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The title compound, [2aS-(2a[alpha],4a[alpha],5[alpha],7b[alpha])]-5-([beta]-D-gluco­pyran­osyl­oxy)-2a,4a,5,7b-tetra­hydro-1-oxo-1H-2,6-dioxa­cyclo­pent­[cd]­inden-4-yl­methyl acetate monohydrate, C18H22O11·H2O, was extracted from the Turkish plant Putoria calabrica (L. fil.) DC. The three fused rings have envelope or distorted envelope conformations and form a bowl in which ring strain causes distortion of some bond angles and significant pyramidalization of two of the Csp2 atoms. The ring junction H atoms are all cis to one another and the glycosidic linkage is in the [beta] axial position. The structure incorporates two symmetry-independent water mol­ecules, each of which is located on a twofold axis. Intermolecular hydrogen bonds involving all the hydroxy groups and water mol­ecules link the mol­ecules into a complex three-dimensional framework.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100003292/sk1376sup1.cif
Contains datablocks L0004, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003292/sk1376Isup2.hkl
Contains datablock I

CCDC reference: 145561

Comment top

As a part of our phytochemical research on the plants of the flora of Turkey, we investigated Putoria calabrica (L. fil.) DC (Rubiaceae) (Ehrendorfer, 1982) and isolated several iridoid glucosides. Among them, two compounds were separated as a mixture from which the major component, the title compound, (I), was crystallized. The spectroscopic data (1H– and 13C-NMR) of this component correspond well with those reported for the known iridoid glucoside, asperuloside (Bobbitt & Segebarth, 1969; Bailleul et al., 1977). A chromatographic comparison with an authentic sample of asperuloside confirmed the identity of (I) and its crystal structure was determined in order to confirm the stereochemistry. The spectroscopic data obtained for the minor component of the mixed fraction are similar to those of asperuloside, but there are subtle differences. A further analysis of this latter compound is in progress. \scheme

Compound (I) crystallizes as a monohydrate, but there are actually two symmetry-independent water molecules in the structure, each of which sits on a twofold axis. The three fused rings in (I) form a bowl with C10 at the base (Fig. 1). The H atoms at the ring junctions C10, C11 and C14 all lie on the outside surface of the bowl and cis to one another. The conformation of the lactone ring lies between an envelope with C10 as the flap and a half-chair twisted on C10—C11. The puckering parameter (Cremer & Pople, 1975) ϕ2 is 240.3 (5)°. Values of 234 and 252° would correspond with an ideal half-chair and an envelope conformation, respectively. Atom C10 is -0.321 (7) Å from the plane defined by O9, C9 and C15, while C11 is only 0.165 (7) Å from this plane. The cyclopentene ring has an envelope conformation [ϕ2 = 357.3 (6)°] with C10, the envelope flap, lying 0.387 (4) Å from the plane defined by C11, C12, C13 and C14. The maximum deviation of these latter four atoms from their mean plane is 0.0059 (15) Å for C12. This conformation is dictated by the steric requirements of the C12C13 bond.

The best description for the conformation of the fused six-membered ring is also an envelope (Boeyens, 1978), as the puckering parameters θ and ϕ2 are 123.8 (2) and 290.6 (3)°, respectively. Atom C14 forms the envelope flap and lies 0.636 (3) Å from the plane defined by C7, O7, C8, C9 and C10. The maximum deviation of these latter five atoms from their mean plane is 0.0437 (15) Å for C9. The fused six-membered ring can be thought of as a pseudo sugar ring in which the glycosidic bridging atom, O1, is in the β axial position. Considering this ring, the torsion angles about the glycosidic linkage, O7—C7—O1—C1 and C14—C7—O1—C2, correspond with the -synclinal (-sc) and +antiperiplanar (+ap) conformations, respectively, which defines the A1 conformer (de Hoog et al., 1969).

The glucoside ring has a normal chair conformation with the puckering parameter θ = 7.9 (2)° and the hydroxymethyl substituent adopts the gauche-trans conformation with respect to O5 and C4, respectively. The torsion angles about the glycosidic linkage, O5—C1—O1—C7 and C2—C1—O1—C7, define the E1 conformer and deviate only very slightly from the most stable -sc and +ap conformations.

The structure of only one other asperuloside derivative has been reported (Böjthe-Horváth et al., 1982). That derivative, (II), possesses a 1-(4-hydroxyphenyl)-propionyl substituent at C2 of the glucoside ring, but is otherwise identical to compound (I). The overall conformations of the fused three-ring systems of (I) and (II) are very similar, as are the orientations of the glucoside ring with respect to the fused rings. However, while the acetyl substituent at C13 in (I) is folded back under the base of the fused rings and lies nearly parallel to the mean C13—C14—C7—O1 vector, the corresponding substituent in (II) lies virtually perpendicular to this direction and tends to head away from the glucoside ring. This difference is presumably dictated by the different crystal packing requirements introduced by the 1-(4-hydroxyphenyl)-propionyl substituent in (II).

The bond lengths in (I) are normal. The O9—C11 bond in the lactone ring is not significantly elongated, unlike the corresponding bond in (II), which was found to be 1.505 (5) Å. The strain of the fused ring system is highlighted by distortions of some bond angles from normal values. In particular, the angles C10—C9—C15 and C12—C13—C14 are about 10° smaller than normally observed about sp2 C atoms, while the C9—C10—C11, C10—C11—C12 and C10—C14—C13 angles are also up to 10° smaller than normal (Table 1). Conversely, the C7—C14—C13 angle is about 10° larger than normal. Similar trends are found in the structure of (II). Although C9 has sp2 hybridization, it is significantly pryamidalized. The sum of the bond angles about C9 is only 355.0 (3)° and this atom lies 0.184 (3) Å from the plane defined by C8, C10 and C15. In (II), this pyramidalization is slightly more severe, with the sum of the angles about the corresponding atom being 353.6°. To a lesser extent, C13 is also slightly pyramidalized and lies 0.073 (3) Å from the plane defined by C12, C14 and C16.

Each hydroxy group in (I) acts as a donor for intermolecular hydrogen bonds (Table 2). The four acceptor atoms are all in different neighbouring molecules and consist of two hydroxy O atoms, the carbonyl O atom of the acetyl substituent and one water molecule (O12). Because this water molecule sits on a twofold axis, it accepts a hydrogen bond from each of two symmetry-related asperuloside molecules. The other water molecule does not accept any hydrogen bonds. Each water molecule acts as a donor for two hydrogen bonds: one donates to the methylhydroxy O atom on the glucoside ring of each of two symmetry-related asperuloside molecules, while the other water molecule donates to the carbonyl O atom of the lactone ring, also in each of two symmetry-related asperuloside molecules. The combination of all these hydrogen-bonding interactions links the molecules into an infinite three-dimensional framework (Fig. 2).

Experimental top

The plant material of Putoria calabrica (L. fil.) DC was collected from Antakya, Turkey in June 1999. The voucher specimen has been deposited at the herbarium of the Faculty of Pharmacy, Hacettepe University, Ankara. The whole dried plant material was extracted with MeOH at 323 K. The water soluble part of the methanolic extract was fractionated over polyamide yielding several fractions. The fractions rich in iridoids were further subjected to column chromatography on silica gel using CH2Cl2/MeOH/H2O (90:10:1 85:15:1.5) as eluants. This produced additional fractions containing two compounds, of which (I) was the major component that subsequently crystallized as a pure compound from the solution. Recrystallization from ethyl acetate yielded needle-shaped crystals (m.p. 404–405 K).

Refinement top

Reflection 004 was omitted from the final refinement because of suspected severe extinction effects. The methyl and hydroxy H atoms were constrained to an ideal geometry with Uiso(H) = 1.5Ueq(parent atom), but were allowed to rotate freely about the C—C or O—C bonds. The two unique water H atoms were located from a difference Fourier map and their positions were refined with Uiso(H) = 1.5Ueq(O). An O—H bond length restraint of 0.82 (2) Å was applied in the case of the water molecule involving O13. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C). The data set included 2213 pairs of Friedel-related reflections, which gave a coverage of 72% of the total possible number of Friedel pairs with θ < θmax. Due to the lack of anomalous scatterers, the absolute configuration could not be established reliably, as illustrated by the value of -0.6 (10) obtained for the Flack x parameter (Flack, 1983) derived during a structure-factor calculation using a data set in which all Friedel-related reflections were treated as independent. The absolute structure was therefore set in accordance with the known configuration of the glucoside moiety. As there was no significant anomalous dispersion, the final refinement cycles were carried out using a data set in which the Friedel-related reflections had been merged.

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary size. The solvent water has been omitted.
[Figure 2] Fig. 2. The crystal packing of (I) viewed down the c axis showing the network of hydrogen bonds (dashed lines). Uninvolved H atoms have been omitted for clarity.
[2aS-(2aα,4aα,5α,7 bα)]-5-(β-D-glucopyranosyloxy)-1-oxo-2a,4a,5,7 b- tetrahydro-1H-2,6-dioxacyclopenta[cd]inden-4-ylmethyl acetate monohydrate top
Crystal data top
C18H22O11·H2ODx = 1.470 Mg m3
Mr = 432.38Melting point = 404–405 K
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
a = 15.1250 (4) ÅCell parameters from 13638 reflections
b = 5.6702 (1) Åθ = 1.0–30.0°
c = 22.8781 (5) ŵ = 0.13 mm1
β = 95.3753 (13)°T = 291 K
V = 1953.44 (8) Å3Needle, colourless
Z = 40.35 × 0.10 × 0.10 mm
F(000) = 912
Data collection top
Nonius KappaCCD area detector
diffractometer
2393 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.032
Graphite monochromatorθmax = 30.0°, θmin = 2.7°
ϕ scans and ω scans with θ offsetsh = 2121
10609 measured reflectionsk = 77
3091 independent reflectionsl = 3131
Refinement top
Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.041 w = 1/[σ2(Fo2) + (0.0544P)2 + 0.1452P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.101(Δ/σ)max < 0.001
S = 1.03Δρmax = 0.23 e Å3
3091 reflectionsΔρmin = 0.19 e Å3
284 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraintsExtinction coefficient: 0.0043 (9)
Primary atom site location: structure-invariant direct methods
Crystal data top
C18H22O11·H2OV = 1953.44 (8) Å3
Mr = 432.38Z = 4
Monoclinic, C2Mo Kα radiation
a = 15.1250 (4) ŵ = 0.13 mm1
b = 5.6702 (1) ÅT = 291 K
c = 22.8781 (5) Å0.35 × 0.10 × 0.10 mm
β = 95.3753 (13)°
Data collection top
Nonius KappaCCD area detector
diffractometer
2393 reflections with I > 2σ(I)
10609 measured reflectionsRint = 0.032
3091 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0412 restraints
wR(F2) = 0.101H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.23 e Å3
3091 reflectionsΔρmin = 0.19 e Å3
284 parameters
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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

8.8967 (0.0448) x - 4.5088 (0.0122) y + 2.0951 (0.0314) z = 1.4055 (0.0148)

* 0.0000 (0.0000) O9 * 0.0000 (0.0000) C15 * 0.0000 (0.0000) C9 - 0.3211 (0.0066) C10 0.1651 (0.0065) C11

Rms deviation of fitted atoms = 0.0000

9.0321 (0.0126) x - 3.1572 (0.0048) y + 11.8714 (0.0161) z = 5.3379 (0.0055)

* 0.0248 (0.0013) O7 * 0.0140 (0.0014) C8 * -0.0437 (0.0015) C9 * 0.0346 (0.0010) C10 * -0.0297 (0.0010) C7 0.6355 (0.0030) C14

Rms deviation of fitted atoms = 0.0310

8.9509 (0.0193) x + 4.2801 (0.0064) y + 5.1743 (0.0281) z = 6.8632 (0.0112)

* -0.0033 (0.0008) C11 * 0.0059 (0.0015) C12 * -0.0058 (0.0015) C13 * 0.0031 (0.0008) C14 - 0.3868 (0.0036) C10

Rms deviation of fitted atoms = 0.0047

10.8828 (0.0145) x - 3.0132 (0.0061) y + 8.6413 (0.0286) z = 4.7715 (0.0096)

* 0.0000 (0.0000) C8 * 0.0000 (0.0000) C10 * 0.0000 (0.0000) C15 - 0.1842 (0.0025) C9

Rms deviation of fitted atoms = 0.0000

7.9869 (0.0186) x + 4.5112 (0.0046) y + 5.6314 (0.0342) z = 6.7692 (0.0111)

* 0.0000 (0.0000) C12 * 0.0000 (0.0000) C14 * 0.0000 (0.0000) C16 - 0.0727 (0.0027) C13

Rms deviation of fitted atoms = 0.0000

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
xyzUiso*/Ueq
O10.30076 (9)0.5295 (3)0.24606 (5)0.0323 (3)
O20.15172 (9)0.7190 (4)0.17372 (6)0.0508 (5)
H20.14820.70140.20900.076*
O30.21203 (12)1.0011 (4)0.08566 (6)0.0491 (4)
H30.20531.02290.05010.074*
O40.33499 (10)0.7546 (3)0.01761 (5)0.0367 (4)
H40.37950.82080.00790.055*
O50.37796 (9)0.5021 (3)0.16558 (5)0.0306 (3)
O60.50084 (10)0.2340 (3)0.09934 (7)0.0423 (4)
H60.54390.23100.12390.063*
O70.28346 (11)0.1391 (3)0.27305 (6)0.0398 (4)
O80.11286 (12)0.1004 (4)0.41739 (9)0.0654 (6)
O90.22201 (11)0.3378 (4)0.45513 (6)0.0474 (5)
O100.48771 (10)0.0206 (3)0.32904 (6)0.0423 (4)
O110.58684 (11)0.1763 (4)0.28166 (7)0.0482 (5)
C10.29141 (13)0.5098 (4)0.18409 (7)0.0288 (4)
H110.25760.36840.17150.035*
C20.24261 (13)0.7318 (4)0.16270 (8)0.0305 (4)
H210.26990.86760.18390.037*
C30.24539 (13)0.7711 (4)0.09720 (8)0.0304 (4)
H310.20640.65650.07560.036*
C40.33944 (13)0.7414 (4)0.08016 (7)0.0273 (4)
H410.37660.87030.09720.033*
C50.37798 (12)0.5066 (4)0.10268 (7)0.0282 (4)
H510.34130.37710.08550.034*
C60.47314 (15)0.4717 (5)0.08935 (9)0.0372 (5)
H610.47870.51300.04870.045*
H620.51150.57580.11400.045*
C70.34217 (15)0.3389 (4)0.27695 (8)0.0327 (5)
H710.39710.29840.25960.039*
C80.22398 (15)0.1247 (4)0.31357 (8)0.0361 (5)
H810.18550.00360.31170.043*
C90.21706 (14)0.2819 (4)0.35579 (9)0.0339 (5)
C100.27994 (14)0.4829 (4)0.36799 (8)0.0330 (5)
H1010.25410.63720.35730.040*
C110.30115 (15)0.4477 (5)0.43447 (9)0.0404 (5)
H1110.31600.59690.45470.048*
C120.37901 (14)0.2842 (5)0.43680 (9)0.0409 (6)
H1210.40040.20180.47030.049*
C130.41442 (13)0.2692 (4)0.38566 (8)0.0337 (5)
C140.36507 (14)0.4300 (4)0.33979 (8)0.0324 (5)
H1410.39870.57700.33780.039*
C150.17543 (15)0.2248 (5)0.40961 (10)0.0434 (6)
C160.49909 (15)0.1452 (6)0.37789 (9)0.0445 (6)
H1610.54430.25980.37050.053*
H1620.51890.06080.41360.053*
C170.53687 (14)0.0125 (5)0.28439 (9)0.0365 (5)
C180.5203 (2)0.1728 (6)0.23879 (13)0.0625 (8)
H1810.56610.16740.21250.094*
H1820.46370.14590.21720.094*
H1830.52040.32490.25720.094*
O120.50.0327 (4)0.00.0428 (6)
H120.5050 (19)0.050 (7)0.0312 (11)0.064*
O130.50.7857 (8)0.50.0954 (12)
H130.537 (3)0.713 (10)0.4775 (18)0.143*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0432 (8)0.0346 (8)0.0200 (6)0.0033 (7)0.0068 (5)0.0042 (6)
O20.0323 (7)0.0906 (15)0.0314 (7)0.0128 (10)0.0126 (6)0.0129 (9)
O30.0629 (10)0.0539 (11)0.0315 (7)0.0249 (10)0.0107 (7)0.0113 (8)
O40.0429 (8)0.0483 (10)0.0195 (6)0.0079 (8)0.0068 (5)0.0036 (7)
O50.0292 (7)0.0430 (8)0.0204 (6)0.0031 (7)0.0057 (5)0.0018 (7)
O60.0377 (8)0.0461 (9)0.0427 (8)0.0107 (8)0.0021 (6)0.0028 (8)
O70.0605 (10)0.0331 (8)0.0265 (7)0.0059 (8)0.0076 (6)0.0026 (7)
O80.0521 (11)0.0783 (16)0.0703 (12)0.0174 (11)0.0291 (9)0.0021 (12)
O90.0483 (9)0.0642 (13)0.0321 (7)0.0027 (10)0.0168 (7)0.0026 (9)
O100.0377 (8)0.0496 (11)0.0413 (8)0.0073 (8)0.0121 (6)0.0005 (8)
O110.0500 (9)0.0541 (12)0.0433 (9)0.0160 (9)0.0188 (8)0.0078 (8)
C10.0294 (9)0.0379 (12)0.0201 (8)0.0033 (10)0.0069 (7)0.0008 (9)
C20.0296 (9)0.0407 (11)0.0222 (8)0.0024 (9)0.0076 (7)0.0013 (9)
C30.0324 (10)0.0373 (12)0.0217 (8)0.0032 (9)0.0035 (7)0.0034 (8)
C40.0322 (9)0.0322 (10)0.0179 (8)0.0044 (9)0.0044 (7)0.0003 (8)
C50.0293 (9)0.0370 (10)0.0190 (8)0.0028 (9)0.0059 (7)0.0009 (9)
C60.0347 (11)0.0448 (14)0.0337 (10)0.0028 (11)0.0113 (8)0.0010 (10)
C70.0411 (11)0.0346 (11)0.0233 (9)0.0012 (10)0.0074 (8)0.0038 (9)
C80.0437 (12)0.0322 (11)0.0318 (10)0.0069 (10)0.0007 (9)0.0058 (10)
C90.0324 (10)0.0384 (13)0.0309 (10)0.0001 (10)0.0030 (8)0.0050 (9)
C100.0434 (11)0.0296 (11)0.0264 (9)0.0007 (10)0.0066 (8)0.0004 (9)
C110.0450 (12)0.0496 (14)0.0277 (10)0.0033 (12)0.0097 (9)0.0034 (10)
C120.0399 (11)0.0597 (16)0.0233 (9)0.0006 (12)0.0038 (8)0.0078 (10)
C130.0318 (10)0.0452 (13)0.0245 (9)0.0043 (10)0.0039 (7)0.0059 (9)
C140.0386 (11)0.0364 (11)0.0225 (9)0.0065 (10)0.0043 (8)0.0028 (8)
C150.0388 (12)0.0507 (14)0.0426 (12)0.0038 (12)0.0139 (10)0.0049 (11)
C160.0346 (11)0.0695 (17)0.0298 (10)0.0003 (12)0.0060 (8)0.0018 (12)
C170.0290 (10)0.0440 (13)0.0372 (10)0.0011 (10)0.0060 (8)0.0007 (11)
C180.0570 (16)0.071 (2)0.0602 (16)0.0227 (16)0.0115 (13)0.0230 (16)
O120.0581 (15)0.0370 (13)0.0355 (11)00.0160 (11)0
O130.114 (3)0.081 (3)0.099 (3)00.055 (2)0
Geometric parameters (Å, º) top
O1—C11.416 (2)C5—C61.512 (3)
O1—C71.406 (3)C5—H510.98
O2—C21.422 (2)C6—H610.97
O2—H20.82C6—H620.97
O3—C31.415 (3)C7—C141.536 (3)
O3—H30.82C7—H710.98
O4—C41.428 (2)C8—C91.326 (3)
O4—H40.82C8—H810.93
O5—C11.414 (2)C9—C151.471 (3)
O5—C51.439 (2)C9—C101.494 (3)
O6—C61.423 (3)C10—C141.523 (3)
O6—H60.82C10—C111.538 (3)
O7—C71.437 (3)C10—H1010.98
O7—C81.353 (3)C11—C121.496 (4)
O8—C151.206 (3)C11—H1110.98
O9—C111.466 (3)C12—C131.334 (3)
O9—C151.362 (3)C12—H1210.93
O10—C171.332 (3)C13—C161.486 (3)
O10—C161.458 (3)C13—C141.531 (3)
O11—C171.203 (3)C14—H1410.98
C1—C21.517 (3)C16—H1610.97
C1—H110.98C16—H1620.97
C2—C31.520 (3)C17—C181.485 (4)
C2—H210.98C18—H1810.96
C3—C41.519 (3)C18—H1820.96
C3—H310.98C18—H1830.96
C4—C51.524 (3)O12—H120.85 (3)
C4—H410.98O13—H130.895 (19)
C7—O1—C1116.15 (16)C9—C8—O7124.2 (2)
C2—O2—H2109.5C9—C8—H81117.9
C3—O3—H3109.5O7—C8—H81117.9
C4—O4—H4109.5C8—C9—C10123.83 (19)
C1—O5—C5112.69 (13)C8—C9—C15122.1 (2)
C6—O6—H6109.5C10—C9—C15109.06 (19)
C8—O7—C7116.83 (17)C9—C10—C1198.99 (17)
C15—O9—C11109.46 (16)C9—C10—C14108.63 (19)
C17—O10—C16117.57 (19)C11—C10—C14106.69 (16)
O5—C1—O1107.08 (14)C9—C10—H101113.8
O5—C1—C2111.44 (16)C14—C10—H101113.8
O1—C1—C2104.92 (17)C11—C10—H101113.8
O5—C1—H11111.1O9—C11—C10105.84 (16)
O1—C1—H11111.1O9—C11—C12112.9 (2)
C2—C1—H11111.1C10—C11—C12101.89 (17)
O2—C2—C1110.47 (18)O9—C11—H111111.9
O2—C2—C3107.38 (15)C12—C11—H111111.9
C1—C2—C3112.46 (17)C10—C11—H111111.9
O2—C2—H21108.8C13—C12—C11112.80 (19)
C1—C2—H21108.8C13—C12—H121123.6
C3—C2—H21108.8C11—C12—H121123.6
O3—C3—C4112.37 (19)C12—C13—C16123.79 (19)
O3—C3—C2106.07 (17)C12—C13—C14110.7 (2)
C4—C3—C2110.48 (15)C16—C13—C14124.77 (17)
O3—C3—H31109.3C7—C14—C10109.70 (17)
C4—C3—H31109.3C7—C14—C13119.6 (2)
C2—C3—H31109.3C10—C14—C13101.77 (16)
O4—C4—C3107.09 (15)C10—C14—H141108.4
O4—C4—C5111.41 (16)C13—C14—H141108.4
C3—C4—C5110.36 (17)C7—C14—H141108.4
O4—C4—H41109.3O8—C15—O9121.3 (2)
C3—C4—H41109.3O8—C15—C9131.0 (2)
C5—C4—H41109.3O9—C15—C9107.8 (2)
O5—C5—C6106.78 (15)O10—C16—C13110.83 (17)
O5—C5—C4108.51 (16)O10—C16—H161109.5
C6—C5—C4112.80 (17)C13—C16—H161109.5
O5—C5—H51109.6O10—C16—H162109.5
C6—C5—H51109.6C13—C16—H162109.5
C4—C5—H51109.6H161—C16—H162108.1
O6—C6—C5111.29 (19)O11—C17—O10123.2 (2)
O6—C6—H61109.4O11—C17—C18125.1 (2)
C5—C6—H61109.4O10—C17—C18111.7 (2)
O6—C6—H62109.4C17—C18—H181109.5
C5—C6—H62109.4C17—C18—H182109.5
H61—C6—H62108.0H181—C18—H182109.5
O1—C7—O7109.35 (15)C17—C18—H183109.5
O1—C7—C14105.23 (18)H181—C18—H183109.5
O7—C7—C14114.02 (16)H182—C18—H183109.5
O1—C7—H71109.4H12i—O12—H12113 (5)
O7—C7—H71109.4H13ii—O13—H13125 (8)
C14—C7—H71109.4
C5—O5—C1—O1173.97 (16)C15—C9—C10—C1125.6 (2)
C5—O5—C1—C259.8 (2)C15—O9—C11—C1287.0 (2)
C1—O1—C7—O771.2 (2)C15—O9—C11—C1023.6 (3)
C1—O1—C7—C14165.98 (16)C9—C10—C11—O929.0 (2)
C7—O1—C1—O563.4 (2)C14—C10—C11—O9141.6 (2)
C7—O1—C1—C2178.07 (16)C9—C10—C11—C1289.2 (2)
O5—C1—C2—O2170.87 (15)C14—C10—C11—C1223.4 (2)
O1—C1—C2—O273.59 (19)O9—C11—C12—C13127.0 (2)
O5—C1—C2—C350.9 (2)C10—C11—C12—C1314.0 (3)
O1—C1—C2—C3166.46 (16)C11—C12—C13—C16171.6 (2)
O2—C2—C3—O368.5 (2)C11—C12—C13—C141.1 (3)
C1—C2—C3—O3169.79 (17)C9—C10—C14—C1381.93 (19)
O2—C2—C3—C4169.49 (19)C11—C10—C14—C1323.9 (2)
C1—C2—C3—C447.8 (2)C9—C10—C14—C745.7 (2)
O3—C3—C4—O468.1 (2)C11—C10—C14—C7151.58 (19)
C2—C3—C4—O4173.65 (17)C12—C13—C14—C1015.9 (3)
O3—C3—C4—C5170.46 (15)C16—C13—C14—C10173.8 (2)
C2—C3—C4—C552.2 (2)C12—C13—C14—C7136.9 (2)
C1—O5—C5—C6174.18 (18)C16—C13—C14—C752.8 (3)
C1—O5—C5—C464.0 (2)O1—C7—C14—C1065.2 (2)
O4—C4—C5—O5178.20 (15)O7—C7—C14—C1054.6 (2)
C3—C4—C5—O559.37 (19)O1—C7—C14—C13177.89 (17)
O4—C4—C5—C663.7 (2)O7—C7—C14—C1362.3 (2)
C3—C4—C5—C6177.47 (16)C11—O9—C15—O8172.0 (2)
O5—C5—C6—O673.4 (2)C11—O9—C15—C96.9 (3)
C4—C5—C6—O6167.47 (16)C8—C9—C15—O836.1 (4)
C8—O7—C7—O186.4 (2)C10—C9—C15—O8168.1 (3)
C8—O7—C7—C1431.0 (3)C8—C9—C15—O9142.6 (2)
C7—O7—C8—C90.0 (3)C10—C9—C15—O913.1 (3)
O7—C8—C9—C15158.6 (2)C17—O10—C16—C13119.6 (2)
O7—C8—C9—C106.4 (3)C12—C13—C16—O10128.8 (2)
C8—C9—C10—C1418.5 (3)C14—C13—C16—O1062.1 (3)
C15—C9—C10—C14136.74 (19)C16—O10—C17—O113.0 (3)
C8—C9—C10—C11129.6 (2)C16—O10—C17—C18178.3 (2)
Symmetry codes: (i) x+1, y, z; (ii) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O11iii0.821.982.752 (2)156
O3—H3···O4iv0.822.082.800 (2)147
O4—H4···O12v0.822.032.8347 (18)169
O6—H6···O2vi0.821.902.717 (2)174
O12—H12···O60.85 (3)1.88 (3)2.729 (2)173 (3)
O13—H13···O8vii0.90 (2)1.98 (2)2.863 (3)169 (5)
Symmetry codes: (iii) x1/2, y+1/2, z; (iv) x+1/2, y+1/2, z; (v) x, y+1, z; (vi) x+1/2, y1/2, z; (vii) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC18H22O11·H2O
Mr432.38
Crystal system, space groupMonoclinic, C2
Temperature (K)291
a, b, c (Å)15.1250 (4), 5.6702 (1), 22.8781 (5)
β (°) 95.3753 (13)
V3)1953.44 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.35 × 0.10 × 0.10
Data collection
DiffractometerNonius KappaCCD area detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10609, 3091, 2393
Rint0.032
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.101, 1.03
No. of reflections3091
No. of parameters284
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.23, 0.19

Computer programs: KappaCCD Server Software (Nonius, 1999), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.

Selected geometric parameters (Å, º) top
O1—C11.416 (2)O7—C81.353 (3)
O1—C71.406 (3)O9—C111.466 (3)
O5—C11.414 (2)O9—C151.362 (3)
O5—C51.439 (2)C8—C91.326 (3)
O7—C71.437 (3)C12—C131.334 (3)
C8—C9—C10123.83 (19)O9—C11—C12112.9 (2)
C8—C9—C15122.1 (2)C10—C11—C12101.89 (17)
C10—C9—C15109.06 (19)C13—C12—C11112.80 (19)
C9—C10—C1198.99 (17)C12—C13—C14110.7 (2)
C9—C10—C14108.63 (19)C7—C14—C10109.70 (17)
C11—C10—C14106.69 (16)C7—C14—C13119.6 (2)
O9—C11—C10105.84 (16)C10—C14—C13101.77 (16)
C1—O1—C7—O771.2 (2)C7—O1—C1—C2178.07 (16)
C1—O1—C7—C14165.98 (16)O5—C5—C6—O673.4 (2)
C7—O1—C1—O563.4 (2)C4—C5—C6—O6167.47 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O11i0.821.982.752 (2)155.8
O3—H3···O4ii0.822.082.800 (2)146.7
O4—H4···O12iii0.822.032.8347 (18)168.7
O6—H6···O2iv0.821.902.717 (2)173.6
O12—H12···O60.85 (3)1.88 (3)2.729 (2)173 (3)
O13—H13···O8v0.895 (19)1.98 (2)2.863 (3)169 (5)
Symmetry codes: (i) x1/2, y+1/2, z; (ii) x+1/2, y+1/2, z; (iii) x, y+1, z; (iv) x+1/2, y1/2, z; (v) x+1/2, y+1/2, z.
 

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