(5R,6S,8S,9R,14R,15R,17R,18S,21S,24R,26S,27R)-5α-Chloro-16,24-cyclo-13,14-secoergost-2-ene-18,26-dioic acid-14:17,14:27-diep­oxy-6β,13,20,22-tetra­hydr­oxy-1,15-dioxo-γ-lactone δ-lactone methanol solvate monohydrate

Choudhary, M.I.; Yousuf, S.; Atta-ur-Rahman; Anjum, S.; Fun, H.-K.; Ali, S.

doi:10.1107/S1600536805030011

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(5R,6S,8S,9R,14R,15R,17R,18S,21S,24R,26S,27R)-5α-Chloro-16,24-cyclo-13,14-secoergost-2-ene-18,26-dioic acid-14:17,14:27-diepoxy-6β,13,20,22-tetrahydroxy-1,15-dioxo-γ-lactone δ-lactone methanol solvate monohydrate

M. I. Choudhary, S. Yousuf, Atta-ur-Rahman, S. Anjum, H.-K. Fun and S. Ali

The title compound, C₂₈H₂₇O₁₀Cl·CH₃OH·H₂O, was isolated from Physalis minima. The rigid molecule consists of eight fused rings involving three lactones. The spiro-fused γ-lactone rings are in half-chair and envelope conformations. The spiro-fused γ-lactone rings are fused to a cyclohexene ring, which is in a half-chair conformation. The outermost cyclohexene ring and δ-lactone rings adopt half-chair and envelope conformations, respectively. Intra- and intermolecular O—H

O, C—H

Cl and C—H

O hydrogen bonds are observed.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030011/ci6649sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030011/ci6649Isup2.hkl Contains datablock I

CCDC reference: 287514

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
Disorder in solvent or counterion
R factor = 0.035
wR factor = 0.095
Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for        C29
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      25.00 Perc.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          4

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.49
           From the CIF: _reflns_number_total               5745
           Count of symmetry unique reflns         3229
           Completeness (_total/calc)            177.92%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2516
           Fraction of Friedel pairs measured     0.779
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Physalins are the steroidal lactone constituents of Physalis and other closely related genera, belonging to the family Solanaceae (Makino et al., 1995a). Normal withanolides like withaferin-A are C-28 steroidal compounds possessing a relatively highly oxidized ergostane-type skeleton and characterized by a six-membered lactone ring in the side chain (Kirson et al., 1971; Glotter et al., 1974). The physalins are biogenetically related to the withanolides and characterized by (a) oxidative C13/C14-bond cleavage yielding a nine-membered ring, (b) formation of a new six-membered carbocycle between C16 and C24, and (c) oxidation of the C13 methyl group to a carboxylic acid, which results in the formation of 18,20-lactonization (Glotter et al., 1974). Physalins are commonly named as 16,24-cyclo-13,14-seco steroids (Makino et al., 1995a).

The title compound, (I), known as physalin H, is a steroidal lactone (physalin) previously isolated from Physalis angulata (Row et al., 1978; Makino et al., 1995b). Steroidal lactones (withanolides and physalins) exhibited a number of biological activities, including antitumor (Antoun et al., 1981), immunomodulatory (Budhiraja et al., 1984), antimycobacterial (Pietro et al., 2000), antifungal, anti-inflammatory (Budhiraja et al., 1984, 1986), insect repellant (Glotter, 1991) and immunostimulating (Bates & Eckert, 1972). Compound (I) showed moderate in-vitro cytotoxic activity against HeLa cells (Makino et al., 1995b). As part of our on-going research on bioactive constituents from medicinal plants, we have isolated compound (I) from Physalis minima for the first time. The fresh plants of Physalis minima, locally known as Aknaaj, were collected from Karachi (Pakistan). In the present investigation we have established the absolute structure and stereochemistry of (I) by single-crystal X-ray diffraction studies (Fig. 1).

Compound (I) is a highly oxygenated steroidal lactone bearing eight fused rings. The six-membered ring A (C1–C5/C10) is in a half-chair conformation, with atoms C5 and C10 deviating from the C1/C2/C3/C4 plane by 0.335 (4) and −0.453 (4) Å, respectively. Ring B (C5–C10) is trans-fused to ring A and adopts a chair conformation. The two spiro-fused five-membered rings D (O8/C14—C17) and E (O9/C18/C13/C17/C20) adopt half-chair and envelope conformations, respectively; in D, the deviations of atoms C16 and C17 from the O8/C14/C15 plane are 0.355 (4) and −0.226 (4) Å, respectively, and in ring E atom C17 deviates 0.638 (3) Å from the O9/C18/C13/C20 plane. Ring F (C16/C17/C20/C22–C24) is in a half-chair conformation, allowing the C24—C16—C17, C16—C17—C20, C17—C20—C22 and C20—C22—C23 bond angles to widen to 114.61 (14), 114.97 (14), 114.43 (14) and 114.83 (16)°, respectively, while the other internal angles remain close to the tetrahedral value. Ring G (O10/C22–C26) adopts an envelope conformation. The two epoxy seven- and eight-membered rings (O7/C14–C16/C24/C25/C27 and C8/C9/C11–C14/C17/O8) are in chair and boat–chair conformations, respectively.

The Csp³—Csp³ bond distances lie in the range 1.508 (3)–1.566 (2) Å. The C24—C25—C26 [117.03 (15)°], C9—C11—C12 [119.48 (14)°] and C11—C12—C13 [119.98 (14)°] angles significantly deviate from ideal tetrahedral values, as reported for this class of compounds (Kawai et al., 1970, 1994; Taga et al., 1991). The bond angles involving the spiro atom C17 range from 102.02 (13) to 115.05 (13)°.

The water and methanol molecules of solvation participate in several hydrogen bonds. A number of O—H···O, C—H···Cl and C—H···O hydrogen bonds are observed in the molecular and crystal structures. The molecules are linked together by these interactions to form a three-dimensional molecular network (Fig. 2). Most of the intramolecular hydrogen bonds form S(5) or S(6) ring motifs (Bernstein et al., 1995).

Experimental top

Air-dried and milled plant of Physalis minima (25.8 kg) was extracted with methanol (120 l) over a period of 21 d at room temperature. After evaporation of the solvent, an extract (2.5 kg) was obtained, which was dissolved in distilled water (5 l) and defatted with petroleum ether (10 l). The defatted aqueous extract was further fractionated with CH₂Cl₂ (35 l) and BuOH (5 l), respectively. The CH₂Cl₂ extract was concentrated to a gum (350.5 g) and subjected to column chromatography. A fraction (1.4 g), obtained on elution with CH₂Cl₂:MeOH (95:5), was subjected to repeated column chromatography, which yielded sub-fractions A (120.5 mg), B (98.8 mg), C (50.5 mg), D (105.8 mg) and E (88.5 mg). Repeated column chromatography on sub-fraction B (silica gel 70–230 mesh size) by using petroleum ether/acetone (80:20), afforded compound (I) (20 mg), which was recrystalized using CH₂Cl₂/MeOH (70:30) [Physalin H (I): 20 mg, 5.7 X 10⁻³% yield, m.p. 548–551 K].

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

Figures top

	Fig. 1. The structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms and methanol and water molecules have been omitted for clarity.
	Fig. 2. The crystal packing of (I), viewed along the c axis. Dashed lines indicated hydrogen bonds.

(5R,6S,8S,9R,14R,15R,17R,18S,21S,24R,26S,27R)-5α-Chloro- 16,24-cyclo-13,14-secoergosta-2-ene-18,26-dioic acid-14:17,14:27-diepoxy- 6β,13,20,22-tetrahydroxy-1,15-dioxo-γ-lactone δ-lactone 5α-chloro methanol solvate monohydrate top

Crystal data top

C₂₈H₃₁ClO₁₀·CH₄O·H₂O	D_x = 1.466 Mg m⁻³
M_r = 613.04	Melting point: 548-551K K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 15020 reflections
a = 13.0931 (5) Å	θ = 2.0–26.5°
b = 13.5932 (6) Å	µ = 0.21 mm⁻¹
c = 15.6098 (6) Å	T = 293 K
V = 2778.19 (19) Å³	Block, colourless
Z = 4	0.54 × 0.33 × 0.21 mm
F(000) = 1296

Data collection top

Siemens SMART CCD area-detector diffractometer	5745 independent reflections
Radiation source: fine-focus sealed tube	5545 reflections with I > 2s(I)
Graphite monochromator	R_int = 0.017
Detector resolution: 8.33 pixels mm^-1	θ_max = 26.5°, θ_min = 2.0°
ω scans	h = −16→14
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −17→16
T_min = 0.897, T_max = 0.957	l = −19→17
15825 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0667P)² + 1.2367P] where P = (F_o² + 2F_c²)/3
S = 0.85	(Δ/σ)_max = 0.002
5745 reflections	Δρ_max = 0.25 e Å⁻³
389 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2520 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (6)

Crystal data top

C₂₈H₃₁ClO₁₀·CH₄O·H₂O	V = 2778.19 (19) Å³
M_r = 613.04	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 13.0931 (5) Å	µ = 0.21 mm⁻¹
b = 13.5932 (6) Å	T = 293 K
c = 15.6098 (6) Å	0.54 × 0.33 × 0.21 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	5745 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5545 reflections with I > 2s(I)
T_min = 0.897, T_max = 0.957	R_int = 0.017
15825 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.095	Δρ_max = 0.25 e Å⁻³
S = 0.85	Δρ_min = −0.25 e Å⁻³
5745 reflections	Absolute structure: Flack (1983), 2520 Friedel pairs
389 parameters	Absolute structure parameter: 0.02 (6)
0 restraints

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.70341 (4)	0.30056 (4)	0.53504 (4)	0.04919 (14)
O1	0.47153 (12)	−0.15284 (12)	0.69242 (10)	0.0508 (4)
O2	0.60685 (10)	0.02900 (9)	0.63390 (8)	0.0333 (3)
H1O2	0.5634	0.0586	0.6616	0.050*
O3	0.45453 (12)	0.23446 (11)	0.59524 (10)	0.0460 (3)
O4	0.64876 (13)	0.28107 (11)	0.28553 (10)	0.0494 (4)
H1O4	0.6682	0.3331	0.2645	0.074*
O5	0.50681 (13)	−0.09199 (11)	0.33522 (10)	0.0467 (4)
O6	0.92432 (11)	−0.14723 (12)	0.40506 (10)	0.0466 (4)
O7	0.72952 (11)	−0.03230 (9)	0.33403 (8)	0.0349 (3)
O8	0.70155 (9)	−0.02856 (8)	0.47939 (7)	0.0262 (2)
O9	0.63215 (11)	−0.18638 (10)	0.65540 (8)	0.0381 (3)
O10	0.85189 (10)	−0.21637 (10)	0.51482 (9)	0.0379 (3)
C1	0.48313 (14)	0.28525 (14)	0.53649 (13)	0.0356 (4)
C2	0.47354 (17)	0.39417 (15)	0.54057 (16)	0.0474 (5)
H2	0.4290	0.4220	0.5801	0.057*
C3	0.52632 (19)	0.45194 (15)	0.48990 (17)	0.0537 (6)
H3	0.5175	0.5196	0.4953	0.064*
C4	0.59990 (18)	0.41515 (14)	0.42397 (16)	0.0478 (5)
H4A	0.6622	0.4536	0.4269	0.057*
H4B	0.5706	0.4242	0.3674	0.057*
C5	0.62581 (14)	0.30661 (14)	0.43658 (13)	0.0346 (4)
C6	0.69655 (15)	0.26717 (13)	0.36651 (12)	0.0360 (4)
H6	0.7607	0.3043	0.3677	0.043*
C7	0.71982 (14)	0.15902 (13)	0.37879 (12)	0.0334 (4)
H7A	0.7616	0.1510	0.4296	0.040*
H7B	0.7589	0.1355	0.3301	0.040*
C8	0.62309 (13)	0.09645 (12)	0.38803 (11)	0.0280 (3)
H8	0.5828	0.1032	0.3355	0.034*
C9	0.55718 (12)	0.13218 (12)	0.46438 (12)	0.0268 (3)
H9	0.5988	0.1264	0.5163	0.032*
C10	0.52911 (13)	0.24338 (12)	0.45306 (12)	0.0296 (3)
C11	0.45929 (13)	0.06956 (13)	0.47809 (12)	0.0321 (4)
H11A	0.4422	0.0395	0.4236	0.039*
H11B	0.4042	0.1145	0.4921	0.039*
C12	0.45925 (13)	−0.01341 (13)	0.54687 (13)	0.0335 (4)
H12A	0.4156	0.0082	0.5934	0.040*
H12B	0.4268	−0.0705	0.5214	0.040*
C13	0.55967 (14)	−0.04772 (12)	0.58633 (11)	0.0292 (3)
C14	0.65590 (13)	−0.01169 (12)	0.39691 (11)	0.0281 (3)
C15	0.56997 (14)	−0.08887 (12)	0.39045 (11)	0.0308 (4)
C16	0.58959 (13)	−0.16217 (12)	0.46101 (11)	0.0285 (3)
H16	0.5252	−0.1887	0.4832	0.034*
C17	0.64152 (12)	−0.09583 (12)	0.52817 (10)	0.0258 (3)
C18	0.54521 (16)	−0.13294 (13)	0.65017 (12)	0.0359 (4)
C19	0.45012 (15)	0.25844 (15)	0.38079 (14)	0.0398 (4)
H19A	0.4314	0.3266	0.3779	0.060*
H19B	0.3905	0.2196	0.3924	0.060*
H19C	0.4793	0.2385	0.3271	0.060*
C20	0.70912 (14)	−0.15085 (13)	0.59430 (11)	0.0305 (3)
C21	0.78881 (16)	−0.08868 (15)	0.63977 (12)	0.0385 (4)
H21A	0.8333	−0.1306	0.6722	0.058*
H21B	0.7555	−0.0432	0.6776	0.058*
H21C	0.8280	−0.0529	0.5982	0.058*
C22	0.75940 (15)	−0.24517 (14)	0.55988 (12)	0.0353 (4)
H22	0.7794	−0.2856	0.6091	0.042*
C23	0.69212 (16)	−0.30686 (13)	0.50272 (13)	0.0375 (4)
H23A	0.6326	−0.3288	0.5344	0.045*
H23B	0.7294	−0.3645	0.4836	0.045*
C24	0.65847 (14)	−0.24626 (13)	0.42542 (12)	0.0319 (4)
C25	0.75629 (14)	−0.21015 (12)	0.37799 (11)	0.0318 (4)
H25	0.7785	−0.2686	0.3463	0.038*
C26	0.84869 (14)	−0.18543 (13)	0.43305 (12)	0.0334 (4)
C27	0.74235 (16)	−0.13267 (14)	0.30708 (12)	0.0361 (4)
H27A	0.8014	−0.1357	0.2696	0.043*
H27B	0.6832	−0.1510	0.2733	0.043*
C28	0.59433 (17)	−0.30946 (15)	0.36517 (14)	0.0439 (5)
H28A	0.5332	−0.3299	0.3940	0.066*
H28B	0.6329	−0.3664	0.3483	0.066*
H28C	0.5766	−0.2719	0.3153	0.066*
O1W	0.47528 (12)	0.12687 (11)	0.74535 (10)	0.0485 (4)
H2W1	0.5033	0.1404	0.7905	0.073*
H1W1	0.4680	0.1810	0.7197	0.073*
O11A	0.7738 (4)	0.4185 (3)	0.2148 (4)	0.0693 (11)	0.602 (6)
O11B	0.7748 (6)	0.4512 (5)	0.2552 (5)	0.0693 (11)	0.398 (6)
H11O	0.843 (3)	0.414 (3)	0.235 (2)	0.101 (13)*
C29	0.7662 (3)	0.5197 (3)	0.1962 (3)	0.0988 (12)
H29A	0.7792	0.5571	0.2472	0.148*	0.602 (6)
H29B	0.6987	0.5341	0.1756	0.148*	0.602 (6)
H29C	0.8154	0.5368	0.1531	0.148*	0.602 (6)
H29D	0.7503	0.5370	0.1381	0.148*	0.398 (6)
H29E	0.7150	0.5462	0.2337	0.148*	0.398 (6)
H29F	0.8317	0.5462	0.2113	0.148*	0.398 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0384 (2)	0.0577 (3)	0.0514 (3)	−0.0093 (2)	−0.0061 (2)	−0.0103 (2)
O1	0.0549 (9)	0.0460 (8)	0.0514 (9)	0.0001 (7)	0.0237 (8)	0.0101 (7)
O2	0.0385 (7)	0.0304 (6)	0.0311 (6)	0.0007 (5)	0.0021 (5)	−0.0068 (5)
O3	0.0507 (8)	0.0442 (8)	0.0429 (8)	0.0028 (7)	0.0087 (7)	0.0009 (7)
O4	0.0654 (10)	0.0401 (8)	0.0427 (8)	0.0016 (7)	0.0026 (7)	0.0126 (6)
O5	0.0550 (9)	0.0422 (8)	0.0429 (8)	−0.0015 (7)	−0.0205 (7)	−0.0036 (6)
O6	0.0403 (8)	0.0519 (8)	0.0478 (8)	−0.0076 (7)	0.0073 (7)	−0.0063 (7)
O7	0.0473 (8)	0.0282 (6)	0.0290 (6)	0.0040 (5)	0.0091 (5)	0.0019 (5)
O8	0.0292 (5)	0.0254 (5)	0.0241 (5)	−0.0031 (5)	−0.0005 (5)	0.0036 (4)
O9	0.0477 (7)	0.0353 (7)	0.0313 (6)	0.0035 (6)	0.0085 (6)	0.0092 (6)
O10	0.0344 (6)	0.0431 (7)	0.0361 (7)	0.0075 (6)	−0.0001 (5)	−0.0003 (6)
C1	0.0292 (8)	0.0339 (9)	0.0436 (10)	0.0016 (7)	0.0013 (8)	−0.0023 (8)
C2	0.0457 (11)	0.0328 (10)	0.0638 (14)	0.0036 (9)	0.0109 (11)	−0.0104 (9)
C3	0.0575 (13)	0.0272 (9)	0.0765 (16)	0.0018 (9)	0.0114 (12)	−0.0059 (10)
C4	0.0508 (12)	0.0262 (9)	0.0665 (14)	−0.0026 (9)	0.0104 (11)	0.0030 (9)
C5	0.0333 (9)	0.0285 (8)	0.0421 (10)	−0.0022 (7)	−0.0002 (7)	0.0006 (8)
C6	0.0364 (9)	0.0303 (9)	0.0413 (10)	−0.0040 (7)	0.0053 (8)	0.0052 (7)
C7	0.0326 (9)	0.0301 (8)	0.0375 (9)	0.0008 (7)	0.0059 (7)	0.0036 (7)
C8	0.0311 (8)	0.0252 (8)	0.0277 (8)	0.0007 (6)	−0.0009 (6)	0.0035 (6)
C9	0.0256 (7)	0.0228 (7)	0.0320 (8)	−0.0003 (6)	−0.0023 (7)	0.0016 (6)
C10	0.0272 (8)	0.0254 (8)	0.0361 (9)	0.0006 (6)	−0.0011 (7)	0.0013 (6)
C11	0.0254 (8)	0.0280 (8)	0.0430 (10)	−0.0005 (7)	−0.0025 (7)	0.0011 (7)
C12	0.0268 (8)	0.0301 (9)	0.0435 (10)	−0.0032 (7)	0.0065 (7)	−0.0003 (7)
C13	0.0338 (9)	0.0250 (8)	0.0287 (8)	−0.0026 (7)	0.0045 (7)	−0.0006 (7)
C14	0.0333 (8)	0.0272 (8)	0.0237 (8)	0.0003 (7)	−0.0016 (7)	0.0015 (6)
C15	0.0383 (9)	0.0248 (8)	0.0293 (8)	0.0021 (7)	−0.0016 (7)	−0.0043 (7)
C16	0.0307 (8)	0.0249 (8)	0.0299 (8)	−0.0022 (6)	0.0006 (7)	−0.0014 (6)
C17	0.0288 (8)	0.0229 (7)	0.0258 (8)	−0.0012 (6)	0.0006 (6)	0.0013 (6)
C18	0.0470 (11)	0.0295 (8)	0.0312 (9)	−0.0023 (8)	0.0081 (8)	0.0011 (7)
C19	0.0353 (9)	0.0373 (10)	0.0466 (11)	0.0036 (8)	−0.0075 (8)	0.0085 (8)
C20	0.0370 (9)	0.0300 (8)	0.0245 (8)	0.0016 (7)	0.0016 (7)	0.0044 (6)
C21	0.0429 (10)	0.0415 (10)	0.0309 (9)	0.0040 (9)	−0.0067 (8)	−0.0017 (7)
C22	0.0418 (10)	0.0306 (9)	0.0335 (9)	0.0062 (8)	0.0001 (8)	0.0068 (7)
C23	0.0483 (10)	0.0240 (8)	0.0402 (10)	0.0039 (8)	0.0056 (8)	0.0028 (7)
C24	0.0393 (9)	0.0234 (8)	0.0330 (9)	−0.0009 (7)	0.0024 (7)	−0.0044 (7)
C25	0.0400 (9)	0.0251 (8)	0.0302 (8)	0.0023 (7)	0.0028 (7)	−0.0044 (7)
C26	0.0359 (9)	0.0281 (8)	0.0363 (9)	0.0051 (7)	0.0033 (7)	−0.0056 (7)
C27	0.0474 (10)	0.0334 (9)	0.0275 (9)	0.0042 (8)	0.0038 (8)	−0.0020 (7)
C28	0.0536 (12)	0.0313 (9)	0.0468 (11)	−0.0067 (9)	−0.0012 (10)	−0.0101 (9)
O1W	0.0566 (9)	0.0474 (8)	0.0413 (8)	0.0055 (7)	−0.0012 (7)	−0.0070 (7)
O11A	0.0609 (14)	0.059 (2)	0.088 (3)	−0.0100 (18)	−0.003 (2)	0.0176 (18)
O11B	0.0609 (14)	0.059 (2)	0.088 (3)	−0.0100 (18)	−0.003 (2)	0.0176 (18)
C29	0.108 (3)	0.0626 (19)	0.126 (3)	−0.0004 (19)	−0.022 (3)	0.017 (2)

Geometric parameters (Å, º) top

Cl1—C5	1.844 (2)	C12—H12B	0.97
O1—C18	1.200 (2)	C13—C18	1.540 (2)
O2—C13	1.421 (2)	C13—C17	1.549 (2)
O2—H1O2	0.82	C14—C15	1.542 (2)
O3—C1	1.207 (2)	C15—C16	1.507 (2)
O4—C6	1.423 (3)	C16—C17	1.541 (2)
O4—H1O4	0.82	C16—C24	1.558 (2)
O5—C15	1.195 (2)	C16—H16	0.98
O6—C26	1.200 (2)	C17—C20	1.552 (2)
O7—C14	1.404 (2)	C19—H19A	0.96
O7—C27	1.438 (2)	C19—H19B	0.96
O8—C17	1.4261 (19)	C19—H19C	0.96
O8—C14	1.438 (2)	C20—C21	1.519 (3)
O9—C18	1.353 (2)	C20—C22	1.538 (2)
O9—C20	1.469 (2)	C21—H21A	0.96
O10—C26	1.344 (2)	C21—H21B	0.96
O10—C22	1.454 (2)	C21—H21C	0.96
C1—C2	1.487 (3)	C22—C23	1.508 (3)
C1—C10	1.543 (3)	C22—H22	0.98
C2—C3	1.311 (3)	C23—C24	1.526 (3)
C2—H2	0.93	C23—H23A	0.97
C3—C4	1.496 (3)	C23—H23B	0.97
C3—H3	0.93	C24—C28	1.526 (3)
C4—C5	1.527 (3)	C24—C25	1.559 (3)
C4—H4A	0.97	C25—C26	1.522 (3)
C4—H4B	0.97	C25—C27	1.539 (3)
C5—C6	1.530 (3)	C25—H25	0.98
C5—C10	1.552 (2)	C27—H27A	0.97
C6—C7	1.514 (2)	C27—H27B	0.97
C6—H6	0.98	C28—H28A	0.96
C7—C8	1.532 (2)	C28—H28B	0.96
C7—H7A	0.97	C28—H28C	0.96
C7—H7B	0.97	O1W—H2W1	0.82
C8—C14	1.538 (2)	O1W—H1W1	0.84
C8—C9	1.550 (2)	O11A—C29	1.410 (6)
C8—H8	0.98	O11A—H11O	0.96 (4)
C9—C11	1.553 (2)	O11B—C29	1.314 (8)
C9—C10	1.566 (2)	O11B—H11O	1.07 (4)
C9—H9	0.98	C29—H29A	0.96
C10—C19	1.544 (2)	C29—H29B	0.96
C11—C12	1.557 (3)	C29—H29C	0.96
C11—H11A	0.97	C29—H29D	0.96
C11—H11B	0.97	C29—H29E	0.96
C12—C13	1.525 (2)	C29—H29F	0.96
C12—H12A	0.97

C13—O2—H1O2	109.5	O8—C17—C20	110.48 (13)
C6—O4—H1O4	109.5	C16—C17—C20	114.97 (14)
C14—O7—C27	118.30 (14)	C13—C17—C20	102.02 (13)
C17—O8—C14	110.56 (12)	O1—C18—O9	121.50 (17)
C18—O9—C20	111.19 (13)	O1—C18—C13	128.64 (18)
C26—O10—C22	121.17 (15)	O9—C18—C13	109.85 (15)
O3—C1—C2	120.70 (19)	C10—C19—H19A	109.5
O3—C1—C10	123.43 (17)	C10—C19—H19B	109.5
C2—C1—C10	115.86 (17)	H19A—C19—H19B	109.5
C3—C2—C1	121.7 (2)	C10—C19—H19C	109.5
C3—C2—H2	119.1	H19A—C19—H19C	109.5
C1—C2—H2	119.1	H19B—C19—H19C	109.5
C2—C3—C4	123.65 (19)	O9—C20—C21	110.53 (14)
C2—C3—H3	118.2	O9—C20—C22	104.26 (14)
C4—C3—H3	118.2	C21—C20—C22	109.45 (16)
C3—C4—C5	112.18 (18)	O9—C20—C17	101.48 (13)
C3—C4—H4A	109.2	C21—C20—C17	115.75 (14)
C5—C4—H4A	109.2	C22—C20—C17	114.43 (14)
C3—C4—H4B	109.2	C20—C21—H21A	109.5
C5—C4—H4B	109.2	C20—C21—H21B	109.5
H4A—C4—H4B	107.9	H21A—C21—H21B	109.5
C4—C5—C6	112.39 (16)	C20—C21—H21C	109.5
C4—C5—C10	112.04 (16)	H21A—C21—H21C	109.5
C6—C5—C10	114.73 (16)	H21B—C21—H21C	109.5
C4—C5—Cl1	105.84 (15)	O10—C22—C23	110.48 (16)
C6—C5—Cl1	104.28 (13)	O10—C22—C20	107.52 (15)
C10—C5—Cl1	106.65 (13)	C23—C22—C20	114.83 (16)
O4—C6—C7	109.26 (16)	O10—C22—H22	107.9
O4—C6—C5	108.81 (16)	C23—C22—H22	107.9
C7—C6—C5	111.82 (15)	C20—C22—H22	107.9
O4—C6—H6	109.0	C22—C23—C24	109.65 (15)
C7—C6—H6	109.0	C22—C23—H23A	109.7
C5—C6—H6	109.0	C24—C23—H23A	109.7
C6—C7—C8	112.62 (15)	C22—C23—H23B	109.7
C6—C7—H7A	109.1	C24—C23—H23B	109.7
C8—C7—H7A	109.1	H23A—C23—H23B	108.2
C6—C7—H7B	109.1	C28—C24—C23	110.02 (15)
C8—C7—H7B	109.1	C28—C24—C16	108.32 (15)
H7A—C7—H7B	107.8	C23—C24—C16	106.33 (14)
C7—C8—C14	107.95 (14)	C28—C24—C25	109.67 (15)
C7—C8—C9	111.02 (14)	C23—C24—C25	107.96 (15)
C14—C8—C9	112.69 (13)	C16—C24—C25	114.45 (14)
C7—C8—H8	108.4	C26—C25—C27	110.45 (15)
C14—C8—H8	108.4	C26—C25—C24	117.03 (15)
C9—C8—H8	108.4	C27—C25—C24	117.37 (16)
C8—C9—C11	113.18 (14)	C26—C25—H25	103.2
C8—C9—C10	110.27 (14)	C27—C25—H25	103.2
C11—C9—C10	110.54 (13)	C24—C25—H25	103.2
C8—C9—H9	107.5	O6—C26—O10	117.08 (18)
C11—C9—H9	107.5	O6—C26—C25	123.07 (18)
C10—C9—H9	107.5	O10—C26—C25	119.46 (16)
C1—C10—C19	107.83 (14)	O7—C27—C25	116.94 (14)
C1—C10—C5	104.71 (14)	O7—C27—H27A	108.1
C19—C10—C5	110.61 (15)	C25—C27—H27A	108.1
C1—C10—C9	110.63 (14)	O7—C27—H27B	108.1
C19—C10—C9	111.57 (15)	C25—C27—H27B	108.1
C5—C10—C9	111.22 (14)	H27A—C27—H27B	107.3
C9—C11—C12	119.48 (14)	C24—C28—H28A	109.5
C9—C11—H11A	107.4	C24—C28—H28B	109.5
C12—C11—H11A	107.4	H28A—C28—H28B	109.5
C9—C11—H11B	107.4	C24—C28—H28C	109.5
C12—C11—H11B	107.4	H28A—C28—H28C	109.5
H11A—C11—H11B	107.0	H28B—C28—H28C	109.5
C13—C12—C11	119.98 (14)	H2W1—O1W—H1W1	105.3
C13—C12—H12A	107.3	C29—O11A—H11O	101 (3)
C11—C12—H12A	107.3	C29—O11B—H11O	101 (2)
C13—C12—H12B	107.3	O11B—C29—H29A	77.2
C11—C12—H12B	107.3	O11A—C29—H29A	109.5
H12A—C12—H12B	106.9	O11B—C29—H29B	117.3
O2—C13—C12	111.18 (14)	O11A—C29—H29B	109.5
O2—C13—C18	105.50 (14)	H29A—C29—H29B	109.5
C12—C13—C18	112.67 (15)	O11B—C29—H29C	127.2
O2—C13—C17	108.37 (13)	O11A—C29—H29C	109.5
C12—C13—C17	119.26 (15)	H29A—C29—H29C	109.5
C18—C13—C17	98.44 (13)	H29B—C29—H29C	109.5
O7—C14—O8	107.99 (13)	O11B—C29—H29D	148.7
O7—C14—C8	108.63 (13)	O11A—C29—H29D	116.7
O8—C14—C8	110.45 (13)	H29A—C29—H29D	133.9
O7—C14—C15	108.63 (14)	H29B—C29—H29D	55.5
O8—C14—C15	104.68 (13)	H29C—C29—H29D	54.8
C8—C14—C15	116.15 (14)	O11B—C29—H29E	84.2
O5—C15—C16	128.43 (17)	O11A—C29—H29E	106.9
O5—C15—C14	125.18 (17)	H29A—C29—H29E	54.5
C16—C15—C14	106.12 (14)	H29B—C29—H29E	59.1
C15—C16—C17	100.69 (13)	H29C—C29—H29E	143.6
C15—C16—C24	108.84 (14)	H29D—C29—H29E	109.5
C17—C16—C24	114.61 (14)	O11B—C29—H29F	91.0
C15—C16—H16	110.8	O11A—C29—H29F	104.6
C17—C16—H16	110.8	H29A—C29—H29F	55.9
C24—C16—H16	110.8	H29B—C29—H29F	145.8
O8—C17—C16	104.79 (13)	H29C—C29—H29F	58.7
O8—C17—C13	115.05 (13)	H29D—C29—H29F	109.5
C16—C17—C13	109.91 (13)	H29E—C29—H29F	109.5

O3—C1—C2—C3	162.0 (2)	C14—O8—C17—C13	−91.43 (16)
C10—C1—C2—C3	−19.2 (3)	C14—O8—C17—C20	153.75 (13)
C1—C2—C3—C4	0.2 (4)	C15—C16—C17—O8	−36.13 (15)
C2—C3—C4—C5	−13.8 (4)	C24—C16—C17—O8	80.49 (17)
C3—C4—C5—C6	176.92 (19)	C15—C16—C17—C13	88.02 (15)
C3—C4—C5—C10	46.0 (3)	C24—C16—C17—C13	−155.36 (14)
C3—C4—C5—Cl1	−69.9 (2)	C15—C16—C17—C20	−157.59 (14)
C4—C5—C6—O4	−58.0 (2)	C24—C16—C17—C20	−40.98 (19)
C10—C5—C6—O4	71.50 (19)	O2—C13—C17—O8	−48.97 (18)
Cl1—C5—C6—O4	−172.21 (12)	C12—C13—C17—O8	79.54 (18)
C4—C5—C6—C7	−178.82 (17)	C18—C13—C17—O8	−158.47 (14)
C10—C5—C6—C7	−49.3 (2)	O2—C13—C17—C16	−166.92 (13)
Cl1—C5—C6—C7	67.01 (17)	C12—C13—C17—C16	−38.42 (19)
O4—C6—C7—C8	−67.5 (2)	C18—C13—C17—C16	83.57 (16)
C5—C6—C7—C8	53.0 (2)	O2—C13—C17—C20	70.66 (16)
C6—C7—C8—C14	178.06 (15)	C12—C13—C17—C20	−160.84 (14)
C6—C7—C8—C9	−58.0 (2)	C18—C13—C17—C20	−38.85 (16)
C7—C8—C9—C11	−178.57 (14)	C20—O9—C18—O1	176.95 (18)
C14—C8—C9—C11	−57.34 (19)	C20—O9—C18—C13	−4.3 (2)
C7—C8—C9—C10	57.01 (18)	O2—C13—C18—O1	94.6 (2)
C14—C8—C9—C10	178.24 (13)	C12—C13—C18—O1	−26.8 (3)
O3—C1—C10—C19	108.7 (2)	C17—C13—C18—O1	−153.5 (2)
C2—C1—C10—C19	−70.2 (2)	O2—C13—C18—O9	−84.05 (17)
O3—C1—C10—C5	−133.51 (19)	C12—C13—C18—O9	154.47 (15)
C2—C1—C10—C5	47.7 (2)	C17—C13—C18—O9	27.78 (18)
O3—C1—C10—C9	−13.6 (2)	C18—O9—C20—C21	101.94 (18)
C2—C1—C10—C9	167.58 (16)	C18—O9—C20—C22	−140.53 (15)
C4—C5—C10—C1	−61.4 (2)	C18—O9—C20—C17	−21.39 (18)
C6—C5—C10—C1	168.92 (15)	O8—C17—C20—O9	160.58 (13)
Cl1—C5—C10—C1	54.00 (15)	C16—C17—C20—O9	−81.11 (16)
C4—C5—C10—C19	54.5 (2)	C13—C17—C20—O9	37.78 (15)
C6—C5—C10—C19	−75.2 (2)	O8—C17—C20—C21	40.89 (19)
Cl1—C5—C10—C19	169.92 (13)	C16—C17—C20—C21	159.21 (15)
C4—C5—C10—C9	179.11 (17)	C13—C17—C20—C21	−81.91 (17)
C6—C5—C10—C9	49.4 (2)	O8—C17—C20—C22	−87.81 (17)
Cl1—C5—C10—C9	−65.52 (17)	C16—C17—C20—C22	30.5 (2)
C8—C9—C10—C1	−168.32 (14)	C13—C17—C20—C22	149.40 (14)
C11—C9—C10—C1	65.77 (18)	C26—O10—C22—C23	42.9 (2)
C8—C9—C10—C19	71.64 (18)	C26—O10—C22—C20	−83.1 (2)
C11—C9—C10—C19	−54.3 (2)	O9—C20—C22—O10	−166.75 (13)
C8—C9—C10—C5	−52.38 (19)	C21—C20—C22—O10	−48.48 (18)
C11—C9—C10—C5	−178.30 (15)	C17—C20—C22—O10	83.31 (18)
C8—C9—C11—C12	97.88 (19)	O9—C20—C22—C23	69.87 (19)
C10—C9—C11—C12	−137.85 (16)	C21—C20—C22—C23	−171.87 (16)
C9—C11—C12—C13	−13.2 (3)	C17—C20—C22—C23	−40.1 (2)
C11—C12—C13—O2	64.2 (2)	O10—C22—C23—C24	−62.67 (19)
C11—C12—C13—C18	−177.63 (15)	C20—C22—C23—C24	59.1 (2)
C11—C12—C13—C17	−63.0 (2)	C22—C23—C24—C28	177.44 (16)
C27—O7—C14—O8	84.22 (17)	C22—C23—C24—C16	−65.47 (19)
C27—O7—C14—C8	−155.97 (15)	C22—C23—C24—C25	57.79 (19)
C27—O7—C14—C15	−28.8 (2)	C15—C16—C24—C28	−72.27 (18)
C17—O8—C14—O7	−125.35 (13)	C17—C16—C24—C28	175.89 (15)
C17—O8—C14—C8	115.99 (14)	C15—C16—C24—C23	169.51 (15)
C17—O8—C14—C15	−9.74 (17)	C17—C16—C24—C23	57.67 (18)
C7—C8—C14—O7	−46.46 (18)	C15—C16—C24—C25	50.42 (19)
C9—C8—C14—O7	−169.43 (13)	C17—C16—C24—C25	−61.4 (2)
C7—C8—C14—O8	71.80 (17)	C28—C24—C25—C26	−154.51 (16)
C9—C8—C14—O8	−51.16 (18)	C23—C24—C25—C26	−34.6 (2)
C7—C8—C14—C15	−169.23 (15)	C16—C24—C25—C26	83.53 (19)
C9—C8—C14—C15	67.81 (19)	C28—C24—C25—C27	70.58 (19)
O7—C14—C15—O5	−73.5 (2)	C23—C24—C25—C27	−169.55 (14)
O8—C14—C15—O5	171.37 (17)	C16—C24—C25—C27	−51.4 (2)
C8—C14—C15—O5	49.3 (2)	C22—O10—C26—O6	167.52 (17)
O7—C14—C15—C16	100.97 (15)	C22—O10—C26—C25	−19.4 (2)
O8—C14—C15—C16	−14.19 (17)	C27—C25—C26—O6	−34.0 (2)
C8—C14—C15—C16	−136.26 (15)	C24—C25—C26—O6	−171.85 (17)
O5—C15—C16—C17	−155.65 (19)	C27—C25—C26—O10	153.29 (15)
C14—C15—C16—C17	30.15 (16)	C24—C25—C26—O10	15.5 (2)
O5—C15—C16—C24	83.5 (2)	C14—O7—C27—C25	−50.5 (2)
C14—C15—C16—C24	−90.66 (16)	C26—C25—C27—O7	−58.2 (2)
C14—O8—C17—C16	29.37 (16)	C24—C25—C27—O7	79.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11A—H11O···O1Wⁱ	0.96 (4)	1.84 (4)	2.780 (5)	163 (4)
O1W—H1W1···O3	0.84	2.08	2.775 (2)	139
O2—H1O2···O1W	0.82	1.98	2.786 (2)	170
O4—H1O4···O11A	0.82	1.97	2.718 (5)	152
O1W—H2W1···O6ⁱⁱ	0.82	2.03	2.832 (2)	170
C4—H4B···O4	0.97	2.54	2.898 (3)	102
C7—H7A···Cl1	0.97	2.72	3.1140 (19)	105
C7—H7B···O7	0.97	2.31	2.696 (2)	102
C9—H9···Cl1	0.98	2.75	3.1814 (17)	107
C9—H9···O2	0.98	2.27	3.065 (2)	138
C11—H11A···O5	0.97	2.41	3.191 (2)	137
C11—H11B···O3	0.97	2.38	2.894 (2)	112
C19—H19B···Cl1ⁱⁱⁱ	0.96	2.71	3.578 (2)	150
C19—H19C···O4	0.96	2.38	3.012 (3)	123
C21—H21B···O2	0.96	2.28	2.871 (2)	119
C21—H21C···O8	0.96	2.51	2.871 (2)	102
C22—H22···O11Aⁱⁱ	0.98	2.54	3.404 (6)	146

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

Experimental details

Crystal data
Chemical formula	C₂₈H₃₁ClO₁₀·CH₄O·H₂O
M_r	613.04
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	13.0931 (5), 13.5932 (6), 15.6098 (6)
V (Å³)	2778.19 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.54 × 0.33 × 0.21

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.897, 0.957
No. of measured, independent and observed [I > 2s(I)] reflections	15825, 5745, 5545
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.095, 0.85
No. of reflections	5745
No. of parameters	389
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.25
Absolute structure	Flack (1983), 2520 Friedel pairs
Absolute structure parameter	0.02 (6)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11A—H11O···O1Wⁱ	0.96 (4)	1.84 (4)	2.780 (5)	163 (4)
O1W—H1W1···O3	0.84	2.08	2.775 (2)	139
O2—H1O2···O1W	0.82	1.98	2.786 (2)	170
O4—H1O4···O11A	0.82	1.97	2.718 (5)	152
O1W—H2W1···O6ⁱⁱ	0.82	2.03	2.832 (2)	170
C4—H4B···O4	0.97	2.54	2.898 (3)	102
C7—H7A···Cl1	0.97	2.72	3.1140 (19)	105
C7—H7B···O7	0.97	2.31	2.696 (2)	102
C9—H9···Cl1	0.98	2.75	3.1814 (17)	107
C9—H9···O2	0.98	2.27	3.065 (2)	138
C11—H11A···O5	0.97	2.41	3.191 (2)	137
C11—H11B···O3	0.97	2.38	2.894 (2)	112
C19—H19B···Cl1ⁱⁱⁱ	0.96	2.71	3.578 (2)	150
C19—H19C···O4	0.96	2.38	3.012 (3)	123
C21—H21B···O2	0.96	2.28	2.871 (2)	119
C21—H21C···O8	0.96	2.51	2.871 (2)	102
C22—H22···O11Aⁱⁱ	0.98	2.54	3.404 (6)	146

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

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