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The title compound, C32H43NO4·CH4O·H2O, has a nearly planar cyano-enone A ring in an otherwise normal oleanane triterpenoid. Rings A, B and C are non-chairs, but rings D and E adopt essentially cyclo­hexane chair conformations. The structure clearly establishes the C-D-E ring stereochemistry as trans-syn-cis, as predicted from a nuclear Overhauser effect (NOE) NMR measurement.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010102176X/fr1352sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010102176X/fr1352Isup2.hkl
Contains datablock I

CCDC reference: 183042

Comment top

We have found that several synthetic triterpenoids derived from the naturally occurring oleanolic and ursolic acids, with an enone functionality in the A and C rings, have significant biological activity. For example, 2-cyano-3,12-dioxooleana-1,9-dien-28-oic acid (CDDO) exhibits potent antiinflammatory, differentiating and antiproliferative activity (Honda et al., 1997, 1998, 1999; Suh et al., 1998, 1999; Honda, Gribble et al., 2000; Honda, Rounds et al., 2000). Furthermore, CDDO is a ligand for the peroxisome proliferator-activated receptor γ (Wang et al., 2000), and it also induces apoptosis in human myeloid leukemia cells (Ito et al., 2000). In order to probe the possible receptor proteins for which CDDO may be a ligand, we now report the crystal-structure determination of the title compound, (I), which is the methyl ester of CDDO. This is the first crystal structure to be reported for a member of these synthetic oleanane enones. Only a few oleanane crystal structures have been previously recorded, including 18-(H)-oleanane (Fowell et al., 1978), methyl 3,16-dihydroxy-12-oxo-13-oleanan-28-oate dihydrate (Dhaneshwar et al., 1987) and methyl 3-acetoxy-12-oxo-18-olean-28-oate (Gzella, 2000). \sch

The crystal structure determination reported herein supports our structural assignments for both CDDO-methyl ester, (I), and CDDO, which were based solely on spectral data and the method of synthesis. The X-ray structure of (I) confirms the ketone functionalities at C3 and C12, the cyano group at C2, the methyl ester at C17, and the CC double bonds at C1—C2 and C9—C11.

The unsaturated carbonyl bond distances, C3—O1 [1.215 (6) Å] and C12—O2 [1.231 (5) Å], are similar to the corresponding values reported for the saturated ketones in allobetulone [C3—O1 1.206 (3) Å; Klinot et al., 1989], 12α-hydroxy-3-oxooleanano-28,13-lactone [C3—O1 1.201 (4) Å; Eggleston, 1987] and avenestergenin A-2 [C12—O2 1.20 (1) Å; Begley et al., 1986]. The carbonyl bond distances in (I) and the cyano group triple bond distance [C31N1 1.137 (7) Å] are normal.

The CC double bonds at C1C2 [1.327 (7) Å] and C9C11 [1.353 (6) Å] are similar to the value for a simple alkene CC double bond (1.316 Å; Batsanov, 2000), which again perhaps reflects the enone character of these double bonds.

Rings A—C are non-chairs, due to the presence of sp2 C atoms at C1, C2, C3, C9, C11 and C12, but rings D and E adopt essentially cyclohexane chair conformations. Ring A is nearly planar, with a mean deviation from the plane of 0.165 Å. The X-ray structure clearly establishes the CDE ring stereochemistry as trans-syn-cis and supports the stereochemistry of the H atom at C13, which was previously assigned from an NOESY experiment on a precursor compound (Honda, Rounds et al., 2000).

Methanol and water solvates both co-crystallize in the unit cell of (I) and provide unique hydrogen-bond intermolecular interactions. The methanol oxygen, O5, is hydrogen-bonded both to O1 in the oleanane and to the water molecule. In addition, the water molecule is also hydrogen-bonded to atom O2 of a symmetry-related oleanane molecule.

Experimental top

Compound (I) was prepared in ten steps from oleanolic acid, as recently described by Honda, Rounds et al. (2000). Recrystallization from methanol gave colourless needles of (I) (m.p. 437–440 K).

Refinement top

The absolute configuration of (I) could not be determined. Water H atoms were refined, with H—O constrained to 0.86 Å. Other H atoms were treated as riding, with C—H = 0.98 for CH3, 0.99 for CH2, 1.00 for CH and 0.95 Å for CH(aromatic), and O—H = 0.84 Å. A torsional parameter was refined for each methyl group, and a common Uiso value was refined for each H-atom type.

Structure description top

We have found that several synthetic triterpenoids derived from the naturally occurring oleanolic and ursolic acids, with an enone functionality in the A and C rings, have significant biological activity. For example, 2-cyano-3,12-dioxooleana-1,9-dien-28-oic acid (CDDO) exhibits potent antiinflammatory, differentiating and antiproliferative activity (Honda et al., 1997, 1998, 1999; Suh et al., 1998, 1999; Honda, Gribble et al., 2000; Honda, Rounds et al., 2000). Furthermore, CDDO is a ligand for the peroxisome proliferator-activated receptor γ (Wang et al., 2000), and it also induces apoptosis in human myeloid leukemia cells (Ito et al., 2000). In order to probe the possible receptor proteins for which CDDO may be a ligand, we now report the crystal-structure determination of the title compound, (I), which is the methyl ester of CDDO. This is the first crystal structure to be reported for a member of these synthetic oleanane enones. Only a few oleanane crystal structures have been previously recorded, including 18-(H)-oleanane (Fowell et al., 1978), methyl 3,16-dihydroxy-12-oxo-13-oleanan-28-oate dihydrate (Dhaneshwar et al., 1987) and methyl 3-acetoxy-12-oxo-18-olean-28-oate (Gzella, 2000). \sch

The crystal structure determination reported herein supports our structural assignments for both CDDO-methyl ester, (I), and CDDO, which were based solely on spectral data and the method of synthesis. The X-ray structure of (I) confirms the ketone functionalities at C3 and C12, the cyano group at C2, the methyl ester at C17, and the CC double bonds at C1—C2 and C9—C11.

The unsaturated carbonyl bond distances, C3—O1 [1.215 (6) Å] and C12—O2 [1.231 (5) Å], are similar to the corresponding values reported for the saturated ketones in allobetulone [C3—O1 1.206 (3) Å; Klinot et al., 1989], 12α-hydroxy-3-oxooleanano-28,13-lactone [C3—O1 1.201 (4) Å; Eggleston, 1987] and avenestergenin A-2 [C12—O2 1.20 (1) Å; Begley et al., 1986]. The carbonyl bond distances in (I) and the cyano group triple bond distance [C31N1 1.137 (7) Å] are normal.

The CC double bonds at C1C2 [1.327 (7) Å] and C9C11 [1.353 (6) Å] are similar to the value for a simple alkene CC double bond (1.316 Å; Batsanov, 2000), which again perhaps reflects the enone character of these double bonds.

Rings A—C are non-chairs, due to the presence of sp2 C atoms at C1, C2, C3, C9, C11 and C12, but rings D and E adopt essentially cyclohexane chair conformations. Ring A is nearly planar, with a mean deviation from the plane of 0.165 Å. The X-ray structure clearly establishes the CDE ring stereochemistry as trans-syn-cis and supports the stereochemistry of the H atom at C13, which was previously assigned from an NOESY experiment on a precursor compound (Honda, Rounds et al., 2000).

Methanol and water solvates both co-crystallize in the unit cell of (I) and provide unique hydrogen-bond intermolecular interactions. The methanol oxygen, O5, is hydrogen-bonded both to O1 in the oleanane and to the water molecule. In addition, the water molecule is also hydrogen-bonded to atom O2 of a symmetry-related oleanane molecule.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I) with the co-crystallized moieties and the atom-numbering scheme. Displacment ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
Methyl 2-cyano-3,12-dioxooleana-1,9(11)-diene-28-oate top
Crystal data top
C32H43NO4·CH4O·H2ODx = 1.234 Mg m3
Mr = 555.73Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 56 reflections
a = 6.537 (1) Åθ = 2.4–12.6°
b = 8.950 (1) ŵ = 0.08 mm1
c = 51.128 (9) ÅT = 173 K
V = 2991.3 (8) Å3Needles, colourless
Z = 40.8 × 0.8 × 0.3 mm
F(000) = 1208
Data collection top
Siemens P4
diffractometer
Rint = 0.065
Radiation source: normal-focus sealed tubeθmax = 27.5°, θmin = 2.6°
Graphite monochromatorh = 88
2θ/ω scansk = 1111
10610 measured reflectionsl = 6566
3985 independent reflections3 standard reflections every 197 reflections
2825 reflections with I > 2σ(I) intensity decay: random variation +/2.0%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.070Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.211H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.1033P)2 + 3.411P]
where P = (Fo2 + 2Fc2)/3
3985 reflections(Δ/σ)max = 0.004
387 parametersΔρmax = 0.37 e Å3
2 restraintsΔρmin = 0.34 e Å3
Crystal data top
C32H43NO4·CH4O·H2OV = 2991.3 (8) Å3
Mr = 555.73Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.537 (1) ŵ = 0.08 mm1
b = 8.950 (1) ÅT = 173 K
c = 51.128 (9) Å0.8 × 0.8 × 0.3 mm
Data collection top
Siemens P4
diffractometer
Rint = 0.065
10610 measured reflections3 standard reflections every 197 reflections
3985 independent reflections intensity decay: random variation +/2.0%
2825 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0702 restraints
wR(F2) = 0.211H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.37 e Å3
3985 reflectionsΔρmin = 0.34 e Å3
387 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.

Refinement. The absolute configuration could not be determined. Additional information on _refine_ls_hydrogen_treatment: H2O All H-atom parameters refined, all others refU. H—O distance in H2O constrained to 0.84, C—H distance in CH3- 0.98, in CH2- 0.99 in CH– 1.00 CH(aromatic)- 0.95 and O—H-groups 0.84.

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
C10.3942 (7)0.6932 (5)0.55329 (9)0.0238 (10)
H10.42400.79520.55670.022 (9)*
C20.3391 (8)0.6534 (5)0.52930 (9)0.0250 (10)
C310.3352 (8)0.7630 (6)0.50822 (9)0.0277 (11)
N10.3273 (8)0.8501 (5)0.49208 (9)0.0423 (12)
C30.2974 (7)0.4954 (5)0.52152 (9)0.0230 (10)
O10.2931 (7)0.4608 (4)0.49854 (7)0.0373 (9)
C40.2601 (8)0.3822 (5)0.54307 (9)0.0247 (10)
C230.4204 (9)0.2547 (6)0.54065 (10)0.0322 (12)
H23A0.40500.20520.52370.051 (4)*
H23B0.39880.18180.55470.051 (4)*
H23C0.55840.29660.54210.051 (4)*
C240.0474 (8)0.3145 (6)0.53706 (10)0.0288 (11)
H24A0.05190.39520.53450.051 (4)*
H24B0.00390.25170.55170.051 (4)*
H24C0.05560.25370.52110.051 (4)*
C50.2516 (7)0.4571 (5)0.57041 (9)0.0199 (9)
H50.11640.50920.57090.025 (8)*
C60.2450 (8)0.3469 (5)0.59324 (9)0.0241 (10)
H6A0.15200.26300.58900.035 (4)*
H6B0.38330.30550.59640.035 (4)*
C70.1706 (7)0.4259 (5)0.61749 (8)0.0218 (9)
H7A0.16930.35370.63220.035 (4)*
H7B0.02800.45900.61460.035 (4)*
C80.3001 (7)0.5622 (5)0.62551 (9)0.0205 (9)
C260.4940 (8)0.4978 (5)0.63931 (9)0.0251 (10)
H26A0.45500.45390.65610.051 (4)*
H26B0.59300.57830.64220.051 (4)*
H26C0.55580.42070.62820.051 (4)*
C90.3776 (7)0.6550 (5)0.60232 (9)0.0195 (9)
C100.4113 (7)0.5815 (5)0.57540 (8)0.0198 (9)
C250.6381 (7)0.5274 (6)0.57426 (10)0.0254 (10)
H25A0.67320.50070.55620.051 (4)*
H25B0.65490.43980.58560.051 (4)*
H25C0.72850.60760.58030.051 (4)*
C110.4363 (8)0.7980 (5)0.60653 (9)0.0240 (10)
H110.49210.85250.59230.022 (9)*
C120.4185 (8)0.8738 (5)0.63200 (10)0.0254 (10)
O20.4933 (7)0.9987 (4)0.63521 (7)0.0377 (10)
C130.3190 (7)0.7913 (5)0.65438 (8)0.0191 (9)
H130.43300.73400.66270.025 (8)*
C140.1723 (7)0.6702 (5)0.64380 (8)0.0183 (9)
C270.0043 (7)0.7412 (5)0.62779 (9)0.0230 (9)
H27A0.03920.67570.61310.018 (12)*
H27B0.03920.83880.62110.06 (2)*
H27C0.12430.75390.63910.018 (12)*
C150.0803 (7)0.5836 (5)0.66707 (8)0.0203 (9)
H15A0.03310.52040.66060.035 (4)*
H15B0.18640.51650.67430.035 (4)*
C160.0004 (8)0.6837 (5)0.68901 (9)0.0200 (9)
H16A0.04790.62010.70360.035 (4)*
H16B0.11950.74090.68250.035 (4)*
C170.1614 (8)0.7936 (5)0.69927 (9)0.0203 (9)
C280.3407 (8)0.7139 (5)0.71142 (9)0.0250 (10)
O30.5145 (6)0.7599 (5)0.71185 (8)0.0425 (10)
O40.2893 (6)0.5841 (4)0.72319 (7)0.0335 (9)
C320.4562 (9)0.5074 (6)0.73594 (11)0.0387 (13)
H32A0.55920.47950.72290.051 (4)*
H32B0.40440.41720.74460.051 (4)*
H32C0.51820.57350.74900.051 (4)*
C180.2363 (7)0.8934 (5)0.67645 (8)0.0203 (9)
H180.35590.95140.68320.025 (8)*
C190.0741 (8)1.0088 (5)0.66814 (9)0.0239 (10)
H19A0.13181.07240.65410.035 (4)*
H19B0.04530.95530.66080.035 (4)*
C200.0012 (9)1.1094 (5)0.69057 (10)0.0289 (11)
C290.1734 (10)1.2096 (5)0.70056 (11)0.0361 (13)
H29A0.23431.26380.68580.051 (4)*
H29B0.27821.14820.70900.051 (4)*
H29C0.11811.28130.71320.051 (4)*
C300.1728 (9)1.2069 (6)0.68053 (12)0.0389 (13)
H30A0.22391.26980.69480.051 (4)*
H30B0.28381.14320.67410.051 (4)*
H30C0.12281.27030.66630.051 (4)*
C210.0803 (8)1.0101 (5)0.71273 (10)0.0294 (11)
H21A0.11701.07420.72780.035 (4)*
H21B0.20650.95970.70670.035 (4)*
C220.0729 (8)0.8914 (5)0.72185 (9)0.0258 (10)
H22A0.00460.82520.73470.035 (4)*
H22B0.18750.94180.73090.035 (4)*
O50.2585 (7)0.5234 (5)0.44415 (8)0.0416 (10)
H5A0.23850.49830.45980.035 (16)*
C1000.4549 (11)0.5940 (7)0.44189 (13)0.0506 (17)
H1000.51290.57290.42460.051 (4)*
H1010.54650.55510.45550.051 (4)*
H1020.43940.70220.44410.051 (4)*
O60.2574 (8)0.3281 (5)0.39864 (10)0.0533 (12)
H6C0.206 (10)0.384 (6)0.3865 (10)0.06 (2)*
H6D0.238 (13)0.379 (7)0.4127 (8)0.06 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.022 (2)0.019 (2)0.031 (2)0.000 (2)0.003 (2)0.0003 (19)
C20.025 (2)0.021 (2)0.029 (2)0.001 (2)0.003 (2)0.0006 (19)
C310.024 (2)0.029 (2)0.030 (2)0.004 (2)0.007 (2)0.001 (2)
N10.045 (3)0.037 (2)0.045 (3)0.012 (3)0.009 (2)0.010 (2)
C30.021 (2)0.022 (2)0.026 (2)0.002 (2)0.0001 (19)0.0031 (19)
O10.048 (2)0.0307 (19)0.0332 (19)0.003 (2)0.0005 (19)0.0043 (15)
C40.025 (2)0.019 (2)0.030 (2)0.001 (2)0.002 (2)0.0034 (19)
C230.035 (3)0.026 (2)0.035 (3)0.009 (3)0.001 (2)0.005 (2)
C240.027 (3)0.027 (2)0.032 (3)0.001 (2)0.005 (2)0.003 (2)
C50.0157 (19)0.0157 (19)0.028 (2)0.0011 (19)0.0010 (18)0.0002 (17)
C60.028 (2)0.0161 (19)0.029 (2)0.006 (2)0.002 (2)0.0010 (18)
C70.024 (2)0.018 (2)0.023 (2)0.005 (2)0.0015 (19)0.0019 (18)
C80.017 (2)0.0172 (19)0.027 (2)0.0040 (19)0.0021 (18)0.0004 (18)
C260.022 (2)0.022 (2)0.031 (2)0.000 (2)0.001 (2)0.001 (2)
C90.014 (2)0.0173 (19)0.027 (2)0.0015 (18)0.0015 (18)0.0012 (19)
C100.019 (2)0.020 (2)0.020 (2)0.002 (2)0.0013 (18)0.0020 (18)
C250.016 (2)0.030 (2)0.030 (2)0.000 (2)0.0043 (19)0.001 (2)
C110.027 (2)0.024 (2)0.021 (2)0.011 (2)0.008 (2)0.0033 (18)
C120.022 (2)0.020 (2)0.034 (3)0.007 (2)0.003 (2)0.002 (2)
O20.045 (2)0.0264 (17)0.042 (2)0.020 (2)0.0110 (19)0.0097 (16)
C130.019 (2)0.0157 (19)0.023 (2)0.0026 (19)0.0021 (18)0.0017 (17)
C140.018 (2)0.0137 (19)0.024 (2)0.0018 (18)0.0016 (18)0.0003 (17)
C270.018 (2)0.019 (2)0.031 (2)0.000 (2)0.002 (2)0.0006 (19)
C150.020 (2)0.0143 (18)0.027 (2)0.0037 (19)0.001 (2)0.0006 (18)
C160.020 (2)0.0162 (19)0.024 (2)0.000 (2)0.002 (2)0.0010 (17)
C170.022 (2)0.0188 (19)0.020 (2)0.005 (2)0.0004 (19)0.0003 (18)
C280.025 (2)0.027 (2)0.023 (2)0.003 (2)0.002 (2)0.001 (2)
O30.0248 (19)0.043 (2)0.060 (3)0.008 (2)0.0093 (19)0.012 (2)
O40.0300 (19)0.0288 (17)0.0415 (19)0.0013 (18)0.0062 (17)0.0130 (16)
C320.036 (3)0.037 (3)0.043 (3)0.012 (3)0.008 (3)0.008 (3)
C180.020 (2)0.0144 (19)0.026 (2)0.0049 (19)0.0032 (19)0.0023 (17)
C190.026 (2)0.0158 (19)0.030 (2)0.001 (2)0.001 (2)0.0003 (19)
C200.032 (3)0.019 (2)0.036 (3)0.004 (2)0.000 (2)0.004 (2)
C290.043 (3)0.019 (2)0.047 (3)0.008 (3)0.001 (3)0.008 (2)
C300.037 (3)0.024 (2)0.056 (3)0.006 (3)0.004 (3)0.002 (2)
C210.030 (2)0.019 (2)0.039 (3)0.002 (2)0.008 (2)0.007 (2)
C220.028 (2)0.022 (2)0.027 (2)0.003 (2)0.005 (2)0.0028 (19)
O50.044 (2)0.042 (2)0.039 (2)0.007 (2)0.0018 (19)0.0029 (19)
C1000.059 (4)0.038 (3)0.054 (4)0.011 (4)0.006 (3)0.006 (3)
O60.057 (3)0.040 (2)0.062 (3)0.015 (2)0.014 (3)0.002 (2)
Geometric parameters (Å, º) top
C1—C21.327 (7)C14—C271.551 (6)
C1—C101.513 (6)C27—H27A0.9800
C1—H10.9500C27—H27B0.9800
C2—C311.457 (7)C27—H27C0.9800
C2—C31.495 (6)C15—C161.530 (6)
C31—N11.137 (7)C15—H15A0.9900
C3—O11.215 (6)C15—H15B0.9900
C3—C41.516 (7)C16—C171.536 (6)
C4—C241.548 (7)C16—H16A0.9900
C4—C51.551 (6)C16—H16B0.9900
C4—C231.554 (7)C17—C281.506 (7)
C23—H23A0.9800C17—C181.549 (6)
C23—H23B0.9800C17—C221.560 (6)
C23—H23C0.9800C28—O31.209 (6)
C24—H24A0.9800C28—O41.351 (6)
C24—H24B0.9800O4—C321.444 (6)
C24—H24C0.9800C32—H32A0.9800
C5—C61.529 (6)C32—H32B0.9800
C5—C101.548 (6)C32—H32C0.9800
C5—H51.0000C18—C191.540 (6)
C6—C71.508 (6)C18—H181.0000
C6—H6A0.9900C19—C201.534 (7)
C6—H6B0.9900C19—H19A0.9900
C7—C81.541 (6)C19—H19B0.9900
C7—H7A0.9900C20—C301.523 (8)
C7—H7B0.9900C20—C291.528 (8)
C8—C91.534 (6)C20—C211.535 (7)
C8—C261.561 (7)C29—H29A0.9800
C8—C141.583 (6)C29—H29B0.9800
C26—H26A0.9800C29—H29C0.9800
C26—H26B0.9800C30—H30A0.9800
C26—H26C0.9800C30—H30B0.9800
C9—C111.353 (6)C30—H30C0.9800
C9—C101.541 (6)C21—C221.533 (7)
C10—C251.561 (6)C21—H21A0.9900
C25—H25A0.9800C21—H21B0.9900
C25—H25B0.9800C22—H22A0.9900
C25—H25C0.9800C22—H22B0.9900
C11—C121.473 (6)O5—C1001.436 (8)
C11—H110.9500O5—H5A0.8400
C12—O21.231 (5)C100—H1000.9800
C12—C131.510 (6)C100—H1010.9800
C13—C141.545 (6)C100—H1020.9800
C13—C181.549 (6)O6—H6C0.87 (5)
C13—H131.0000O6—H6D0.86 (5)
C14—C151.541 (6)
C2—C1—C10122.3 (4)C15—C14—C8110.8 (3)
C2—C1—H1118.9C13—C14—C8107.9 (4)
C10—C1—H1118.9C27—C14—C8109.3 (4)
C1—C2—C31120.5 (4)C14—C27—H27A109.5
C1—C2—C3123.3 (4)C14—C27—H27B109.5
C31—C2—C3115.9 (4)H27A—C27—H27B109.5
N1—C31—C2178.0 (6)C14—C27—H27C109.5
O1—C3—C2120.2 (4)H27A—C27—H27C109.5
O1—C3—C4121.9 (4)H27B—C27—H27C109.5
C2—C3—C4117.9 (4)C16—C15—C14114.0 (4)
C3—C4—C24105.2 (4)C16—C15—H15A108.8
C3—C4—C5111.8 (4)C14—C15—H15A108.8
C24—C4—C5108.4 (4)C16—C15—H15B108.8
C3—C4—C23108.9 (4)C14—C15—H15B108.8
C24—C4—C23107.6 (4)H15A—C15—H15B107.7
C5—C4—C23114.4 (4)C15—C16—C17112.8 (4)
C4—C23—H23A109.5C15—C16—H16A109.0
C4—C23—H23B109.5C17—C16—H16A109.0
H23A—C23—H23B109.5C15—C16—H16B109.0
C4—C23—H23C109.5C17—C16—H16B109.0
H23A—C23—H23C109.5H16A—C16—H16B107.8
H23B—C23—H23C109.5C28—C17—C16111.9 (4)
C4—C24—H24A109.5C28—C17—C18109.7 (4)
C4—C24—H24B109.5C16—C17—C18109.3 (4)
H24A—C24—H24B109.5C28—C17—C22104.4 (4)
C4—C24—H24C109.5C16—C17—C22110.9 (4)
H24A—C24—H24C109.5C18—C17—C22110.5 (4)
H24B—C24—H24C109.5O3—C28—O4121.2 (5)
C6—C5—C10110.9 (4)O3—C28—C17125.3 (5)
C6—C5—C4114.2 (3)O4—C28—C17113.4 (4)
C10—C5—C4115.8 (4)C28—O4—C32114.9 (4)
C6—C5—H5104.9O4—C32—H32A109.5
C10—C5—H5104.9O4—C32—H32B109.5
C4—C5—H5104.9H32A—C32—H32B109.5
C7—C6—C5109.5 (4)O4—C32—H32C109.5
C7—C6—H6A109.8H32A—C32—H32C109.5
C5—C6—H6A109.8H32B—C32—H32C109.5
C7—C6—H6B109.8C19—C18—C13115.8 (4)
C5—C6—H6B109.8C19—C18—C17112.1 (4)
H6A—C6—H6B108.2C13—C18—C17108.6 (3)
C6—C7—C8114.4 (4)C19—C18—H18106.6
C6—C7—H7A108.7C13—C18—H18106.6
C8—C7—H7A108.7C17—C18—H18106.6
C6—C7—H7B108.7C20—C19—C18113.7 (4)
C8—C7—H7B108.7C20—C19—H19A108.8
H7A—C7—H7B107.6C18—C19—H19A108.8
C9—C8—C7113.9 (4)C20—C19—H19B108.8
C9—C8—C26106.3 (4)C18—C19—H19B108.8
C7—C8—C26105.9 (4)H19A—C19—H19B107.7
C9—C8—C14107.5 (3)C30—C20—C29109.0 (4)
C7—C8—C14110.5 (4)C30—C20—C19108.5 (4)
C26—C8—C14112.8 (4)C29—C20—C19111.4 (5)
C8—C26—H26A109.5C30—C20—C21108.7 (5)
C8—C26—H26B109.5C29—C20—C21110.4 (4)
H26A—C26—H26B109.5C19—C20—C21108.7 (4)
C8—C26—H26C109.5C20—C29—H29A109.5
H26A—C26—H26C109.5C20—C29—H29B109.5
H26B—C26—H26C109.5H29A—C29—H29B109.5
C11—C9—C8118.9 (4)C20—C29—H29C109.5
C11—C9—C10120.3 (4)H29A—C29—H29C109.5
C8—C9—C10120.4 (4)H29B—C29—H29C109.5
C1—C10—C9112.0 (4)C20—C30—H30A109.5
C1—C10—C5107.6 (4)C20—C30—H30B109.5
C9—C10—C5111.0 (4)H30A—C30—H30B109.5
C1—C10—C25104.3 (4)C20—C30—H30C109.5
C9—C10—C25107.6 (4)H30A—C30—H30C109.5
C5—C10—C25114.3 (4)H30B—C30—H30C109.5
C10—C25—H25A109.5C22—C21—C20113.5 (4)
C10—C25—H25B109.5C22—C21—H21A108.9
H25A—C25—H25B109.5C20—C21—H21A108.9
C10—C25—H25C109.5C22—C21—H21B108.9
H25A—C25—H25C109.5C20—C21—H21B108.9
H25B—C25—H25C109.5H21A—C21—H21B107.7
C9—C11—C12123.6 (4)C21—C22—C17114.0 (4)
C9—C11—H11118.2C21—C22—H22A108.8
C12—C11—H11118.2C17—C22—H22A108.8
O2—C12—C11120.3 (4)C21—C22—H22B108.8
O2—C12—C13121.0 (4)C17—C22—H22B108.8
C11—C12—C13118.6 (4)H22A—C22—H22B107.7
C12—C13—C14110.2 (4)C100—O5—H5A109.5
C12—C13—C18114.4 (4)O5—C100—H100109.5
C14—C13—C18116.9 (4)O5—C100—H101109.5
C12—C13—H13104.6H100—C100—H101109.5
C14—C13—H13104.6O5—C100—H102109.5
C18—C13—H13104.6H100—C100—H102109.5
C15—C14—C13108.9 (3)H101—C100—H102109.5
C15—C14—C27108.9 (4)H6C—O6—H6D104 (6)
C13—C14—C27111.0 (3)
C10—C1—C2—C31176.6 (4)C11—C12—C13—C18158.8 (4)
C10—C1—C2—C32.7 (8)C12—C13—C14—C15177.6 (4)
C1—C2—C31—N174 (17)C18—C13—C14—C1549.5 (5)
C3—C2—C31—N1112 (17)C12—C13—C14—C2762.5 (5)
C1—C2—C3—O1163.3 (5)C18—C13—C14—C2770.4 (5)
C31—C2—C3—O110.9 (7)C12—C13—C14—C857.3 (5)
C1—C2—C3—C417.0 (7)C18—C13—C14—C8169.8 (4)
C31—C2—C3—C4168.8 (4)C9—C8—C14—C15177.5 (4)
O1—C3—C4—C2456.6 (6)C7—C8—C14—C1552.6 (5)
C2—C3—C4—C24123.0 (4)C26—C8—C14—C1565.7 (5)
O1—C3—C4—C5174.1 (5)C9—C8—C14—C1363.4 (4)
C2—C3—C4—C55.6 (6)C7—C8—C14—C13171.8 (3)
O1—C3—C4—C2358.5 (6)C26—C8—C14—C1353.5 (5)
C2—C3—C4—C23121.9 (5)C9—C8—C14—C2757.5 (4)
C3—C4—C5—C6171.7 (4)C7—C8—C14—C2767.3 (4)
C24—C4—C5—C672.8 (5)C26—C8—C14—C27174.4 (4)
C23—C4—C5—C647.3 (6)C13—C14—C15—C1647.4 (5)
C3—C4—C5—C1041.0 (5)C27—C14—C15—C1673.8 (5)
C24—C4—C5—C10156.4 (4)C8—C14—C15—C16165.9 (4)
C23—C4—C5—C1083.5 (5)C14—C15—C16—C1754.9 (5)
C10—C5—C6—C764.8 (5)C15—C16—C17—C2863.0 (5)
C4—C5—C6—C7162.1 (4)C15—C16—C17—C1858.7 (5)
C5—C6—C7—C857.5 (5)C15—C16—C17—C22179.2 (4)
C6—C7—C8—C938.1 (5)C16—C17—C28—O3150.0 (5)
C6—C7—C8—C2678.4 (5)C18—C17—C28—O328.5 (7)
C6—C7—C8—C14159.2 (4)C22—C17—C28—O390.0 (6)
C7—C8—C9—C11159.9 (4)C16—C17—C28—O432.5 (5)
C26—C8—C9—C1183.9 (5)C18—C17—C28—O4154.0 (4)
C14—C8—C9—C1137.1 (6)C22—C17—C28—O487.5 (5)
C7—C8—C9—C1027.1 (6)O3—C28—O4—C320.1 (7)
C26—C8—C9—C1089.1 (5)C17—C28—O4—C32177.7 (4)
C14—C8—C9—C10149.9 (4)C12—C13—C18—C1959.2 (5)
C2—C1—C10—C9153.4 (5)C14—C13—C18—C1971.8 (5)
C2—C1—C10—C531.2 (6)C12—C13—C18—C17173.7 (4)
C2—C1—C10—C2590.6 (5)C14—C13—C18—C1755.3 (5)
C11—C9—C10—C132.6 (6)C28—C17—C18—C19164.5 (4)
C8—C9—C10—C1154.4 (4)C16—C17—C18—C1972.5 (5)
C11—C9—C10—C5152.9 (4)C22—C17—C18—C1949.8 (5)
C8—C9—C10—C534.2 (5)C28—C17—C18—C1366.4 (5)
C11—C9—C10—C2581.5 (5)C16—C17—C18—C1356.7 (5)
C8—C9—C10—C2591.5 (5)C22—C17—C18—C13179.0 (4)
C6—C5—C10—C1174.7 (4)C13—C18—C19—C20178.7 (4)
C4—C5—C10—C153.0 (5)C17—C18—C19—C2056.0 (5)
C6—C5—C10—C951.9 (5)C18—C19—C20—C30174.4 (4)
C4—C5—C10—C9175.8 (4)C18—C19—C20—C2965.6 (5)
C6—C5—C10—C2569.9 (5)C18—C19—C20—C2156.3 (6)
C4—C5—C10—C2562.3 (5)C30—C20—C21—C22171.9 (4)
C8—C9—C11—C123.9 (7)C29—C20—C21—C2268.5 (5)
C10—C9—C11—C12177.0 (5)C19—C20—C21—C2254.0 (6)
C9—C11—C12—O2172.7 (5)C20—C21—C22—C1752.3 (5)
C9—C11—C12—C133.5 (8)C28—C17—C22—C21166.6 (4)
O2—C12—C13—C14159.2 (5)C16—C17—C22—C2172.6 (5)
C11—C12—C13—C1424.6 (6)C18—C17—C22—C2148.7 (5)
O2—C12—C13—C1825.1 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O10.842.042.846 (5)160
O6—H6C···O2i0.87 (5)2.07 (6)2.895 (6)160 (7)
O6—H6D···O50.87 (5)2.07 (5)2.910 (6)166 (8)
Symmetry code: (i) x1/2, y+3/2, z+1.

Experimental details

Crystal data
Chemical formulaC32H43NO4·CH4O·H2O
Mr555.73
Crystal system, space groupOrthorhombic, P212121
Temperature (K)173
a, b, c (Å)6.537 (1), 8.950 (1), 51.128 (9)
V3)2991.3 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.8 × 0.8 × 0.3
Data collection
DiffractometerSiemens P4
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10610, 3985, 2825
Rint0.065
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.070, 0.211, 1.05
No. of reflections3985
No. of parameters387
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.37, 0.34

Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O10.842.042.846 (5)160
O6—H6C···O2i0.87 (5)2.07 (6)2.895 (6)160 (7)
O6—H6D···O50.87 (5)2.07 (5)2.910 (6)166 (8)
Symmetry code: (i) x1/2, y+3/2, z+1.
 

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