Redetermnation of lagochiline monohydrate

Ibragimov, A.; Dolimov, D.; Talipov, S.; Izotova, L.; Zainutdinov, U.

doi:10.1107/S1600536810017800

organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1392

https://doi.org/10.1107/S1600536810017800

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Redetermnation of lagochiline monohydrate

Aziz Ibragimov,^a Davron Dolimov,^a Samat Talipov,^b Lidiya Izotova ^b ^* and Umardjon Zainutdinov ^a

^aNational University of Uzbekistan, The Faculty of Chemistry, Vuzgorodok 174, Tashkent 100174, Uzbekistan, and ^bInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, H. Abdullaev Str. 83, Tashkent 100125, Uzbekistan
^*Correspondence e-mail: l_izotova@yahoo.com

(Received 11 May 2010; accepted 14 May 2010; online 19 May 2010)

In the title compound, C₂₀H₃₆O₅·H₂O, previously studied by film methods [Vorontsova et al. (1975 ). Izvest. USSR Ser. Chem. 2, 338–343], the H atoms have been located and the absolute structure (seven stereogenic centres) established. An intramolecular O—H⋯O hydrogen bond generates an S(6) ring. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For biological and medicinal background to lagochiline [systematic name (6S,2R)-2,12-bis(hydroxymethyl)-12-(2-hydroxyethyl)-2,6,8-trimethylspiro[bicyclo[4.4.0]decane-7,5′-oxolane]-3-ol, see: Abramov et al. (1958 ); Akopov & Ibragimov (1961 ); Islamov et al. (1990 ); Izotova et al. (1997 ). For the previous structure determination, see: Vorontsova et al. (1975). For ring conformations, see: Evans & Boeyens (1989 ).

Experimental

Crystal data

C₂₀H₃₆O₅·H₂O
M_r = 374.50
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.28495 (14) Å
b = 12.5933 (3) Å
c = 22.7324 (5) Å
V = 2085.51 (7) Å³
Z = 4
Cu Kα radiation
μ = 0.70 mm⁻¹
T = 293 K
0.05 × 0.01 × 0.01 mm

Data collection

Oxford Diffraction Xcalibur Ruby diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.899, T_max = 0.993
8185 measured reflections
4155 independent reflections
3464 reflections with I > 2σ(I)
R_int = 0.036
3 standard reflections every 100 reflections intensity decay: 2.6%

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.111
S = 0.98
4155 reflections
258 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack (1983 ), 1674 Friedel pairs
Flack parameter: 0.2 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4O⋯O5	0.81 (4)	1.87 (4)	2.605 (3)	149 (3)
O5—H5O⋯O1W	0.77 (5)	1.89 (5)	2.653 (3)	171 (5)
O2—H2O⋯O3ⁱ	0.74 (3)	2.00 (4)	2.732 (2)	173 (3)
O3—H3O⋯O2ⁱⁱ	0.71 (3)	1.98 (3)	2.684 (2)	177 (3)
O1W—H1W⋯O3ⁱⁱⁱ	0.98 (5)	1.97 (5)	2.916 (4)	161 (4)
O1W—H2W⋯O4^iv	0.94 (5)	1.82 (5)	2.722 (3)	160 (5)
Symmetry codes: (i) x+1, y, z; (ii) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, -z]$ ; (iii) $[-x+{\script{1\over 2}}, -y+2, z+{\script{1\over 2}}]$ ; (iv) x-1, y, z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810017800/hb5443sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810017800/hb5443Isup2.hkl

checkCIF report

Comment top

Lagochiline (I, scheme) is a biologically active diterpenoid isolated from plants of the Lagochilus kind (Abramov et al., 1958). It can be used as starting materials for preparing of the important medicinal substances, in particular as high effective hemostatic drug lagochiline (Akopov & Ibragimov,1961) and its synthetic derivative lagodene (Islamov et al., 1990). Lagochiline may be obtained in two crystal forms: as monohydrate at ambient conditions and as anhydrate by crystallization at high temperatures (Izotova et al.,1997). The crystal structure of the monohydrate form has been solved 35 years ago (Vorontsova et al., 1975). In this study we report improved structure of the lagochiline monohydrate. Six-membered rings A and B are slightly distorted from the chair form and trans-conjugated, while five-membered ring C is in the half-chair conformation (Evans & Boeyens, 1989).The molecule I has following 7 asymmetric atoms - C3, C4, C5, C8, C9, C10, C13. The value of the Flack parameters 0.2 (2) (Flack, 1983) allows to establish the absolute configuration of the asymmetric centers as: C(3)—S, C(4)—R, C(5)—S, C(8)—R, C(9)—R, C(10)—S, C(13)—S (Spek, 2009). Lagochiline molecule has intramolecular H-bond [H···O 1.87 (4) Å] between O(4)—H and O(5) atoms (Table). Four hydroxyl groups of the molecule (Fig.1), showing protonodonor as well protonoacceptor properties, are involved in the formation of the complicated system of the intermolecular H-bonds in the crystalline state (Table). The water molecule is H-bonded to three molecules of lagochiline: as acceptor (O5—H···O1W) and twice as donors (O1W—H···O4, O1W—H···O3) of protons. In result, three molecules of lagochiline and one water molecule form two-dimensional sheet parallel to the [010]. These sheets are sewed one with another via H-bonds O(3)—H···O(2) and O(2)—H···O(3) into three-dimensional network.(Table)(Fig.2)

Related literature top

For biological and medicinal background to lagochiline [systematic name (6S,2R)-2,12-bis(hydroxymethyl)-12-(2-hydroxyethyl)-2,6,8-trimethylspiro[bicyclo[4.4.0]decane-7,5'-oxolane]-3-ol, see: Abramov et al. (1958); Akopov & Ibragimov (1961); Islamov et al. (1990); Izotova et al. (1997). For the previous structure determination, see: Vorontsova et al. (1975). For ring conformations, see: Evans & Boeyens (1989).

Experimental top

The extracting of the lagochiline was preformed according to the method in Abramov et al. (1958). Colourless needles of (I) were grown by slow evaporation of a solution in acetone.

Structure description top

For biological and medicinal background to lagochiline [systematic name (6S,2R)-2,12-bis(hydroxymethyl)-12-(2-hydroxyethyl)-2,6,8-trimethylspiro[bicyclo[4.4.0]decane-7,5'-oxolane]-3-ol, see: Abramov et al. (1958); Akopov & Ibragimov (1961); Islamov et al. (1990); Izotova et al. (1997). For the previous structure determination, see: Vorontsova et al. (1975). For ring conformations, see: Evans & Boeyens (1989).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Perspective view of the title compound, showing 30% probability displacement ellipsoids for the non-H atoms. Dashed lines represent hydrogen bonds.
	Fig. 2. Packing diagram of the title compound (I) viewed down the a axis. H atoms have been ommited for clarity. Hydrogen bonds are shown as dashed lines

lagochiline monohydrate top

Crystal data top

C₂₀H₃₆O₅·H₂O	F(000) = 824
M_r = 374.50	D_x = 1.193 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1210 reflections
a = 7.28495 (14) Å	θ = 3.5–72.7°
b = 12.5933 (3) Å	µ = 0.70 mm⁻¹
c = 22.7324 (5) Å	T = 293 K
V = 2085.51 (7) Å³	Needle, colourless
Z = 4	0.05 × 0.01 × 0.01 mm

Data collection top

Oxford Diffraction Xcalibur Ruby diffractometer	3464 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.036
Graphite monochromator	θ_max = 75.5°, θ_min = 3.9°
/ω scans	h = −8→5
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	k = −15→9
T_min = 0.899, T_max = 0.993	l = −28→27
8185 measured reflections	3 standard reflections every 100 reflections
4155 independent reflections	intensity decay: 2.6%

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.042	w = 1/[σ²(F_o²) + (0.0695P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.111	(Δ/σ)_max < 0.001
S = 0.98	Δρ_max = 0.31 e Å⁻³
4155 reflections	Δρ_min = −0.22 e Å⁻³
258 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0016 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1674 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.2 (2)

Crystal data top

C₂₀H₃₆O₅·H₂O	V = 2085.51 (7) Å³
M_r = 374.50	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 7.28495 (14) Å	µ = 0.70 mm⁻¹
b = 12.5933 (3) Å	T = 293 K
c = 22.7324 (5) Å	0.05 × 0.01 × 0.01 mm

Data collection top

Oxford Diffraction Xcalibur Ruby diffractometer	3464 reflections with I > 2σ(I)
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	R_int = 0.036
T_min = 0.899, T_max = 0.993	3 standard reflections every 100 reflections
8185 measured reflections	intensity decay: 2.6%
4155 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.111	Δρ_max = 0.31 e Å⁻³
S = 0.98	Δρ_min = −0.22 e Å⁻³
4155 reflections	Absolute structure: Flack (1983), 1674 Friedel pairs
258 parameters	Absolute structure parameter: 0.2 (2)
0 restraints

Special details top

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.

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
O1	0.73266 (16)	0.98222 (10)	0.12261 (5)	0.0312 (3)
O2	1.0119 (2)	1.17914 (15)	0.04457 (8)	0.0533 (4)
O3	0.3784 (2)	1.16130 (15)	0.02097 (8)	0.0512 (4)
O4	0.8884 (3)	1.03744 (17)	0.37419 (7)	0.0586 (5)
O5	0.5340 (3)	1.0208 (2)	0.38640 (8)	0.0722 (6)
C1	0.9928 (3)	0.96481 (16)	0.21908 (8)	0.0373 (4)
H1A	1.1088	0.9470	0.2006	0.045*
H1B	0.9504	1.0311	0.2022	0.045*
C2	1.0239 (3)	0.98044 (17)	0.28469 (8)	0.0402 (4)
H2B	1.0692	0.9150	0.3019	0.048*
H2C	1.1154	1.0353	0.2909	0.048*
C3	0.8467 (3)	1.01203 (16)	0.31406 (8)	0.0389 (4)
H3B	0.8025	1.0769	0.2950	0.047*
C4	0.6962 (3)	0.92706 (16)	0.30779 (8)	0.0387 (4)
C6	0.5214 (3)	0.82102 (19)	0.22804 (10)	0.0495 (5)
H5B	0.5608	0.7516	0.2415	0.059*
H5C	0.4112	0.8402	0.2495	0.059*
C7	0.4793 (3)	0.81639 (19)	0.16225 (10)	0.0525 (5)
H6A	0.3889	0.7613	0.1551	0.063*
H6B	0.4264	0.8835	0.1500	0.063*
C8	0.6494 (3)	0.79387 (16)	0.12516 (10)	0.0473 (5)
H7A	0.6976	0.7249	0.1378	0.057*
C9	0.8019 (3)	0.87750 (15)	0.13720 (8)	0.0355 (4)
C10	0.8523 (3)	0.87711 (14)	0.20524 (8)	0.0336 (4)
C5	0.6724 (3)	0.90276 (14)	0.24047 (8)	0.0338 (4)
H10A	0.6268	0.9692	0.2234	0.041*
C11	0.9684 (3)	0.86188 (17)	0.09623 (9)	0.0451 (5)
H11A	1.0817	0.8789	0.1166	0.054*
H11B	0.9748	0.7891	0.0824	0.054*
C12	0.9369 (3)	0.93826 (18)	0.04478 (9)	0.0453 (5)
H12A	0.8718	0.9033	0.0130	0.054*
H12B	1.0524	0.9656	0.0299	0.054*
C13	0.8204 (3)	1.02751 (15)	0.07156 (7)	0.0336 (4)
C14	0.6692 (3)	1.06778 (16)	0.03011 (8)	0.0369 (4)
H14A	0.7257	1.1085	−0.0013	0.044*
H14B	0.6087	1.0071	0.0123	0.044*
C15	0.5266 (3)	1.1358 (2)	0.05985 (9)	0.0508 (5)
H15A	0.4788	1.0985	0.0939	0.061*
H15B	0.5835	1.2010	0.0735	0.061*
C16	0.9416 (3)	1.11968 (17)	0.09280 (9)	0.0403 (4)
H16A	0.8700	1.1660	0.1180	0.048*
H16B	1.0428	1.0917	0.1158	0.048*
C17	0.5903 (5)	0.7817 (2)	0.06070 (12)	0.0669 (7)
H17A	0.4957	0.7289	0.0579	0.100*
H17B	0.6938	0.7602	0.0374	0.100*
H17C	0.5444	0.8483	0.0464	0.100*
C18	0.5140 (3)	0.9768 (2)	0.32897 (10)	0.0543 (5)
H18A	0.4766	1.0320	0.3018	0.065*
H18B	0.4190	0.9228	0.3295	0.065*
C19	0.7368 (4)	0.8292 (2)	0.34618 (10)	0.0564 (6)
H19A	0.7492	0.8508	0.3865	0.085*
H19B	0.8488	0.7965	0.3333	0.085*
H19C	0.6378	0.7793	0.3427	0.085*
C20	0.9383 (3)	0.76842 (17)	0.22045 (11)	0.0516 (6)
H20A	0.9698	0.7668	0.2614	0.077*
H20B	1.0470	0.7580	0.1973	0.077*
H20C	0.8517	0.7130	0.2121	0.077*
H2O	1.112 (5)	1.176 (2)	0.0410 (13)	0.052 (8)*
H3O	0.415 (4)	1.202 (2)	0.0029 (13)	0.044 (7)*
H4O	0.789 (5)	1.038 (3)	0.3905 (14)	0.065 (9)*
H5O	0.443 (7)	1.011 (4)	0.4031 (18)	0.103 (15)*
O1W	0.2045 (3)	1.0041 (3)	0.43526 (9)	0.1024 (11)
H1W	0.195 (7)	0.939 (4)	0.459 (2)	0.123*
H2W	0.099 (8)	0.999 (4)	0.412 (2)	0.123*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0317 (6)	0.0317 (6)	0.0301 (5)	0.0050 (5)	0.0028 (5)	0.0027 (5)
O2	0.0319 (8)	0.0696 (10)	0.0584 (9)	−0.0018 (7)	0.0029 (7)	0.0311 (8)
O3	0.0348 (7)	0.0619 (10)	0.0569 (9)	0.0052 (7)	0.0039 (7)	0.0269 (8)
O4	0.0480 (9)	0.0895 (13)	0.0381 (8)	−0.0059 (8)	−0.0057 (7)	−0.0100 (8)
O5	0.0485 (10)	0.1158 (17)	0.0522 (9)	−0.0073 (11)	0.0150 (8)	−0.0232 (11)
C1	0.0300 (8)	0.0431 (9)	0.0390 (9)	−0.0009 (8)	0.0012 (8)	0.0070 (8)
C2	0.0329 (9)	0.0469 (10)	0.0407 (9)	−0.0035 (8)	−0.0050 (8)	0.0078 (8)
C3	0.0391 (10)	0.0444 (10)	0.0332 (8)	0.0022 (8)	−0.0061 (7)	0.0019 (7)
C4	0.0351 (9)	0.0455 (10)	0.0354 (9)	−0.0002 (8)	0.0015 (8)	0.0064 (8)
C6	0.0455 (11)	0.0516 (11)	0.0515 (11)	−0.0167 (10)	0.0020 (10)	0.0032 (10)
C7	0.0499 (13)	0.0519 (11)	0.0557 (13)	−0.0209 (10)	−0.0035 (11)	−0.0052 (10)
C8	0.0576 (13)	0.0356 (10)	0.0486 (11)	−0.0041 (9)	−0.0036 (10)	−0.0061 (8)
C9	0.0377 (9)	0.0311 (8)	0.0378 (9)	0.0071 (7)	−0.0005 (7)	0.0001 (7)
C10	0.0355 (9)	0.0282 (8)	0.0372 (9)	0.0053 (7)	0.0011 (7)	0.0048 (7)
C5	0.0337 (9)	0.0324 (8)	0.0352 (8)	−0.0015 (7)	−0.0021 (7)	0.0068 (7)
C11	0.0489 (12)	0.0437 (10)	0.0426 (10)	0.0164 (9)	0.0054 (9)	−0.0039 (8)
C12	0.0468 (11)	0.0524 (11)	0.0368 (9)	0.0135 (9)	0.0084 (8)	−0.0008 (9)
C13	0.0329 (8)	0.0395 (9)	0.0284 (8)	0.0046 (8)	0.0030 (7)	0.0032 (7)
C14	0.0365 (10)	0.0444 (9)	0.0297 (8)	0.0017 (8)	−0.0011 (7)	0.0026 (7)
C15	0.0469 (11)	0.0659 (13)	0.0396 (10)	0.0200 (11)	0.0006 (9)	0.0080 (10)
C16	0.0348 (10)	0.0479 (10)	0.0382 (9)	−0.0012 (8)	0.0010 (7)	0.0109 (8)
C17	0.0856 (19)	0.0593 (14)	0.0558 (14)	−0.0175 (14)	−0.0086 (13)	−0.0154 (12)
C18	0.0393 (11)	0.0784 (15)	0.0453 (10)	−0.0003 (11)	0.0036 (9)	−0.0044 (11)
C19	0.0661 (15)	0.0584 (13)	0.0447 (11)	−0.0082 (12)	0.0003 (11)	0.0210 (11)
C20	0.0593 (14)	0.0355 (10)	0.0600 (13)	0.0172 (9)	−0.0007 (11)	0.0073 (9)
O1W	0.0453 (10)	0.200 (3)	0.0617 (12)	−0.0183 (15)	−0.0003 (9)	0.0361 (17)

Geometric parameters (Å, º) top

O1—C13	1.442 (2)	C9—C10	1.590 (3)
O1—C9	1.450 (2)	C10—C20	1.545 (2)
O2—C16	1.423 (2)	C10—C5	1.569 (3)
O2—H2O	0.74 (3)	C5—H10A	0.9800
O3—C15	1.432 (3)	C11—C12	1.532 (3)
O3—H3O	0.71 (3)	C11—H11A	0.9700
O4—C3	1.436 (2)	C11—H11B	0.9700
O4—H4O	0.81 (4)	C12—C13	1.534 (3)
O5—C18	1.426 (3)	C12—H12A	0.9700
O5—H5O	0.77 (5)	C12—H12B	0.9700
C1—C2	1.521 (3)	C13—C14	1.536 (3)
C1—C10	1.538 (3)	C13—C16	1.536 (3)
C1—H1A	0.9700	C14—C15	1.507 (3)
C1—H1B	0.9700	C14—H14A	0.9700
C2—C3	1.507 (3)	C14—H14B	0.9700
C2—H2B	0.9700	C15—H15A	0.9700
C2—H2C	0.9700	C15—H15B	0.9700
C3—C4	1.539 (3)	C16—H16A	0.9700
C3—H3B	0.9800	C16—H16B	0.9700
C4—C19	1.539 (3)	C17—H17A	0.9600
C4—C18	1.544 (3)	C17—H17B	0.9600
C4—C5	1.570 (3)	C17—H17C	0.9600
C6—C7	1.528 (3)	C18—H18A	0.9700
C6—C5	1.533 (3)	C18—H18B	0.9700
C6—H5B	0.9700	C19—H19A	0.9600
C6—H5C	0.9700	C19—H19B	0.9600
C7—C8	1.526 (3)	C19—H19C	0.9600
C7—H6A	0.9700	C20—H20A	0.9600
C7—H6B	0.9700	C20—H20B	0.9600
C8—C17	1.535 (3)	C20—H20C	0.9600
C8—C9	1.555 (3)	O1W—H1W	0.98 (5)
C8—H7A	0.9800	O1W—H2W	0.94 (5)
C9—C11	1.542 (3)

C13—O1—C9	112.92 (13)	C10—C5—H10A	104.9
C16—O2—H2O	114 (2)	C4—C5—H10A	104.9
C15—O3—H3O	103 (2)	C12—C11—C9	105.25 (16)
C3—O4—H4O	104 (2)	C12—C11—H11A	110.7
C18—O5—H5O	108 (3)	C9—C11—H11A	110.7
C2—C1—C10	113.10 (15)	C12—C11—H11B	110.7
C2—C1—H1A	109.0	C9—C11—H11B	110.7
C10—C1—H1A	109.0	H11A—C11—H11B	108.8
C2—C1—H1B	109.0	C11—C12—C13	103.90 (15)
C10—C1—H1B	109.0	C11—C12—H12A	111.0
H1A—C1—H1B	107.8	C13—C12—H12A	111.0
C3—C2—C1	109.95 (15)	C11—C12—H12B	111.0
C3—C2—H2B	109.7	C13—C12—H12B	111.0
C1—C2—H2B	109.7	H12A—C12—H12B	109.0
C3—C2—H2C	109.7	O1—C13—C12	105.94 (15)
C1—C2—H2C	109.7	O1—C13—C14	107.83 (14)
H2B—C2—H2C	108.2	C12—C13—C14	113.27 (16)
O4—C3—C2	107.42 (16)	O1—C13—C16	107.50 (14)
O4—C3—C4	113.20 (17)	C12—C13—C16	111.15 (17)
C2—C3—C4	112.69 (17)	C14—C13—C16	110.82 (16)
O4—C3—H3B	107.8	C15—C14—C13	114.03 (15)
C2—C3—H3B	107.8	C15—C14—H14A	108.7
C4—C3—H3B	107.8	C13—C14—H14A	108.7
C3—C4—C19	111.55 (18)	C15—C14—H14B	108.7
C3—C4—C18	107.55 (18)	C13—C14—H14B	108.7
C19—C4—C18	108.23 (19)	H14A—C14—H14B	107.6
C3—C4—C5	107.74 (15)	O3—C15—C14	111.75 (18)
C19—C4—C5	114.70 (18)	O3—C15—H15A	109.3
C18—C4—C5	106.74 (16)	C14—C15—H15A	109.3
C7—C6—C5	110.50 (17)	O3—C15—H15B	109.3
C7—C6—H5B	109.5	C14—C15—H15B	109.3
C5—C6—H5B	109.5	H15A—C15—H15B	107.9
C7—C6—H5C	109.5	O2—C16—C13	111.24 (16)
C5—C6—H5C	109.5	O2—C16—H16A	109.4
H5B—C6—H5C	108.1	C13—C16—H16A	109.4
C8—C7—C6	112.6 (2)	O2—C16—H16B	109.4
C8—C7—H6A	109.1	C13—C16—H16B	109.4
C6—C7—H6A	109.1	H16A—C16—H16B	108.0
C8—C7—H6B	109.1	C8—C17—H17A	109.5
C6—C7—H6B	109.1	C8—C17—H17B	109.5
H6A—C7—H6B	107.8	H17A—C17—H17B	109.5
C7—C8—C17	108.6 (2)	C8—C17—H17C	109.5
C7—C8—C9	110.92 (16)	H17A—C17—H17C	109.5
C17—C8—C9	115.9 (2)	H17B—C17—H17C	109.5
C7—C8—H7A	107.0	O5—C18—C4	110.81 (19)
C17—C8—H7A	107.0	O5—C18—H18A	109.5
C9—C8—H7A	107.0	C4—C18—H18A	109.5
O1—C9—C11	104.56 (15)	O5—C18—H18B	109.5
O1—C9—C8	109.09 (15)	C4—C18—H18B	109.5
C11—C9—C8	111.67 (17)	H18A—C18—H18B	108.1
O1—C9—C10	107.80 (14)	C4—C19—H19A	109.5
C11—C9—C10	113.92 (16)	C4—C19—H19B	109.5
C8—C9—C10	109.53 (16)	H19A—C19—H19B	109.5
C1—C10—C20	108.68 (17)	C4—C19—H19C	109.5
C1—C10—C5	107.68 (15)	H19A—C19—H19C	109.5
C20—C10—C5	114.02 (16)	H19B—C19—H19C	109.5
C1—C10—C9	110.52 (14)	C10—C20—H20A	109.5
C20—C10—C9	108.31 (16)	C10—C20—H20B	109.5
C5—C10—C9	107.63 (14)	H20A—C20—H20B	109.5
C6—C5—C10	111.53 (16)	C10—C20—H20C	109.5
C6—C5—C4	112.94 (16)	H20A—C20—H20C	109.5
C10—C5—C4	116.43 (15)	H20B—C20—H20C	109.5
C6—C5—H10A	104.9	H1W—O1W—H2W	101 (4)

C10—C1—C2—C3	−60.6 (2)	C7—C6—C5—C4	169.13 (19)
C1—C2—C3—O4	−173.49 (17)	C1—C10—C5—C6	178.34 (16)
C1—C2—C3—C4	61.1 (2)	C20—C10—C5—C6	−61.0 (2)
O4—C3—C4—C19	−50.2 (2)	C9—C10—C5—C6	59.18 (19)
C2—C3—C4—C19	71.9 (2)	C1—C10—C5—C4	−50.0 (2)
O4—C3—C4—C18	68.3 (2)	C20—C10—C5—C4	70.6 (2)
C2—C3—C4—C18	−169.56 (16)	C9—C10—C5—C4	−169.21 (15)
O4—C3—C4—C5	−176.98 (17)	C3—C4—C5—C6	−178.34 (17)
C2—C3—C4—C5	−54.8 (2)	C19—C4—C5—C6	56.8 (2)
C5—C6—C7—C8	55.4 (3)	C18—C4—C5—C6	−63.1 (2)
C6—C7—C8—C17	175.38 (19)	C3—C4—C5—C10	50.7 (2)
C6—C7—C8—C9	−56.2 (2)	C19—C4—C5—C10	−74.2 (2)
C13—O1—C9—C11	8.33 (19)	C18—C4—C5—C10	165.97 (17)
C13—O1—C9—C8	−111.25 (16)	O1—C9—C11—C12	−22.3 (2)
C13—O1—C9—C10	129.90 (15)	C8—C9—C11—C12	95.5 (2)
C7—C8—C9—O1	−60.0 (2)	C10—C9—C11—C12	−139.73 (17)
C17—C8—C9—O1	64.4 (2)	C9—C11—C12—C13	27.4 (2)
C7—C8—C9—C11	−175.03 (18)	C9—O1—C13—C12	9.1 (2)
C17—C8—C9—C11	−50.7 (3)	C9—O1—C13—C14	130.62 (16)
C7—C8—C9—C10	57.8 (2)	C9—O1—C13—C16	−109.86 (16)
C17—C8—C9—C10	−177.9 (2)	C11—C12—C13—O1	−22.6 (2)
C2—C1—C10—C20	−70.5 (2)	C11—C12—C13—C14	−140.56 (18)
C2—C1—C10—C5	53.5 (2)	C11—C12—C13—C16	93.9 (2)
C2—C1—C10—C9	170.76 (15)	O1—C13—C14—C15	49.4 (2)
O1—C9—C10—C1	−57.31 (19)	C12—C13—C14—C15	166.26 (19)
C11—C9—C10—C1	58.2 (2)	C16—C13—C14—C15	−68.0 (2)
C8—C9—C10—C1	−175.89 (16)	C13—C14—C15—O3	−173.44 (18)
O1—C9—C10—C20	−176.26 (16)	O1—C13—C16—O2	−171.20 (15)
C11—C9—C10—C20	−60.7 (2)	C12—C13—C16—O2	73.3 (2)
C8—C9—C10—C20	65.2 (2)	C14—C13—C16—O2	−53.6 (2)
O1—C9—C10—C5	60.03 (18)	C3—C4—C18—O5	−53.1 (3)
C11—C9—C10—C5	175.57 (16)	C19—C4—C18—O5	67.6 (3)
C8—C9—C10—C5	−58.55 (18)	C5—C4—C18—O5	−168.5 (2)
C7—C6—C5—C10	−57.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O5	0.81 (4)	1.87 (4)	2.605 (3)	149 (3)
O5—H5O···O1W	0.77 (5)	1.89 (5)	2.653 (3)	171 (5)
O2—H2O···O3ⁱ	0.74 (3)	2.00 (4)	2.732 (2)	173 (3)
O3—H3O···O2ⁱⁱ	0.71 (3)	1.98 (3)	2.684 (2)	177 (3)
O1W—H1W···O3ⁱⁱⁱ	0.98 (5)	1.97 (5)	2.916 (4)	161 (4)
O1W—H2W···O4^iv	0.94 (5)	1.82 (5)	2.722 (3)	160 (5)

Symmetry codes: (i) x+1, y, z; (ii) x−1/2, −y+5/2, −z; (iii) −x+1/2, −y+2, z+1/2; (iv) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₀H₃₆O₅·H₂O
M_r	374.50
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	7.28495 (14), 12.5933 (3), 22.7324 (5)
V (Å³)	2085.51 (7)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.70
Crystal size (mm)	0.05 × 0.01 × 0.01

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)
T_min, T_max	0.899, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	8185, 4155, 3464
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.111, 0.98
No. of reflections	4155
No. of parameters	258
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.22
Absolute structure	Flack (1983), 1674 Friedel pairs
Absolute structure parameter	0.2 (2)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), XP (Siemens, 1994), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O5	0.81 (4)	1.87 (4)	2.605 (3)	149 (3)
O5—H5O···O1W	0.77 (5)	1.89 (5)	2.653 (3)	171 (5)
O2—H2O···O3ⁱ	0.74 (3)	2.00 (4)	2.732 (2)	173 (3)
O3—H3O···O2ⁱⁱ	0.71 (3)	1.98 (3)	2.684 (2)	177 (3)
O1W—H1W···O3ⁱⁱⁱ	0.98 (5)	1.97 (5)	2.916 (4)	161 (4)
O1W—H2W···O4^iv	0.94 (5)	1.82 (5)	2.722 (3)	160 (5)

Symmetry codes: (i) x+1, y, z; (ii) x−1/2, −y+5/2, −z; (iii) −x+1/2, −y+2, z+1/2; (iv) x−1, y, z.

Acknowledgements

Support of this research by the Uzbek Academy of Sciences (grant Nos. FA-A12-T175 and FA-F3-T141) is gratefully acknowledged

References

Abramov, M. M., Japarova, S. A. & Ikramov, M. I. (1958). Uzb. Biol. Zh. 6, 55–60 Google Scholar
Akopov, I. E. & Ibragimov, I. I. (1961). Pharmacol. Toxicol. 6, 39–40. Google Scholar
Evans, D. G. & Boeyens, J. C. A. (1989). Acta Cryst. B45, 581–590. CrossRef CAS Web of Science IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Islamov, R., Zainutdinov, U. N., Aslanov, Kh. A., Sadykov, A. S., Danil'chuk, D. N., Yankovskiy, B. A. & Zacharov, V. P. (1990). USSR Patent AS 1293990. Google Scholar
Izotova, L. Yu., Beketov, K. M., Talipov, S. A. & Ibragimov, B. T. (1997). Pol. J. Chem. 71, 1037–1044. CAS Google Scholar
Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1994). XP. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vorontsova, L. G., Tchijov, O. S., Tarnopolsky, B. L. & Andrianov, V. I. (1975). Izv. USSR Ser. Chem. 2, 338–343. Google Scholar