 605.95 | 488.60 |
| Crystal system, space group | Monoclinic, P21 | Triclinic, P1 |
| Temperature (K) | 290 | 290 |
| a, b, c (Å) | 7.3633 (15), 15.952 (3), 12.657 (3) | 6.2374 (12), 9.5938 (19), 11.351 (2) |
| α, β, γ (°) | 90, 94.14 (3), 90 | 112.81 (3), 96.49 (3), 93.13 (3) |
| V (Å3) | 1482.9 (5) | 618.5 (2) |
| Z | 2 | 1 |
| Radiation type | Cu Kα | Cu Kα |
| μ (mm−1) | 3.17 | 0.76 |
| Crystal size (mm) | 0.50 × 0.34 × 0.31 | 0.42 × 0.28 × 0.21 |
| Data collection | ||
| Diffractometer | Rigaku Xcalibur, Ruby | Rigaku Xcalibur, Ruby |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 2003 ▸) | Multi-scan (SADABS; Sheldrick, 2003 ▸) |
| T min, T max | 0.316, 0.376 | 0.776, 0.853 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 13820, 5743, 5622 | 4169, 2812, 2545 |
| R int | 0.028 | 0.025 |
| (sin θ/λ)max (Å−1) | 0.629 | 0.631 |
| Refinement | ||
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.042, 0.113, 1.04 | 0.041, 0.110, 1.04 |
| No. of reflections | 5743 | 2812 |
| No. of parameters | 365 | 333 |
| No. of restraints | 1 | 3 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.41, −0.34 | 0.17, −0.19 |
| Absolute structure | Flack x determined using 2401 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸) | Classical Flack method preferred over Parsons because s.u. lower |
| Absolute structure parameter | 0.014 (6) | −0.1 (2) |
Supplementary Material
Crystal structure: contains datablock(s) I, II, Global. DOI: 10.1107/S205698902100709X/dj2029sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S205698902100709X/dj2029Isup2.hkl
Structure factors: contains datablock(s) II. DOI: 10.1107/S205698902100709X/dj2029IIsup3.hkl
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
We are especially grateful to Dr Kambarali Turgunov for help in discussing the results.
supplementary crystallographic information
(17S,20R,22R,24R,25S)-5β,6β:20,24-Diepoxy-4β,25-dihydroxy-1-oxowith-2-en-26,22-olide chloroform solvate (I) . Crystal data
| C28H38O7·CHCl3 | Dx = 1.357 Mg m−3 |
| Mr = 605.95 | Melting point: 553(2) K |
| Monoclinic, P21 | Cu Kα radiation, λ = 1.54184 Å |
| a = 7.3633 (15) Å | Cell parameters from 7825 reflections |
| b = 15.952 (3) Å | θ = 5.5–76.0° |
| c = 12.657 (3) Å | µ = 3.17 mm−1 |
| β = 94.14 (3)° | T = 290 K |
| V = 1482.9 (5) Å3 | Prizmatic, colorless |
| Z = 2 | 0.50 × 0.34 × 0.31 mm |
| F(000) = 640 |
(17S,20R,22R,24R,25S)-5β,6β:20,24-Diepoxy-4β,25-dihydroxy-1-oxowith-2-en-26,22-olide chloroform solvate (I) . Data collection
| Rigaku Xcalibur, Ruby diffractometer | 5743 independent reflections |
| Radiation source: Enhance (Cu) X-ray Source | 5622 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.028 |
| Detector resolution: 10.2576 pixels mm-1 | θmax = 75.9°, θmin = 3.5° |
| ω scans | h = −9→9 |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −19→19 |
| Tmin = 0.316, Tmax = 0.376 | l = −13→15 |
| 13820 measured reflections |
(17S,20R,22R,24R,25S)-5β,6β:20,24-Diepoxy-4β,25-dihydroxy-1-oxowith-2-en-26,22-olide chloroform solvate (I) . Refinement
| Refinement on F2 | Hydrogen site location: mixed |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.042 | w = 1/[σ2(Fo2) + (0.0643P)2 + 0.4392P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.113 | (Δ/σ)max < 0.001 |
| S = 1.04 | Δρmax = 0.41 e Å−3 |
| 5743 reflections | Δρmin = −0.34 e Å−3 |
| 365 parameters | Absolute structure: Flack x determined using 2401 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
| 1 restraint | Absolute structure parameter: 0.014 (6) |
| Primary atom site location: structure-invariant direct methods |
(17S,20R,22R,24R,25S)-5β,6β:20,24-Diepoxy-4β,25-dihydroxy-1-oxowith-2-en-26,22-olide chloroform solvate (I) . Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
(17S,20R,22R,24R,25S)-5β,6β:20,24-Diepoxy-4β,25-dihydroxy-1-oxowith-2-en-26,22-olide chloroform solvate (I) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.5252 (5) | 0.9171 (2) | 0.5852 (2) | 0.0678 (9) | |
| O2 | 1.0029 (3) | 0.76628 (14) | 0.21727 (16) | 0.0380 (5) | |
| O3 | 1.1887 (3) | 0.60670 (14) | 0.22825 (16) | 0.0357 (4) | |
| O4 | 0.5431 (5) | 0.8210 (2) | 0.9630 (2) | 0.0619 (8) | |
| O25 | 1.0440 (4) | 0.6971 (2) | −0.02618 (18) | 0.0534 (7) | |
| O26 | 0.7584 (3) | 0.7338 (2) | 0.1201 (2) | 0.0598 (7) | |
| O56 | 0.7082 (3) | 0.70353 (16) | 0.84614 (16) | 0.0419 (5) | |
| C1 | 0.5220 (5) | 0.8852 (2) | 0.6718 (3) | 0.0402 (7) | |
| C2 | 0.3764 (5) | 0.9089 (3) | 0.7396 (3) | 0.0530 (9) | |
| H2A | 0.3045 | 0.9551 | 0.7202 | 0.064* | |
| C3 | 0.3425 (5) | 0.8679 (3) | 0.8265 (3) | 0.0513 (9) | |
| H3A | 0.2463 | 0.8858 | 0.8646 | 0.062* | |
| C4 | 0.4509 (5) | 0.7944 (2) | 0.8665 (3) | 0.0442 (7) | |
| H4B | 0.3664 | 0.7494 | 0.8824 | 0.053* | |
| C5 | 0.5835 (4) | 0.7603 (2) | 0.7888 (2) | 0.0322 (6) | |
| C6 | 0.5780 (4) | 0.6705 (2) | 0.7655 (2) | 0.0352 (6) | |
| H6A | 0.4750 | 0.6394 | 0.7912 | 0.042* | |
| C7 | 0.6634 (4) | 0.63329 (18) | 0.6726 (2) | 0.0330 (6) | |
| H7A | 0.5713 | 0.6264 | 0.6145 | 0.040* | |
| H7B | 0.7116 | 0.5783 | 0.6915 | 0.040* | |
| C8 | 0.8166 (4) | 0.68855 (17) | 0.63666 (19) | 0.0271 (5) | |
| H8A | 0.9182 | 0.6886 | 0.6911 | 0.032* | |
| C9 | 0.7496 (4) | 0.77894 (17) | 0.6166 (2) | 0.0277 (5) | |
| H9A | 0.6484 | 0.7747 | 0.5622 | 0.033* | |
| C10 | 0.6687 (4) | 0.82253 (18) | 0.7140 (2) | 0.0298 (5) | |
| C11 | 0.8951 (5) | 0.83293 (19) | 0.5672 (3) | 0.0394 (7) | |
| H11A | 0.8440 | 0.8877 | 0.5499 | 0.047* | |
| H11B | 0.9972 | 0.8408 | 0.6191 | 0.047* | |
| C12 | 0.9643 (5) | 0.79385 (19) | 0.4669 (3) | 0.0385 (7) | |
| H12A | 0.8658 | 0.7922 | 0.4117 | 0.046* | |
| H12B | 1.0607 | 0.8285 | 0.4420 | 0.046* | |
| C13 | 1.0362 (3) | 0.70547 (18) | 0.4875 (2) | 0.0283 (5) | |
| C14 | 0.8816 (4) | 0.65438 (16) | 0.53265 (19) | 0.0269 (5) | |
| H14A | 0.7772 | 0.6588 | 0.4804 | 0.032* | |
| C15 | 0.9460 (5) | 0.5629 (2) | 0.5285 (3) | 0.0420 (7) | |
| H15A | 0.8432 | 0.5248 | 0.5209 | 0.050* | |
| H15B | 1.0208 | 0.5483 | 0.5921 | 0.050* | |
| C16 | 1.0582 (5) | 0.5598 (2) | 0.4299 (3) | 0.0401 (7) | |
| H16A | 1.0015 | 0.5225 | 0.3767 | 0.048* | |
| H16B | 1.1809 | 0.5402 | 0.4490 | 0.048* | |
| C17 | 1.0614 (4) | 0.65077 (18) | 0.3875 (2) | 0.0292 (5) | |
| H17A | 0.9476 | 0.6571 | 0.3431 | 0.035* | |
| C18 | 1.2062 (4) | 0.7062 (3) | 0.5657 (3) | 0.0479 (8) | |
| H18A | 1.1720 | 0.7221 | 0.6347 | 0.072* | |
| H18B | 1.2929 | 0.7458 | 0.5422 | 0.072* | |
| H18C | 1.2596 | 0.6513 | 0.5691 | 0.072* | |
| C19 | 0.8116 (5) | 0.8745 (2) | 0.7823 (3) | 0.0434 (7) | |
| H19A | 0.7590 | 0.8937 | 0.8451 | 0.065* | |
| H19B | 0.8486 | 0.9219 | 0.7423 | 0.065* | |
| H19C | 0.9157 | 0.8401 | 0.8016 | 0.065* | |
| C20 | 1.2141 (4) | 0.6683 (2) | 0.3131 (2) | 0.0332 (6) | |
| C21 | 1.4095 (4) | 0.6596 (3) | 0.3637 (3) | 0.0509 (9) | |
| H21A | 1.4926 | 0.6545 | 0.3090 | 0.076* | |
| H21B | 1.4176 | 0.6105 | 0.4078 | 0.076* | |
| H21C | 1.4401 | 0.7082 | 0.4059 | 0.076* | |
| C22 | 1.1939 (4) | 0.7507 (2) | 0.2501 (2) | 0.0371 (6) | |
| H22A | 1.2487 | 0.7980 | 0.2902 | 0.045* | |
| C23 | 1.2941 (4) | 0.7319 (2) | 0.1529 (3) | 0.0406 (7) | |
| H23A | 1.4249 | 0.7303 | 0.1687 | 0.049* | |
| H23B | 1.2645 | 0.7717 | 0.0964 | 0.049* | |
| C24 | 1.2164 (4) | 0.6451 (2) | 0.1265 (2) | 0.0336 (6) | |
| C25 | 1.0239 (4) | 0.6579 (2) | 0.0736 (2) | 0.0378 (6) | |
| C26 | 0.9179 (4) | 0.7211 (2) | 0.1396 (2) | 0.0389 (7) | |
| C27 | 0.9140 (6) | 0.5779 (3) | 0.0607 (3) | 0.0568 (9) | |
| H27A | 0.9777 | 0.5384 | 0.0197 | 0.085* | |
| H27B | 0.7975 | 0.5900 | 0.0251 | 0.085* | |
| H27C | 0.8972 | 0.5545 | 0.1292 | 0.085* | |
| C28 | 1.3367 (5) | 0.5895 (3) | 0.0646 (3) | 0.0470 (8) | |
| H28A | 1.4541 | 0.5844 | 0.1021 | 0.070* | |
| H28B | 1.3501 | 0.6138 | −0.0038 | 0.070* | |
| H28C | 1.2822 | 0.5351 | 0.0560 | 0.070* | |
| C1S | 0.6099 (7) | 0.9209 (3) | 0.2081 (4) | 0.0664 (11) | |
| H1SA | 0.6333 | 0.8640 | 0.1832 | 0.080* | |
| Cl1 | 0.4179 (2) | 0.96088 (8) | 0.13542 (10) | 0.0782 (4) | |
| Cl2 | 0.5718 (2) | 0.91662 (10) | 0.34355 (10) | 0.0863 (4) | |
| Cl3 | 0.8008 (3) | 0.98341 (14) | 0.18974 (14) | 0.1059 (5) | |
| H4 | 0.605 (7) | 0.785 (4) | 0.989 (4) | 0.063 (15)* | |
| H25 | 0.958 (7) | 0.692 (3) | −0.060 (4) | 0.051 (13)* |
(17S,20R,22R,24R,25S)-5β,6β:20,24-Diepoxy-4β,25-dihydroxy-1-oxowith-2-en-26,22-olide chloroform solvate (I) . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.085 (2) | 0.0663 (18) | 0.0546 (15) | 0.0371 (16) | 0.0221 (14) | 0.0254 (14) |
| O2 | 0.0421 (11) | 0.0384 (11) | 0.0345 (10) | 0.0095 (9) | 0.0089 (8) | 0.0018 (9) |
| O3 | 0.0427 (11) | 0.0366 (11) | 0.0287 (9) | 0.0043 (9) | 0.0091 (8) | −0.0020 (8) |
| O4 | 0.080 (2) | 0.075 (2) | 0.0318 (12) | 0.0277 (17) | 0.0112 (12) | −0.0065 (12) |
| O25 | 0.0432 (13) | 0.088 (2) | 0.0295 (11) | 0.0046 (13) | 0.0045 (10) | 0.0098 (12) |
| O26 | 0.0373 (12) | 0.091 (2) | 0.0506 (14) | 0.0193 (13) | 0.0029 (10) | −0.0003 (14) |
| O56 | 0.0490 (12) | 0.0505 (13) | 0.0262 (9) | 0.0114 (10) | 0.0030 (8) | 0.0049 (9) |
| C1 | 0.0474 (17) | 0.0348 (15) | 0.0387 (15) | 0.0085 (13) | 0.0053 (13) | 0.0011 (12) |
| C2 | 0.0483 (19) | 0.059 (2) | 0.053 (2) | 0.0247 (17) | 0.0064 (15) | 0.0003 (17) |
| C3 | 0.0397 (17) | 0.069 (2) | 0.0473 (18) | 0.0138 (17) | 0.0137 (14) | −0.0081 (16) |
| C4 | 0.0468 (17) | 0.0505 (19) | 0.0378 (16) | 0.0021 (15) | 0.0187 (13) | −0.0022 (13) |
| C5 | 0.0333 (13) | 0.0391 (15) | 0.0246 (12) | 0.0024 (12) | 0.0054 (10) | 0.0014 (11) |
| C6 | 0.0389 (14) | 0.0351 (14) | 0.0329 (13) | −0.0017 (12) | 0.0103 (11) | 0.0062 (11) |
| C7 | 0.0392 (15) | 0.0277 (13) | 0.0328 (13) | −0.0013 (11) | 0.0073 (11) | 0.0025 (10) |
| C8 | 0.0294 (12) | 0.0292 (13) | 0.0227 (11) | 0.0003 (10) | 0.0024 (9) | 0.0000 (9) |
| C9 | 0.0314 (13) | 0.0270 (13) | 0.0250 (12) | −0.0003 (10) | 0.0047 (9) | −0.0021 (9) |
| C10 | 0.0322 (13) | 0.0309 (13) | 0.0273 (12) | 0.0023 (11) | 0.0081 (10) | −0.0029 (10) |
| C11 | 0.0497 (18) | 0.0273 (14) | 0.0438 (16) | −0.0060 (13) | 0.0213 (13) | −0.0064 (12) |
| C12 | 0.0487 (17) | 0.0290 (14) | 0.0405 (16) | −0.0010 (12) | 0.0211 (13) | 0.0006 (11) |
| C13 | 0.0265 (12) | 0.0343 (14) | 0.0244 (11) | 0.0002 (10) | 0.0040 (9) | −0.0038 (10) |
| C14 | 0.0303 (12) | 0.0259 (13) | 0.0246 (11) | 0.0012 (10) | 0.0030 (9) | 0.0002 (9) |
| C15 | 0.059 (2) | 0.0291 (15) | 0.0398 (15) | 0.0091 (14) | 0.0154 (14) | 0.0044 (12) |
| C16 | 0.0487 (17) | 0.0335 (15) | 0.0393 (15) | 0.0095 (13) | 0.0118 (13) | −0.0007 (12) |
| C17 | 0.0288 (12) | 0.0326 (14) | 0.0260 (12) | 0.0038 (10) | 0.0008 (9) | −0.0025 (10) |
| C18 | 0.0309 (14) | 0.075 (2) | 0.0369 (15) | −0.0029 (16) | −0.0012 (11) | −0.0169 (16) |
| C19 | 0.0470 (17) | 0.0451 (17) | 0.0389 (15) | −0.0091 (14) | 0.0085 (13) | −0.0156 (13) |
| C20 | 0.0280 (12) | 0.0431 (16) | 0.0285 (12) | 0.0027 (11) | 0.0028 (10) | −0.0063 (11) |
| C21 | 0.0295 (14) | 0.083 (3) | 0.0400 (16) | 0.0072 (16) | 0.0036 (12) | −0.0052 (17) |
| C22 | 0.0344 (14) | 0.0407 (16) | 0.0369 (14) | −0.0052 (12) | 0.0073 (11) | −0.0061 (12) |
| C23 | 0.0353 (15) | 0.0499 (18) | 0.0379 (15) | −0.0082 (13) | 0.0112 (12) | −0.0015 (13) |
| C24 | 0.0305 (13) | 0.0444 (16) | 0.0267 (12) | 0.0014 (12) | 0.0067 (10) | −0.0012 (11) |
| C25 | 0.0340 (14) | 0.0517 (18) | 0.0284 (13) | −0.0010 (13) | 0.0072 (10) | 0.0006 (12) |
| C26 | 0.0361 (15) | 0.0492 (18) | 0.0322 (14) | 0.0049 (13) | 0.0071 (11) | 0.0087 (12) |
| C27 | 0.048 (2) | 0.066 (2) | 0.057 (2) | −0.0129 (18) | 0.0001 (16) | −0.0146 (19) |
| C28 | 0.0440 (17) | 0.060 (2) | 0.0383 (16) | 0.0092 (15) | 0.0133 (13) | −0.0056 (14) |
| C1S | 0.092 (3) | 0.048 (2) | 0.060 (2) | 0.014 (2) | 0.009 (2) | 0.0038 (19) |
| Cl1 | 0.1089 (10) | 0.0598 (6) | 0.0632 (6) | 0.0123 (6) | −0.0128 (6) | −0.0165 (5) |
| Cl2 | 0.1101 (10) | 0.0872 (9) | 0.0626 (6) | 0.0276 (8) | 0.0136 (6) | 0.0239 (6) |
| Cl3 | 0.1052 (11) | 0.1223 (14) | 0.0904 (10) | −0.0186 (10) | 0.0085 (8) | 0.0238 (9) |
(17S,20R,22R,24R,25S)-5β,6β:20,24-Diepoxy-4β,25-dihydroxy-1-oxowith-2-en-26,22-olide chloroform solvate (I) . Geometric parameters (Å, º)
| O1—C1 | 1.211 (4) | C13—C17 | 1.559 (4) |
| O2—C26 | 1.338 (4) | C14—C15 | 1.536 (4) |
| O2—C22 | 1.459 (4) | C14—H14A | 0.9800 |
| O3—C24 | 1.454 (3) | C15—C16 | 1.547 (4) |
| O3—C20 | 1.458 (3) | C15—H15A | 0.9700 |
| O4—C4 | 1.418 (5) | C15—H15B | 0.9700 |
| O4—H4 | 0.79 (6) | C16—C17 | 1.547 (4) |
| O25—C25 | 1.427 (4) | C16—H16A | 0.9700 |
| O25—H25 | 0.74 (5) | C16—H16B | 0.9700 |
| O26—C26 | 1.200 (4) | C17—C20 | 1.544 (4) |
| O56—C5 | 1.447 (4) | C17—H17A | 0.9800 |
| O56—C6 | 1.448 (4) | C18—H18A | 0.9600 |
| C1—C2 | 1.470 (5) | C18—H18B | 0.9600 |
| C1—C10 | 1.539 (4) | C18—H18C | 0.9600 |
| C2—C3 | 1.319 (6) | C19—H19A | 0.9600 |
| C2—H2A | 0.9300 | C19—H19B | 0.9600 |
| C3—C4 | 1.486 (5) | C19—H19C | 0.9600 |
| C3—H3A | 0.9300 | C20—C22 | 1.538 (5) |
| C4—C5 | 1.536 (4) | C20—C21 | 1.538 (4) |
| C4—H4B | 0.9800 | C21—H21A | 0.9600 |
| C5—C6 | 1.463 (4) | C21—H21B | 0.9600 |
| C5—C10 | 1.537 (4) | C21—H21C | 0.9600 |
| C6—C7 | 1.496 (4) | C22—C23 | 1.511 (4) |
| C6—H6A | 0.9800 | C22—H22A | 0.9800 |
| C7—C8 | 1.526 (4) | C23—C24 | 1.525 (5) |
| C7—H7A | 0.9700 | C23—H23A | 0.9700 |
| C7—H7B | 0.9700 | C23—H23B | 0.9700 |
| C8—C14 | 1.533 (3) | C24—C28 | 1.511 (4) |
| C8—C9 | 1.539 (4) | C24—C25 | 1.537 (4) |
| C8—H8A | 0.9800 | C25—C27 | 1.515 (5) |
| C9—C11 | 1.541 (4) | C25—C26 | 1.554 (4) |
| C9—C10 | 1.570 (3) | C27—H27A | 0.9600 |
| C9—H9A | 0.9800 | C27—H27B | 0.9600 |
| C10—C19 | 1.553 (4) | C27—H27C | 0.9600 |
| C11—C12 | 1.535 (4) | C28—H28A | 0.9600 |
| C11—H11A | 0.9700 | C28—H28B | 0.9600 |
| C11—H11B | 0.9700 | C28—H28C | 0.9600 |
| C12—C13 | 1.522 (4) | C1S—Cl1 | 1.751 (5) |
| C12—H12A | 0.9700 | C1S—Cl3 | 1.753 (6) |
| C12—H12B | 0.9700 | C1S—Cl2 | 1.758 (5) |
| C13—C18 | 1.539 (4) | C1S—H1SA | 0.9800 |
| C13—C14 | 1.543 (4) | ||
| C26—O2—C22 | 120.5 (2) | C16—C15—H15B | 111.0 |
| C24—O3—C20 | 110.5 (2) | H15A—C15—H15B | 109.0 |
| C4—O4—H4 | 112 (4) | C15—C16—C17 | 105.8 (2) |
| C25—O25—H25 | 109 (4) | C15—C16—H16A | 110.6 |
| C5—O56—C6 | 60.70 (19) | C17—C16—H16A | 110.6 |
| O1—C1—C2 | 118.9 (3) | C15—C16—H16B | 110.6 |
| O1—C1—C10 | 121.9 (3) | C17—C16—H16B | 110.6 |
| C2—C1—C10 | 119.2 (3) | H16A—C16—H16B | 108.7 |
| C3—C2—C1 | 123.3 (3) | C20—C17—C16 | 114.3 (2) |
| C3—C2—H2A | 118.3 | C20—C17—C13 | 121.9 (2) |
| C1—C2—H2A | 118.3 | C16—C17—C13 | 103.8 (2) |
| C2—C3—C4 | 123.1 (3) | C20—C17—H17A | 105.1 |
| C2—C3—H3A | 118.5 | C16—C17—H17A | 105.1 |
| C4—C3—H3A | 118.5 | C13—C17—H17A | 105.1 |
| O4—C4—C3 | 105.7 (3) | C13—C18—H18A | 109.5 |
| O4—C4—C5 | 111.8 (3) | C13—C18—H18B | 109.5 |
| C3—C4—C5 | 114.3 (3) | H18A—C18—H18B | 109.5 |
| O4—C4—H4B | 108.3 | C13—C18—H18C | 109.5 |
| C3—C4—H4B | 108.3 | H18A—C18—H18C | 109.5 |
| C5—C4—H4B | 108.3 | H18B—C18—H18C | 109.5 |
| O56—C5—C6 | 59.7 (2) | C10—C19—H19A | 109.5 |
| O56—C5—C4 | 108.1 (2) | C10—C19—H19B | 109.5 |
| C6—C5—C4 | 117.8 (3) | H19A—C19—H19B | 109.5 |
| O56—C5—C10 | 116.2 (2) | C10—C19—H19C | 109.5 |
| C6—C5—C10 | 121.1 (2) | H19A—C19—H19C | 109.5 |
| C4—C5—C10 | 118.2 (3) | H19B—C19—H19C | 109.5 |
| O56—C6—C5 | 59.61 (19) | O3—C20—C22 | 101.0 (2) |
| O56—C6—C7 | 113.8 (2) | O3—C20—C21 | 108.2 (2) |
| C5—C6—C7 | 122.6 (2) | C22—C20—C21 | 110.2 (3) |
| O56—C6—H6A | 116.1 | O3—C20—C17 | 105.5 (2) |
| C5—C6—H6A | 116.1 | C22—C20—C17 | 115.1 (2) |
| C7—C6—H6A | 116.1 | C21—C20—C17 | 115.5 (2) |
| C6—C7—C8 | 111.5 (2) | C20—C21—H21A | 109.5 |
| C6—C7—H7A | 109.3 | C20—C21—H21B | 109.5 |
| C8—C7—H7A | 109.3 | H21A—C21—H21B | 109.5 |
| C6—C7—H7B | 109.3 | C20—C21—H21C | 109.5 |
| C8—C7—H7B | 109.3 | H21A—C21—H21C | 109.5 |
| H7A—C7—H7B | 108.0 | H21B—C21—H21C | 109.5 |
| C7—C8—C14 | 109.5 (2) | O2—C22—C23 | 108.6 (2) |
| C7—C8—C9 | 110.8 (2) | O2—C22—C20 | 110.4 (2) |
| C14—C8—C9 | 107.9 (2) | C23—C22—C20 | 102.6 (3) |
| C7—C8—H8A | 109.5 | O2—C22—H22A | 111.6 |
| C14—C8—H8A | 109.5 | C23—C22—H22A | 111.6 |
| C9—C8—H8A | 109.5 | C20—C22—H22A | 111.6 |
| C8—C9—C11 | 111.5 (2) | C22—C23—C24 | 99.3 (2) |
| C8—C9—C10 | 114.9 (2) | C22—C23—H23A | 111.9 |
| C11—C9—C10 | 112.6 (2) | C24—C23—H23A | 111.9 |
| C8—C9—H9A | 105.6 | C22—C23—H23B | 111.9 |
| C11—C9—H9A | 105.6 | C24—C23—H23B | 111.9 |
| C10—C9—H9A | 105.6 | H23A—C23—H23B | 109.6 |
| C5—C10—C1 | 109.0 (2) | O3—C24—C28 | 109.7 (3) |
| C5—C10—C19 | 107.0 (2) | O3—C24—C23 | 105.2 (2) |
| C1—C10—C19 | 106.1 (3) | C28—C24—C23 | 114.9 (3) |
| C5—C10—C9 | 113.1 (2) | O3—C24—C25 | 104.9 (2) |
| C1—C10—C9 | 108.2 (2) | C28—C24—C25 | 114.1 (3) |
| C19—C10—C9 | 113.2 (2) | C23—C24—C25 | 107.1 (3) |
| C12—C11—C9 | 113.0 (2) | O25—C25—C27 | 111.3 (3) |
| C12—C11—H11A | 109.0 | O25—C25—C24 | 107.0 (2) |
| C9—C11—H11A | 109.0 | C27—C25—C24 | 113.8 (3) |
| C12—C11—H11B | 109.0 | O25—C25—C26 | 106.3 (3) |
| C9—C11—H11B | 109.0 | C27—C25—C26 | 108.6 (3) |
| H11A—C11—H11B | 107.8 | C24—C25—C26 | 109.6 (2) |
| C13—C12—C11 | 111.5 (3) | O26—C26—O2 | 117.3 (3) |
| C13—C12—H12A | 109.3 | O26—C26—C25 | 121.5 (3) |
| C11—C12—H12A | 109.3 | O2—C26—C25 | 121.1 (3) |
| C13—C12—H12B | 109.3 | C25—C27—H27A | 109.5 |
| C11—C12—H12B | 109.3 | C25—C27—H27B | 109.5 |
| H12A—C12—H12B | 108.0 | H27A—C27—H27B | 109.5 |
| C12—C13—C18 | 111.1 (3) | C25—C27—H27C | 109.5 |
| C12—C13—C14 | 107.2 (2) | H27A—C27—H27C | 109.5 |
| C18—C13—C14 | 110.7 (2) | H27B—C27—H27C | 109.5 |
| C12—C13—C17 | 116.1 (2) | C24—C28—H28A | 109.5 |
| C18—C13—C17 | 112.8 (2) | C24—C28—H28B | 109.5 |
| C14—C13—C17 | 98.0 (2) | H28A—C28—H28B | 109.5 |
| C8—C14—C15 | 118.9 (2) | C24—C28—H28C | 109.5 |
| C8—C14—C13 | 114.5 (2) | H28A—C28—H28C | 109.5 |
| C15—C14—C13 | 104.6 (2) | H28B—C28—H28C | 109.5 |
| C8—C14—H14A | 106.0 | Cl1—C1S—Cl3 | 110.3 (3) |
| C15—C14—H14A | 106.0 | Cl1—C1S—Cl2 | 110.3 (3) |
| C13—C14—H14A | 106.0 | Cl3—C1S—Cl2 | 109.7 (3) |
| C14—C15—C16 | 104.0 (2) | Cl1—C1S—H1SA | 108.8 |
| C14—C15—H15A | 111.0 | Cl3—C1S—H1SA | 108.8 |
| C16—C15—H15A | 111.0 | Cl2—C1S—H1SA | 108.8 |
| C14—C15—H15B | 111.0 | ||
| O1—C1—C2—C3 | 168.0 (4) | C18—C13—C14—C8 | 61.1 (3) |
| C10—C1—C2—C3 | −13.6 (6) | C17—C13—C14—C8 | 179.2 (2) |
| C1—C2—C3—C4 | 1.4 (7) | C12—C13—C14—C15 | 167.9 (2) |
| C2—C3—C4—O4 | 113.0 (4) | C18—C13—C14—C15 | −70.8 (3) |
| C2—C3—C4—C5 | −10.3 (6) | C17—C13—C14—C15 | 47.4 (3) |
| C6—O56—C5—C4 | 112.2 (3) | C8—C14—C15—C16 | −161.5 (3) |
| C6—O56—C5—C10 | −112.2 (3) | C13—C14—C15—C16 | −32.3 (3) |
| O4—C4—C5—O56 | 46.6 (4) | C14—C15—C16—C17 | 3.4 (3) |
| C3—C4—C5—O56 | 166.5 (3) | C15—C16—C17—C20 | 161.1 (3) |
| O4—C4—C5—C6 | 111.2 (3) | C15—C16—C17—C13 | 26.1 (3) |
| C3—C4—C5—C6 | −128.8 (3) | C12—C13—C17—C20 | 71.2 (3) |
| O4—C4—C5—C10 | −88.0 (4) | C18—C13—C17—C20 | −58.6 (4) |
| C3—C4—C5—C10 | 32.0 (4) | C14—C13—C17—C20 | −175.1 (2) |
| C5—O56—C6—C7 | 115.1 (3) | C12—C13—C17—C16 | −158.1 (3) |
| C4—C5—C6—O56 | −95.6 (3) | C18—C13—C17—C16 | 72.1 (3) |
| C10—C5—C6—O56 | 104.1 (3) | C14—C13—C17—C16 | −44.4 (3) |
| O56—C5—C6—C7 | −100.4 (3) | C24—O3—C20—C22 | 18.6 (3) |
| C4—C5—C6—C7 | 164.0 (3) | C24—O3—C20—C21 | −97.2 (3) |
| C10—C5—C6—C7 | 3.8 (5) | C24—O3—C20—C17 | 138.7 (2) |
| O56—C6—C7—C8 | −43.7 (3) | C16—C17—C20—O3 | 56.0 (3) |
| C5—C6—C7—C8 | 24.3 (4) | C13—C17—C20—O3 | −177.9 (2) |
| C6—C7—C8—C14 | −172.2 (2) | C16—C17—C20—C22 | 166.4 (2) |
| C6—C7—C8—C9 | −53.3 (3) | C13—C17—C20—C22 | −67.5 (3) |
| C7—C8—C9—C11 | −173.0 (2) | C16—C17—C20—C21 | −63.3 (4) |
| C14—C8—C9—C11 | −53.1 (3) | C13—C17—C20—C21 | 62.7 (4) |
| C7—C8—C9—C10 | 57.3 (3) | C26—O2—C22—C23 | 38.6 (4) |
| C14—C8—C9—C10 | 177.2 (2) | C26—O2—C22—C20 | −73.1 (3) |
| O56—C5—C10—C1 | −172.3 (2) | O3—C20—C22—O2 | 75.4 (3) |
| C6—C5—C10—C1 | 118.8 (3) | C21—C20—C22—O2 | −170.3 (2) |
| C4—C5—C10—C1 | −41.4 (4) | C17—C20—C22—O2 | −37.6 (3) |
| O56—C5—C10—C19 | −58.1 (3) | O3—C20—C22—C23 | −40.2 (3) |
| C6—C5—C10—C19 | −126.9 (3) | C21—C20—C22—C23 | 74.1 (3) |
| C4—C5—C10—C19 | 72.9 (3) | C17—C20—C22—C23 | −153.2 (2) |
| O56—C5—C10—C9 | 67.3 (3) | O2—C22—C23—C24 | −71.4 (3) |
| C6—C5—C10—C9 | −1.6 (4) | C20—C22—C23—C24 | 45.4 (3) |
| C4—C5—C10—C9 | −161.8 (3) | C20—O3—C24—C28 | 133.8 (3) |
| O1—C1—C10—C5 | −149.7 (4) | C20—O3—C24—C23 | 9.7 (3) |
| C2—C1—C10—C5 | 32.0 (4) | C20—O3—C24—C25 | −103.1 (3) |
| O1—C1—C10—C19 | 95.4 (4) | C22—C23—C24—O3 | −34.1 (3) |
| C2—C1—C10—C19 | −82.9 (4) | C22—C23—C24—C28 | −154.9 (3) |
| O1—C1—C10—C9 | −26.4 (5) | C22—C23—C24—C25 | 77.2 (3) |
| C2—C1—C10—C9 | 155.4 (3) | O3—C24—C25—O25 | 178.9 (3) |
| C8—C9—C10—C5 | −28.7 (3) | C28—C24—C25—O25 | −60.9 (4) |
| C11—C9—C10—C5 | −157.8 (2) | C23—C24—C25—O25 | 67.4 (3) |
| C8—C9—C10—C1 | −149.5 (2) | O3—C24—C25—C27 | −57.7 (3) |
| C11—C9—C10—C1 | 81.3 (3) | C28—C24—C25—C27 | 62.4 (4) |
| C8—C9—C10—C19 | 93.2 (3) | C23—C24—C25—C27 | −169.3 (3) |
| C11—C9—C10—C19 | −35.9 (3) | O3—C24—C25—C26 | 64.1 (3) |
| C8—C9—C11—C12 | 53.6 (3) | C28—C24—C25—C26 | −175.8 (3) |
| C10—C9—C11—C12 | −175.6 (3) | C23—C24—C25—C26 | −47.4 (3) |
| C9—C11—C12—C13 | −55.3 (4) | C22—O2—C26—O26 | 176.1 (3) |
| C11—C12—C13—C18 | −65.2 (3) | C22—O2—C26—C25 | −7.0 (4) |
| C11—C12—C13—C14 | 55.9 (3) | O25—C25—C26—O26 | 72.9 (4) |
| C11—C12—C13—C17 | 164.2 (3) | C27—C25—C26—O26 | −46.8 (4) |
| C7—C8—C14—C15 | −55.9 (3) | C24—C25—C26—O26 | −171.7 (3) |
| C9—C8—C14—C15 | −176.6 (3) | O25—C25—C26—O2 | −103.9 (3) |
| C7—C8—C14—C13 | 179.6 (2) | C27—C25—C26—O2 | 136.4 (3) |
| C9—C8—C14—C13 | 58.9 (3) | C24—C25—C26—O2 | 11.5 (4) |
| C12—C13—C14—C8 | −60.3 (3) |
(17S,20R,22R,24R,25S)-5β,6β:20,24-Diepoxy-4β,25-dihydroxy-1-oxowith-2-en-26,22-olide chloroform solvate (I) . Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4···O26i | 0.79 (6) | 2.10 (6) | 2.819 (4) | 151 |
| O25—H25···O56ii | 0.74 (5) | 2.12 (5) | 2.856 (4) | 169 |
| C23—H23A···O26iii | 0.97 | 2.57 | 3.473 (4) | 154 |
| C1S—H1SA···O26 | 0.98 | 2.43 | 3.393 (6) | 168 |
Symmetry codes: (i) x, y, z+1; (ii) x, y, z−1; (iii) x+1, y, z.
(20R,22R)-5α,14α,20-Trihydroxy-1-oxo-6α,7α-epoxywitha-2-enolide (II) . Crystal data
| C28H40O7 | F(000) = 264 |
| Mr = 488.60 | Dx = 1.312 Mg m−3 |
| Triclinic, P1 | Melting point: 528(3) K |
| a = 6.2374 (12) Å | Cu Kα radiation, λ = 1.54184 Å |
| b = 9.5938 (19) Å | Cell parameters from 1941 reflections |
| c = 11.351 (2) Å | θ = 4.3–75.5° |
| α = 112.81 (3)° | µ = 0.76 mm−1 |
| β = 96.49 (3)° | T = 290 K |
| γ = 93.13 (3)° | Prizmatic, colorless |
| V = 618.5 (2) Å3 | 0.42 × 0.28 × 0.21 mm |
| Z = 1 |
(20R,22R)-5α,14α,20-Trihydroxy-1-oxo-6α,7α-epoxywitha-2-enolide (II) . Data collection
| Rigaku Xcalibur, Ruby diffractometer | 2812 independent reflections |
| Radiation source: Enhance (Cu) X-ray Source | 2545 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.025 |
| Detector resolution: 10.2576 pixels mm-1 | θmax = 76.7°, θmin = 4.3° |
| ω scans | h = −7→7 |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→11 |
| Tmin = 0.776, Tmax = 0.853 | l = −14→10 |
| 4169 measured reflections |
(20R,22R)-5α,14α,20-Trihydroxy-1-oxo-6α,7α-epoxywitha-2-enolide (II) . Refinement
| Refinement on F2 | Hydrogen site location: mixed |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.041 | w = 1/[σ2(Fo2) + (0.0647P)2 + 0.0383P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.110 | (Δ/σ)max < 0.001 |
| S = 1.03 | Δρmax = 0.17 e Å−3 |
| 2812 reflections | Δρmin = −0.19 e Å−3 |
| 333 parameters | Absolute structure: Classical Flack method preferred over Parsons because s.u. lower. |
| 3 restraints | Absolute structure parameter: −0.1 (2) |
| Primary atom site location: structure-invariant direct methods |
(20R,22R)-5α,14α,20-Trihydroxy-1-oxo-6α,7α-epoxywitha-2-enolide (II) . Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
(20R,22R)-5α,14α,20-Trihydroxy-1-oxo-6α,7α-epoxywitha-2-enolide (II) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| O1 | 1.0734 (4) | 1.2216 (4) | 0.3845 (3) | 0.0674 (8) | |
| O2 | 1.0070 (4) | 0.6040 (2) | 0.9120 (2) | 0.0441 (5) | |
| O5 | 0.8575 (4) | 0.8791 (3) | 0.0969 (2) | 0.0524 (6) | |
| O14 | 0.9050 (4) | 0.6585 (3) | 0.3671 (2) | 0.0468 (5) | |
| O20 | 0.7306 (4) | 0.7378 (3) | 0.8118 (2) | 0.0444 (5) | |
| O26 | 1.0412 (5) | 0.5281 (3) | 1.0706 (2) | 0.0591 (7) | |
| O67 | 0.6045 (4) | 0.6709 (3) | 0.1319 (2) | 0.0555 (6) | |
| C1 | 0.9157 (5) | 1.1689 (4) | 0.3017 (3) | 0.0431 (7) | |
| C2 | 0.8775 (6) | 1.2312 (5) | 0.2017 (4) | 0.0551 (9) | |
| H2A | 0.9624 | 1.3185 | 0.2108 | 0.066* | |
| C3 | 0.7256 (6) | 1.1664 (5) | 0.0993 (4) | 0.0605 (10) | |
| H3A | 0.7103 | 1.2095 | 0.0387 | 0.073* | |
| C4 | 0.5794 (6) | 1.0290 (4) | 0.0768 (3) | 0.0534 (8) | |
| H4A | 0.5570 | 0.9639 | −0.0146 | 0.064* | |
| H4B | 0.4396 | 1.0589 | 0.1014 | 0.064* | |
| C5 | 0.6713 (5) | 0.9395 (4) | 0.1537 (3) | 0.0417 (7) | |
| C6 | 0.5077 (6) | 0.8077 (4) | 0.1384 (3) | 0.0472 (7) | |
| H6A | 0.3725 | 0.7928 | 0.0798 | 0.057* | |
| C7 | 0.4970 (5) | 0.7531 (4) | 0.2412 (3) | 0.0444 (7) | |
| H7A | 0.3550 | 0.7054 | 0.2427 | 0.053* | |
| C8 | 0.6366 (4) | 0.8339 (3) | 0.3704 (3) | 0.0346 (6) | |
| H8A | 0.5414 | 0.8946 | 0.4290 | 0.042* | |
| C9 | 0.8236 (5) | 0.9479 (3) | 0.3713 (3) | 0.0357 (6) | |
| H9A | 0.9315 | 0.8878 | 0.3238 | 0.043* | |
| C10 | 0.7426 (5) | 1.0460 (3) | 0.2988 (3) | 0.0358 (6) | |
| C11 | 0.9330 (6) | 1.0353 (4) | 0.5127 (3) | 0.0535 (9) | |
| H11A | 1.0577 | 1.1011 | 0.5140 | 0.064* | |
| H11B | 0.8316 | 1.0994 | 0.5613 | 0.064* | |
| C12 | 1.0074 (5) | 0.9316 (4) | 0.5799 (3) | 0.0490 (8) | |
| H12A | 1.0653 | 0.9934 | 0.6694 | 0.059* | |
| H12B | 1.1229 | 0.8769 | 0.5387 | 0.059* | |
| C13 | 0.8206 (4) | 0.8163 (3) | 0.5748 (3) | 0.0343 (6) | |
| C14 | 0.7262 (4) | 0.7268 (3) | 0.4299 (3) | 0.0360 (6) | |
| C15 | 0.5738 (5) | 0.5985 (4) | 0.4314 (3) | 0.0471 (7) | |
| H15A | 0.5507 | 0.5132 | 0.3481 | 0.056* | |
| H15B | 0.4347 | 0.6329 | 0.4535 | 0.056* | |
| C16 | 0.6930 (5) | 0.5546 (4) | 0.5361 (3) | 0.0451 (7) | |
| H16A | 0.7500 | 0.4576 | 0.4966 | 0.054* | |
| H16B | 0.5941 | 0.5457 | 0.5935 | 0.054* | |
| C17 | 0.8822 (4) | 0.6823 (3) | 0.6131 (3) | 0.0353 (6) | |
| H17A | 1.0134 | 0.6476 | 0.5756 | 0.042* | |
| C18 | 0.6480 (6) | 0.9019 (4) | 0.6520 (3) | 0.0478 (7) | |
| H18A | 0.5306 | 0.8303 | 0.6479 | 0.072* | |
| H18B | 0.5940 | 0.9709 | 0.6161 | 0.072* | |
| H18C | 0.7113 | 0.9579 | 0.7405 | 0.072* | |
| C19 | 0.5529 (5) | 1.1315 (4) | 0.3550 (3) | 0.0459 (7) | |
| H19A | 0.5891 | 1.1821 | 0.4472 | 0.069* | |
| H19B | 0.4257 | 1.0605 | 0.3342 | 0.069* | |
| H19C | 0.5250 | 1.2052 | 0.3189 | 0.069* | |
| C20 | 0.9287 (5) | 0.7102 (3) | 0.7577 (3) | 0.0367 (6) | |
| C21 | 1.0997 (5) | 0.8455 (4) | 0.8335 (3) | 0.0458 (7) | |
| H21A | 1.0430 | 0.9375 | 0.8361 | 0.069* | |
| H21B | 1.2274 | 0.8323 | 0.7921 | 0.069* | |
| H21C | 1.1360 | 0.8517 | 0.9200 | 0.069* | |
| C22 | 1.0006 (5) | 0.5651 (3) | 0.7731 (3) | 0.0378 (6) | |
| H22A | 0.8854 | 0.4817 | 0.7265 | 0.045* | |
| C23 | 1.2147 (6) | 0.5111 (4) | 0.7296 (3) | 0.0461 (7) | |
| H23A | 1.3111 | 0.5980 | 0.7375 | 0.055* | |
| H23B | 1.1877 | 0.4423 | 0.6392 | 0.055* | |
| C24 | 1.3270 (5) | 0.4300 (3) | 0.8076 (3) | 0.0404 (6) | |
| H24A | 1.4316 | 0.5062 | 0.8766 | 0.048* | |
| C25 | 1.1654 (5) | 0.3683 (4) | 0.8731 (3) | 0.0430 (7) | |
| H25A | 1.0508 | 0.3003 | 0.8057 | 0.052* | |
| C26 | 1.0632 (5) | 0.5015 (4) | 0.9602 (3) | 0.0414 (7) | |
| C27 | 1.2617 (7) | 0.2800 (5) | 0.9482 (4) | 0.0610 (9) | |
| H27A | 1.1503 | 0.2463 | 0.9859 | 0.091* | |
| H27B | 1.3742 | 0.3445 | 1.0153 | 0.091* | |
| H27C | 1.3216 | 0.1935 | 0.8909 | 0.091* | |
| C28 | 1.4558 (6) | 0.3074 (4) | 0.7249 (4) | 0.0525 (8) | |
| H28A | 1.5525 | 0.2760 | 0.7797 | 0.079* | |
| H28B | 1.5384 | 0.3474 | 0.6764 | 0.079* | |
| H28C | 1.3576 | 0.2216 | 0.6666 | 0.079* | |
| H5 | 0.858 (7) | 0.793 (6) | 0.113 (4) | 0.069 (13)* | |
| H14 | 0.884 (8) | 0.628 (6) | 0.289 (5) | 0.069 (14)* | |
| H20 | 0.768 (9) | 0.767 (7) | 0.884 (6) | 0.09 (2)* |
(20R,22R)-5α,14α,20-Trihydroxy-1-oxo-6α,7α-epoxywitha-2-enolide (II) . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0566 (14) | 0.0798 (18) | 0.0761 (19) | −0.0157 (13) | −0.0101 (13) | 0.0506 (16) |
| O2 | 0.0575 (13) | 0.0457 (12) | 0.0372 (11) | 0.0172 (10) | 0.0157 (9) | 0.0214 (10) |
| O5 | 0.0675 (15) | 0.0570 (15) | 0.0387 (12) | 0.0261 (12) | 0.0205 (10) | 0.0197 (11) |
| O14 | 0.0572 (14) | 0.0504 (13) | 0.0346 (12) | 0.0207 (11) | 0.0123 (10) | 0.0153 (10) |
| O20 | 0.0445 (12) | 0.0573 (14) | 0.0371 (12) | 0.0169 (10) | 0.0125 (9) | 0.0218 (11) |
| O26 | 0.0718 (17) | 0.0731 (17) | 0.0456 (14) | 0.0210 (13) | 0.0187 (12) | 0.0335 (13) |
| O67 | 0.0801 (17) | 0.0401 (12) | 0.0352 (12) | 0.0108 (11) | −0.0037 (11) | 0.0057 (9) |
| C1 | 0.0428 (16) | 0.0457 (17) | 0.0456 (17) | 0.0093 (13) | 0.0078 (13) | 0.0222 (14) |
| C2 | 0.059 (2) | 0.058 (2) | 0.063 (2) | 0.0067 (16) | 0.0102 (17) | 0.0395 (19) |
| C3 | 0.070 (2) | 0.071 (2) | 0.059 (2) | 0.0197 (19) | 0.0074 (18) | 0.044 (2) |
| C4 | 0.065 (2) | 0.059 (2) | 0.0408 (17) | 0.0164 (17) | −0.0008 (15) | 0.0253 (16) |
| C5 | 0.0501 (17) | 0.0462 (17) | 0.0301 (14) | 0.0166 (14) | 0.0064 (12) | 0.0148 (13) |
| C6 | 0.0545 (18) | 0.0424 (17) | 0.0366 (15) | 0.0054 (13) | −0.0093 (13) | 0.0112 (13) |
| C7 | 0.0449 (16) | 0.0414 (17) | 0.0397 (16) | 0.0014 (13) | −0.0063 (13) | 0.0121 (13) |
| C8 | 0.0354 (14) | 0.0361 (14) | 0.0293 (14) | 0.0030 (11) | 0.0002 (11) | 0.0110 (11) |
| C9 | 0.0377 (14) | 0.0393 (15) | 0.0300 (13) | 0.0042 (11) | 0.0031 (10) | 0.0142 (12) |
| C10 | 0.0387 (14) | 0.0382 (14) | 0.0315 (13) | 0.0074 (11) | 0.0057 (10) | 0.0145 (11) |
| C11 | 0.070 (2) | 0.0465 (18) | 0.0395 (17) | −0.0196 (16) | −0.0160 (16) | 0.0223 (15) |
| C12 | 0.0541 (19) | 0.0528 (19) | 0.0384 (16) | −0.0158 (15) | −0.0106 (13) | 0.0238 (15) |
| C13 | 0.0405 (15) | 0.0327 (13) | 0.0299 (13) | 0.0017 (11) | 0.0014 (11) | 0.0141 (11) |
| C14 | 0.0381 (14) | 0.0351 (14) | 0.0305 (14) | 0.0032 (11) | 0.0030 (11) | 0.0090 (11) |
| C15 | 0.0500 (18) | 0.0387 (15) | 0.0466 (17) | −0.0078 (13) | −0.0078 (13) | 0.0161 (14) |
| C16 | 0.0537 (18) | 0.0377 (16) | 0.0410 (16) | −0.0037 (13) | 0.0007 (13) | 0.0153 (13) |
| C17 | 0.0382 (14) | 0.0354 (14) | 0.0321 (14) | 0.0030 (11) | 0.0067 (11) | 0.0128 (12) |
| C18 | 0.065 (2) | 0.0458 (17) | 0.0371 (16) | 0.0202 (15) | 0.0126 (14) | 0.0179 (14) |
| C19 | 0.0497 (18) | 0.0423 (16) | 0.0476 (18) | 0.0135 (14) | 0.0146 (14) | 0.0167 (14) |
| C20 | 0.0390 (14) | 0.0392 (14) | 0.0313 (14) | 0.0046 (11) | 0.0066 (11) | 0.0130 (12) |
| C21 | 0.0556 (19) | 0.0444 (16) | 0.0356 (15) | −0.0026 (14) | −0.0020 (13) | 0.0171 (13) |
| C22 | 0.0416 (15) | 0.0408 (15) | 0.0311 (14) | 0.0043 (12) | 0.0054 (11) | 0.0145 (12) |
| C23 | 0.0491 (17) | 0.0510 (18) | 0.0441 (17) | 0.0133 (14) | 0.0138 (13) | 0.0223 (15) |
| C24 | 0.0429 (15) | 0.0365 (14) | 0.0404 (15) | 0.0057 (12) | 0.0044 (12) | 0.0141 (12) |
| C25 | 0.0443 (15) | 0.0414 (16) | 0.0460 (17) | 0.0057 (12) | 0.0047 (13) | 0.0207 (14) |
| C26 | 0.0421 (15) | 0.0464 (17) | 0.0419 (16) | 0.0052 (13) | 0.0091 (12) | 0.0235 (14) |
| C27 | 0.075 (2) | 0.055 (2) | 0.068 (2) | 0.0181 (19) | 0.0158 (19) | 0.0374 (19) |
| C28 | 0.0481 (17) | 0.0475 (18) | 0.063 (2) | 0.0124 (14) | 0.0125 (15) | 0.0211 (16) |
(20R,22R)-5α,14α,20-Trihydroxy-1-oxo-6α,7α-epoxywitha-2-enolide (II) . Geometric parameters (Å, º)
| O1—C1 | 1.214 (4) | C13—C18 | 1.534 (4) |
| O2—C26 | 1.341 (4) | C13—C14 | 1.555 (4) |
| O2—C22 | 1.468 (3) | C13—C17 | 1.562 (4) |
| O5—C5 | 1.433 (4) | C14—C15 | 1.520 (4) |
| O5—H5 | 0.92 (5) | C15—C16 | 1.538 (5) |
| O14—C14 | 1.442 (4) | C15—H15A | 0.9700 |
| O14—H14 | 0.81 (5) | C15—H15B | 0.9700 |
| O20—C20 | 1.434 (4) | C16—C17 | 1.561 (4) |
| O20—H20 | 0.76 (6) | C16—H16A | 0.9700 |
| O26—C26 | 1.204 (4) | C16—H16B | 0.9700 |
| O67—C7 | 1.448 (4) | C17—C20 | 1.546 (4) |
| O67—C6 | 1.454 (4) | C17—H17A | 0.9800 |
| C1—C2 | 1.478 (5) | C18—H18A | 0.9600 |
| C1—C10 | 1.542 (4) | C18—H18B | 0.9600 |
| C2—C3 | 1.327 (6) | C18—H18C | 0.9600 |
| C2—H2A | 0.9300 | C19—H19A | 0.9600 |
| C3—C4 | 1.480 (6) | C19—H19B | 0.9600 |
| C3—H3A | 0.9300 | C19—H19C | 0.9600 |
| C4—C5 | 1.532 (4) | C20—C21 | 1.530 (4) |
| C4—H4A | 0.9700 | C20—C22 | 1.552 (4) |
| C4—H4B | 0.9700 | C21—H21A | 0.9600 |
| C5—C6 | 1.523 (5) | C21—H21B | 0.9600 |
| C5—C10 | 1.560 (4) | C21—H21C | 0.9600 |
| C6—C7 | 1.458 (5) | C22—C23 | 1.523 (4) |
| C6—H6A | 0.9800 | C22—H22A | 0.9800 |
| C7—C8 | 1.506 (4) | C23—C24 | 1.527 (5) |
| C7—H7A | 0.9800 | C23—H23A | 0.9700 |
| C8—C14 | 1.530 (4) | C23—H23B | 0.9700 |
| C8—C9 | 1.551 (4) | C24—C28 | 1.526 (5) |
| C8—H8A | 0.9800 | C24—C25 | 1.539 (4) |
| C9—C10 | 1.542 (4) | C24—H24A | 0.9800 |
| C9—C11 | 1.546 (4) | C25—C26 | 1.507 (5) |
| C9—H9A | 0.9800 | C25—C27 | 1.518 (5) |
| C10—C19 | 1.534 (4) | C25—H25A | 0.9800 |
| C11—C12 | 1.532 (5) | C27—H27A | 0.9600 |
| C11—H11A | 0.9700 | C27—H27B | 0.9600 |
| C11—H11B | 0.9700 | C27—H27C | 0.9600 |
| C12—C13 | 1.542 (4) | C28—H28A | 0.9600 |
| C12—H12A | 0.9700 | C28—H28B | 0.9600 |
| C12—H12B | 0.9700 | C28—H28C | 0.9600 |
| C26—O2—C22 | 119.2 (2) | C14—C15—H15A | 111.0 |
| C5—O5—H5 | 100 (3) | C16—C15—H15A | 111.0 |
| C14—O14—H14 | 114 (3) | C14—C15—H15B | 111.0 |
| C20—O20—H20 | 103 (4) | C16—C15—H15B | 111.0 |
| C7—O67—C6 | 60.3 (2) | H15A—C15—H15B | 109.0 |
| O1—C1—C2 | 118.9 (3) | C15—C16—C17 | 107.5 (2) |
| O1—C1—C10 | 123.8 (3) | C15—C16—H16A | 110.2 |
| C2—C1—C10 | 117.1 (3) | C17—C16—H16A | 110.2 |
| C3—C2—C1 | 122.0 (3) | C15—C16—H16B | 110.2 |
| C3—C2—H2A | 119.0 | C17—C16—H16B | 110.2 |
| C1—C2—H2A | 119.0 | H16A—C16—H16B | 108.5 |
| C2—C3—C4 | 123.3 (3) | C20—C17—C16 | 113.2 (2) |
| C2—C3—H3A | 118.3 | C20—C17—C13 | 119.4 (2) |
| C4—C3—H3A | 118.3 | C16—C17—C13 | 103.1 (2) |
| C3—C4—C5 | 112.1 (3) | C20—C17—H17A | 106.8 |
| C3—C4—H4A | 109.2 | C16—C17—H17A | 106.8 |
| C5—C4—H4A | 109.2 | C13—C17—H17A | 106.8 |
| C3—C4—H4B | 109.2 | C13—C18—H18A | 109.5 |
| C5—C4—H4B | 109.2 | C13—C18—H18B | 109.5 |
| H4A—C4—H4B | 107.9 | H18A—C18—H18B | 109.5 |
| O5—C5—C6 | 108.7 (3) | C13—C18—H18C | 109.5 |
| O5—C5—C4 | 105.4 (3) | H18A—C18—H18C | 109.5 |
| C6—C5—C4 | 110.6 (3) | H18B—C18—H18C | 109.5 |
| O5—C5—C10 | 109.5 (2) | C10—C19—H19A | 109.5 |
| C6—C5—C10 | 111.4 (2) | C10—C19—H19B | 109.5 |
| C4—C5—C10 | 111.0 (3) | H19A—C19—H19B | 109.5 |
| O67—C6—C7 | 59.6 (2) | C10—C19—H19C | 109.5 |
| O67—C6—C5 | 114.1 (3) | H19A—C19—H19C | 109.5 |
| C7—C6—C5 | 121.6 (3) | H19B—C19—H19C | 109.5 |
| O67—C6—H6A | 116.3 | O20—C20—C21 | 109.3 (3) |
| C7—C6—H6A | 116.3 | O20—C20—C17 | 108.7 (2) |
| C5—C6—H6A | 116.3 | C21—C20—C17 | 112.1 (2) |
| O67—C7—C6 | 60.0 (2) | O20—C20—C22 | 105.9 (2) |
| O67—C7—C8 | 117.5 (3) | C21—C20—C22 | 110.1 (2) |
| C6—C7—C8 | 120.6 (3) | C17—C20—C22 | 110.5 (2) |
| O67—C7—H7A | 115.7 | C20—C21—H21A | 109.5 |
| C6—C7—H7A | 115.7 | C20—C21—H21B | 109.5 |
| C8—C7—H7A | 115.7 | H21A—C21—H21B | 109.5 |
| C7—C8—C14 | 113.8 (2) | C20—C21—H21C | 109.5 |
| C7—C8—C9 | 114.2 (2) | H21A—C21—H21C | 109.5 |
| C14—C8—C9 | 109.8 (2) | H21B—C21—H21C | 109.5 |
| C7—C8—H8A | 106.1 | O2—C22—C23 | 110.7 (2) |
| C14—C8—H8A | 106.1 | O2—C22—C20 | 103.0 (2) |
| C9—C8—H8A | 106.1 | C23—C22—C20 | 118.2 (2) |
| C10—C9—C11 | 116.2 (2) | O2—C22—H22A | 108.2 |
| C10—C9—C8 | 111.0 (2) | C23—C22—H22A | 108.2 |
| C11—C9—C8 | 108.0 (2) | C20—C22—H22A | 108.2 |
| C10—C9—H9A | 107.1 | C22—C23—C24 | 113.1 (3) |
| C11—C9—H9A | 107.1 | C22—C23—H23A | 109.0 |
| C8—C9—H9A | 107.1 | C24—C23—H23A | 109.0 |
| C19—C10—C9 | 111.9 (2) | C22—C23—H23B | 109.0 |
| C19—C10—C1 | 105.6 (2) | C24—C23—H23B | 109.0 |
| C9—C10—C1 | 114.3 (2) | H23A—C23—H23B | 107.8 |
| C19—C10—C5 | 110.1 (2) | C28—C24—C23 | 111.1 (3) |
| C9—C10—C5 | 108.3 (2) | C28—C24—C25 | 112.6 (3) |
| C1—C10—C5 | 106.5 (2) | C23—C24—C25 | 111.5 (3) |
| C12—C11—C9 | 113.7 (3) | C28—C24—H24A | 107.1 |
| C12—C11—H11A | 108.8 | C23—C24—H24A | 107.1 |
| C9—C11—H11A | 108.8 | C25—C24—H24A | 107.1 |
| C12—C11—H11B | 108.8 | C26—C25—C27 | 110.4 (3) |
| C9—C11—H11B | 108.8 | C26—C25—C24 | 107.4 (2) |
| H11A—C11—H11B | 107.7 | C27—C25—C24 | 115.1 (3) |
| C11—C12—C13 | 112.1 (3) | C26—C25—H25A | 107.9 |
| C11—C12—H12A | 109.2 | C27—C25—H25A | 107.9 |
| C13—C12—H12A | 109.2 | C24—C25—H25A | 107.9 |
| C11—C12—H12B | 109.2 | O26—C26—O2 | 118.0 (3) |
| C13—C12—H12B | 109.2 | O26—C26—C25 | 125.7 (3) |
| H12A—C12—H12B | 107.9 | O2—C26—C25 | 116.2 (3) |
| C18—C13—C12 | 109.4 (3) | C25—C27—H27A | 109.5 |
| C18—C13—C14 | 111.2 (2) | C25—C27—H27B | 109.5 |
| C12—C13—C14 | 106.9 (2) | H27A—C27—H27B | 109.5 |
| C18—C13—C17 | 111.2 (2) | C25—C27—H27C | 109.5 |
| C12—C13—C17 | 117.4 (2) | H27A—C27—H27C | 109.5 |
| C14—C13—C17 | 100.3 (2) | H27B—C27—H27C | 109.5 |
| O14—C14—C15 | 107.0 (2) | C24—C28—H28A | 109.5 |
| O14—C14—C8 | 109.7 (2) | C24—C28—H28B | 109.5 |
| C15—C14—C8 | 119.1 (2) | H28A—C28—H28B | 109.5 |
| O14—C14—C13 | 105.9 (2) | C24—C28—H28C | 109.5 |
| C15—C14—C13 | 103.5 (2) | H28A—C28—H28C | 109.5 |
| C8—C14—C13 | 110.8 (2) | H28B—C28—H28C | 109.5 |
| C14—C15—C16 | 103.8 (2) | ||
| O1—C1—C2—C3 | 171.0 (4) | C9—C8—C14—O14 | −52.5 (3) |
| C10—C1—C2—C3 | −12.6 (5) | C7—C8—C14—C15 | −46.7 (4) |
| C1—C2—C3—C4 | 1.1 (6) | C9—C8—C14—C15 | −176.2 (3) |
| C2—C3—C4—C5 | −20.5 (6) | C7—C8—C14—C13 | −166.4 (3) |
| C3—C4—C5—O5 | −68.1 (4) | C9—C8—C14—C13 | 64.1 (3) |
| C3—C4—C5—C6 | 174.6 (3) | C18—C13—C14—O14 | 177.1 (2) |
| C3—C4—C5—C10 | 50.3 (4) | C12—C13—C14—O14 | 57.8 (3) |
| C7—O67—C6—C5 | 113.8 (3) | C17—C13—C14—O14 | −65.2 (3) |
| O5—C5—C6—O67 | 27.8 (3) | C18—C13—C14—C15 | −70.5 (3) |
| C4—C5—C6—O67 | 143.1 (3) | C12—C13—C14—C15 | 170.1 (3) |
| C10—C5—C6—O67 | −92.9 (3) | C17—C13—C14—C15 | 47.2 (3) |
| O5—C5—C6—C7 | 95.8 (4) | C18—C13—C14—C8 | 58.2 (3) |
| C4—C5—C6—C7 | −148.9 (3) | C12—C13—C14—C8 | −61.2 (3) |
| C10—C5—C6—C7 | −25.0 (4) | C17—C13—C14—C8 | 175.9 (2) |
| C6—O67—C7—C8 | −111.3 (3) | O14—C14—C15—C16 | 74.2 (3) |
| C5—C6—C7—O67 | −101.2 (3) | C8—C14—C15—C16 | −160.8 (3) |
| O67—C6—C7—C8 | 106.1 (3) | C13—C14—C15—C16 | −37.3 (3) |
| C5—C6—C7—C8 | 4.9 (5) | C14—C15—C16—C17 | 13.0 (3) |
| O67—C7—C8—C14 | −71.8 (3) | C15—C16—C17—C20 | 146.3 (3) |
| C6—C7—C8—C14 | −141.6 (3) | C15—C16—C17—C13 | 16.0 (3) |
| O67—C7—C8—C9 | 55.4 (4) | C18—C13—C17—C20 | −46.5 (3) |
| C6—C7—C8—C9 | −14.4 (4) | C12—C13—C17—C20 | 80.5 (3) |
| C7—C8—C9—C10 | 44.7 (3) | C14—C13—C17—C20 | −164.2 (2) |
| C14—C8—C9—C10 | 173.9 (2) | C18—C13—C17—C16 | 79.9 (3) |
| C7—C8—C9—C11 | 173.1 (3) | C12—C13—C17—C16 | −153.1 (3) |
| C14—C8—C9—C11 | −57.7 (3) | C14—C13—C17—C16 | −37.8 (3) |
| C11—C9—C10—C19 | −67.2 (3) | C16—C17—C20—O20 | −53.7 (3) |
| C8—C9—C10—C19 | 56.7 (3) | C13—C17—C20—O20 | 67.9 (3) |
| C11—C9—C10—C1 | 52.9 (4) | C16—C17—C20—C21 | −174.6 (3) |
| C8—C9—C10—C1 | 176.7 (2) | C13—C17—C20—C21 | −53.1 (3) |
| C11—C9—C10—C5 | 171.4 (3) | C16—C17—C20—C22 | 62.1 (3) |
| C8—C9—C10—C5 | −64.8 (3) | C13—C17—C20—C22 | −176.3 (2) |
| O1—C1—C10—C19 | 99.7 (4) | C26—O2—C22—C23 | −53.1 (3) |
| C2—C1—C10—C19 | −76.5 (4) | C26—O2—C22—C20 | 179.6 (2) |
| O1—C1—C10—C9 | −23.8 (5) | O20—C20—C22—O2 | −54.7 (3) |
| C2—C1—C10—C9 | 160.0 (3) | C21—C20—C22—O2 | 63.4 (3) |
| O1—C1—C10—C5 | −143.3 (4) | C17—C20—C22—O2 | −172.2 (2) |
| C2—C1—C10—C5 | 40.5 (4) | O20—C20—C22—C23 | −177.1 (3) |
| O5—C5—C10—C19 | 170.9 (3) | C21—C20—C22—C23 | −59.1 (3) |
| C6—C5—C10—C19 | −68.9 (3) | C17—C20—C22—C23 | 65.4 (3) |
| C4—C5—C10—C19 | 54.9 (3) | O2—C22—C23—C24 | 31.1 (4) |
| O5—C5—C10—C9 | −66.6 (3) | C20—C22—C23—C24 | 149.5 (3) |
| C6—C5—C10—C9 | 53.7 (3) | C22—C23—C24—C28 | 148.4 (3) |
| C4—C5—C10—C9 | 177.5 (3) | C22—C23—C24—C25 | 21.9 (4) |
| O5—C5—C10—C1 | 56.8 (3) | C28—C24—C25—C26 | 175.2 (3) |
| C6—C5—C10—C1 | 177.1 (3) | C23—C24—C25—C26 | −59.1 (3) |
| C4—C5—C10—C1 | −59.1 (3) | C28—C24—C25—C27 | 51.8 (4) |
| C10—C9—C11—C12 | 179.3 (3) | C23—C24—C25—C27 | 177.5 (3) |
| C8—C9—C11—C12 | 53.9 (4) | C22—O2—C26—O26 | −170.9 (3) |
| C9—C11—C12—C13 | −55.1 (4) | C22—O2—C26—C25 | 13.8 (4) |
| C11—C12—C13—C18 | −64.7 (3) | C27—C25—C26—O26 | −6.5 (5) |
| C11—C12—C13—C14 | 55.8 (3) | C24—C25—C26—O26 | −132.7 (3) |
| C11—C12—C13—C17 | 167.4 (3) | C27—C25—C26—O2 | 168.4 (3) |
| C7—C8—C14—O14 | 76.9 (3) | C24—C25—C26—O2 | 42.2 (4) |
(20R,22R)-5α,14α,20-Trihydroxy-1-oxo-6α,7α-epoxywitha-2-enolide (II) . Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O20—H20···O5i | 0.76 (6) | 2.22 (6) | 2.973 (4) | 173 |
| C7—H7A···O26ii | 0.98 | 2.59 | 3.367 (5) | 136 |
Symmetry codes: (i) x, y, z+1; (ii) x−1, y, z−1.
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I, II, Global. DOI: 10.1107/S205698902100709X/dj2029sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S205698902100709X/dj2029Isup2.hkl
Structure factors: contains datablock(s) II. DOI: 10.1107/S205698902100709X/dj2029IIsup3.hkl
Additional supporting information: crystallographic information; 3D view; checkCIF report