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The title compound, C15H22O3, derived from a naturally occurring sesquiterpenoid, has two mol­ecules in the asymmetric unit, differing principally in the rotational conformation of the carboxyl group. Each species aggregates separately as a carboxyl-to-ketone hydrogen-bonding catemer [O...O = 2.752 (4) and 2.682 (4) Å, and O—H...O = 161 (4) and 168 (4)°], producing two crystallographically independent single-strand hydrogen-bonding helices, with opposite end-to-end orientations, passing through the cell in the b direction. Three intermolecular C—H...O=C close contacts exist for the ketone.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102004365/fr1365sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102004365/fr1365Isup2.hkl
Contains datablock I

CCDC reference: 187922

Comment top

Our crystallographic studies of keto carboxylic acids explore the molecular characteristics that control their hydrogen-bonding patterns. Functionally unelaborated acids commonly aggregate in the solid as dimers, rarely as catemers (chains). An added ketone function provides opportunities for at least three additional hydrogen-bonding modes, the commonest of which, the acid-to-ketone catemer, forms a sizable overall minority of keto acid hydrogen-bonding cases. As we have previously suggested, carboxyl dimerization is suppressed in monoenantiomeric species (Lalancette et al., 1998) and by the presence of conformational restrictions (Brunskill et al., 1999). In the presence of such molecular features, catemer formation may become the dominant hydrogen-bonding mode (Brunskill et al., 1997).

The title compound (1), derived from a sesquiterpenoid isolate of Artemisia, is a bicyclic ζ-keto acid, present as a single enantiomer. We have previously (Brunskill et al., 2001) described a related diketo-dienoic acid (plus its hydrate) and Khanina et al. (1998) have recently published the X-ray structure of the Δ9 - 11 derivative of (I). Both those compounds display catemeric carboxyl-to-ketone hydrogen bonding, and we report here that (I) also adopts this hydrogen-bonding mode in the solid state.

Fig. 1 shows the asymmetric unit, consisting of two molecules, I and I', which differ principally in the rotation of the carboxyl group about the C9—C10 bond. The substituents at C9, which has an S configuration, are staggered with respect to those at C2, so that the methyl group is anti to C1; the C1—C2—C9—C11 torsion angle is -178.0 (3)° in molecule I and 179.9 (3)° in molecule I', a difference of only 2.1 (4)°. However, in I, the carboxyl group is rotated so that its CO is turned toward the molecular face bearing the angular methyl group, a cisoid arrangement, in which the C2—C9—C10—O3 torsion angle is 73.7 (4)°, while in I', this relationship is transoid and the corresponding angle is -123.6 (4)°, a difference of 162.7 (6)°.

The partial averaging of C—O bond lengths and C—C—O angles by disorder often seen in acids occurs only in the carboxyl-pairing hydrogen-bonding mode. As in other catemers, no significant averaging is observed for molecule I, whose bond lengths are 1.193 (4)/1.316 (5) Å, with angles of 124.5 (4)/112.1 (3)°; for molecule I', these values are 1.190 (5)/1.320 (5) Å and 124.4 (4)/112.4 (4)°. Our own survey of 56 keto acid structures which are not acid dimers gives average values of 1.200 (10)/1.32 (2) Å and 124.5 (14)/112.7 (17)° for these lengths and angles, in accord with typical values of 1.21/1.31 Å and 123/112° cited for highly ordered dimeric carboxyls (Borthwick, 1980). The three methyl groups are fully ordered in molecules I and I', and atoms C11 and C13 are staggered relative to the substituents at their points of attachment.

Fig. 2 illustrates the packing of molecules I and I' in the cell, with extracellular molecules included to show the two crystallographically independent single-strand hydrogen-bonding catemers, in which each chain proceeds from the carboxyl group of one molecule to the ketone group of a neighbor of its own type. Among such catemers, the observed prevalence of subtypes, describing the relation of adjacent molecules, is screw > translation > glide. Here, adjacent intrachain units are related by a twofold screw along b; helices of type-I follow an axis through the cell center, while the axis for the counterdirectionally aligned type-I' helices lies in the bc face of the chosen cell.

Consistent with the difference found between molecules I and I' for the rotation of the COOH group about C9—C10, the intramolecular ketone versus carboxyl dihedral angles for I and I' differ only by 11.04 (14)°. The intermolecular ketone versus carboxyl dihedral angles for adjacent hydrogen-bonded molecules are also similar, at 65.06 (15)° for the type-I chains and 57.67 (15)° for the type-I' chains.

Considering the difference of 162.7 (6)° in carboxyl rotation, the geometry of the hydrogen bonding itself for I versus I' adheres remarkably closely to standard patterns for O—H···OC situations. We characterize the geometry of hydrogen bonding to carbonyls using a combination of the H···O C angle and the H···OC—C torsion angle. These describe the approach of the H atom to the O atom in terms of its deviation from, respectively, CO axiality (ideal = 120°) and planarity with the carbonyl group (ideal = 0°). In molecule I, these angles are 119.9 (13) and -14 (2)°, respectively, while in molecule I', the they are 122.9 (13) and 16 (2)°, respectively.

Three intermolecular C—H···O close contacts exist, all for the type-I carboxyl CO group, within the 2.7 Å range we usually employ for non-bonded C—H···O packing interactions (Steiner, 1997). These involve H5'B (2.63 Å) and H6'B (2.65 Å) within the same type-I' molecule, related translationally in a, plus H6B (2.59 Å) in a type-I molecule, its own hydrogen-bonding partner, screw related in b. Using compiled data for a large number of C—H···O contacts, Steiner & Desiraju (1998) find significant statistical directionality, even as far out as 3.0 Å, and conclude that these are legitimately viewed as `weak hydrogen bonds', with a greater contribution to packing forces than simple van der Waals attractions.

The KBr IR spectrum of (I) displays absorptions at 1726 and 1627 cm-1, consistent with known hydrogen-bonding shifts due, respectively, to its removal from acid CO and its addition to an unsaturated ketone; a minor peak appears at 1675 cm-1 and a shoulder at ca 1599 cm-1 (CC). In CHCl3 solution, where dimers predominate, the major peaks appear, more normally, at 1708 and 1656 cm-1, with a smaller CC peak at 1608 cm-1 and a typical carboxyl-dilution shoulder near 1750 cm-1.

Experimental top

Commercial (-)-α-santonin of known relative and absolute stereochemistry (Barton et al., 1962; Nakazaki & Arakawa, 1962; Asher & Sim, 1965; Coggin & Sim, 1969) was obtained from Aldrich Chemical Co., Milwaukee, Wisconsin, USA, and subjected to the LiNH3 reductive procedure described by Bruderer et al. (1956) and Howe et al. (1959), who have also assigned the optical rotation. Crystals of (I) (m.p. 398 K) were obtained from an acetone–water solution.

Refinement top

The H atoms of molecules I and I were found in electron-density difference maps but were placed in calculated positions (0.96 Å for methyl, 0.97 Å for methylene and 0.98 Å for methine H atoms) and allowed to refine as riding models on their respective C atoms. The displacement parameters were fixed at 120% of those of their respective C atoms, except for the methyl H atoms, which were fixed at 150% of those of their respective C atoms. The postitional parameters of the carboxyl H atoms were allowed to refine, but their displacement parameters were fixed at 0.08 Å2. The absolute configuration was not directly determined, and Friedel pairs were averaged.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; 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.

Figures top
[Figure 1] Fig. 1. The asymmetric unit for (I) with the atom-numbering scheme. Displacement ellipsoids are set at the 20% probability level.
[Figure 2] Fig. 2. A packing diagram, with extracellular molecules to illustrate the two kinds of single-strand helical catemers proceeding in the b direction. Those of type-I follow an axis in the center of the cell at a = 1/2, while those of type-I' follow an axis in the bc face. Methylene and methine H atoms have been omitted for clarity. Displacement ellipsoids are set at the 20% probability level.
(+)-2-(1,2,3,4,4a,5,6,7-Octahydro-4a,8-dimethyl-7-oxo-2- naphthyl)propionic acid top
Crystal data top
C15H22O3Dx = 1.183 Mg m3
Mr = 250.33Melting point: 398 K
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 10.0225 (14) ÅCell parameters from 25 reflections
b = 14.862 (2) Åθ = 4.5–13.8°
c = 10.0873 (14) ŵ = 0.08 mm1
β = 110.758 (11)°T = 296 K
V = 1405.0 (3) Å3Parallelepiped, colourless
Z = 40.44 × 0.30 × 0.22 mm
F(000) = 544
Data collection top
Siemens P4
diffractometer
Rint = 0.029
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.2°
Graphite monochromatorh = 1111
2θ/θ scansk = 1717
5441 measured reflectionsl = 1111
2579 independent reflections3 standard reflections every 97 reflections
1977 reflections with I > 2σ(I) intensity decay: variation < 1.5%
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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0451P)2 + 0.1708P]
where P = (Fo2 + 2Fc2)/3
2579 reflections(Δ/σ)max < 0.001
337 parametersΔρmax = 0.14 e Å3
1 restraintΔρmin = 0.10 e Å3
Crystal data top
C15H22O3V = 1405.0 (3) Å3
Mr = 250.33Z = 4
Monoclinic, P21Mo Kα radiation
a = 10.0225 (14) ŵ = 0.08 mm1
b = 14.862 (2) ÅT = 296 K
c = 10.0873 (14) Å0.44 × 0.30 × 0.22 mm
β = 110.758 (11)°
Data collection top
Siemens P4
diffractometer
Rint = 0.029
5441 measured reflections3 standard reflections every 97 reflections
2579 independent reflections intensity decay: variation < 1.5%
1977 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0421 restraint
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.14 e Å3
2579 reflectionsΔρmin = 0.10 e Å3
337 parameters
Special details top

Experimental. Crystal mounted on glass fiber with epoxy resin

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.5796 (3)0.82699 (19)0.3203 (3)0.0803 (8)
O20.2136 (3)0.5202 (2)0.6780 (3)0.0838 (8)
O30.4239 (4)0.4810 (2)0.8324 (3)0.0856 (9)
C10.4028 (4)0.7012 (2)0.6672 (3)0.0556 (9)
C20.4504 (3)0.6838 (2)0.8276 (3)0.0479 (8)
C30.4758 (4)0.7724 (2)0.9070 (3)0.0556 (9)
C40.5732 (4)0.8340 (2)0.8626 (3)0.0587 (9)
C4A0.5191 (3)0.8568 (2)0.7043 (3)0.0510 (8)
C50.6333 (4)0.9097 (3)0.6718 (4)0.0631 (9)
C60.5978 (4)0.9218 (2)0.5129 (4)0.0642 (10)
C70.5667 (4)0.8344 (2)0.4359 (4)0.0568 (9)
C80.5119 (4)0.7600 (2)0.4970 (4)0.0603 (9)
C8A0.4885 (3)0.7694 (2)0.6204 (3)0.0511 (8)
C90.3395 (4)0.6243 (2)0.8613 (3)0.0524 (8)
C100.3158 (4)0.5367 (3)0.7803 (4)0.0590 (9)
C110.3770 (4)0.6068 (3)1.0196 (4)0.0704 (11)
C120.4927 (5)0.6721 (3)0.4177 (4)0.0753 (12)
C130.3832 (4)0.9138 (3)0.6673 (4)0.0713 (11)
O1'0.9312 (4)0.68963 (19)0.6684 (3)0.0870 (9)
O2'1.2432 (4)0.9889 (2)0.2969 (3)0.0945 (10)
O3'1.0430 (4)1.0506 (2)0.1547 (3)0.0899 (11)
C1'0.9853 (4)0.8318 (2)0.2603 (4)0.0591 (9)
C2'1.0897 (4)0.8203 (2)0.1815 (4)0.0567 (9)
C3'1.0515 (5)0.7354 (2)0.0906 (4)0.0705 (11)
C4'1.0497 (4)0.6549 (2)0.1819 (4)0.0659 (10)
C4A'0.9482 (4)0.6622 (2)0.2650 (3)0.0527 (8)
C5'0.9773 (4)0.5835 (2)0.3681 (4)0.0639 (10)
C6'0.9043 (4)0.5921 (2)0.4744 (4)0.0658 (10)
C7'0.9346 (4)0.6811 (2)0.5499 (4)0.0553 (9)
C8'0.9633 (4)0.7591 (2)0.4744 (3)0.0529 (8)
C8A'0.9714 (3)0.7511 (2)0.3449 (3)0.0508 (8)
C9'1.0952 (4)0.9048 (3)0.0969 (4)0.0629 (10)
C10'1.1376 (5)0.9849 (3)0.1943 (4)0.0637 (10)
C11'1.1982 (6)0.8962 (3)0.0169 (5)0.0985 (16)
C12'0.9820 (5)0.8470 (2)0.5546 (4)0.0658 (10)
C13'0.7921 (4)0.6592 (3)0.1618 (4)0.0828 (13)
H30.403 (4)0.432 (3)0.781 (5)0.080*
H1A0.40590.64450.62060.067*
H1B0.30420.72090.63390.067*
H2A0.54100.65090.85680.058*
H3A0.51820.76081.00800.067*
H3B0.38510.80230.88940.067*
H4A0.66610.80570.88760.070*
H4B0.58570.88960.91610.070*
H5A0.72380.87850.71180.076*
H5B0.64340.96840.71650.076*
H6A0.51550.96100.47550.077*
H6B0.67760.95060.49680.077*
H9A0.24870.65700.82820.063*
H11A0.38170.66301.06800.106*
H11B0.46780.57711.05670.106*
H11C0.30510.56941.03360.106*
H12A0.52710.67810.34060.113*
H12B0.39330.65650.38110.113*
H12C0.54530.62570.48080.113*
H13A0.40410.96850.72160.107*
H13B0.31140.88070.68910.107*
H13C0.34910.92810.56800.107*
H3'1.064 (4)1.092 (3)0.213 (5)0.080*
H1'A1.01580.88280.32390.071*
H1'B0.89190.84590.19160.071*
H2'A1.18500.81140.25290.068*
H3'A0.95840.74270.01710.085*
H3'B1.12090.72590.04520.085*
H4'A1.14560.64530.24890.079*
H4'B1.02350.60210.12160.079*
H5'A0.94580.52840.31460.077*
H5'B1.07940.57880.41830.077*
H6'A0.80210.58560.42630.079*
H6'B0.93630.54400.54350.079*
H9'A0.99950.91580.02760.075*
H11D1.16530.84990.05360.148*
H11E1.29140.88080.08220.148*
H11F1.20290.95240.02820.148*
H12D0.99870.83500.65270.099*
H12E0.89720.88270.51540.099*
H12F1.06190.87920.54660.099*
H13D0.77640.70640.09300.124*
H13E0.72920.66720.21380.124*
H13F0.77350.60200.11440.124*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.126 (2)0.0705 (18)0.0657 (16)0.0136 (17)0.0599 (17)0.0019 (15)
O20.0721 (17)0.096 (2)0.0763 (18)0.0099 (17)0.0178 (15)0.0227 (17)
O30.116 (2)0.0689 (19)0.0636 (17)0.0261 (19)0.0212 (17)0.0067 (15)
C10.072 (2)0.055 (2)0.0417 (17)0.0102 (18)0.0222 (16)0.0069 (16)
C20.0521 (19)0.0507 (19)0.0426 (17)0.0079 (15)0.0186 (14)0.0011 (14)
C30.071 (2)0.057 (2)0.0404 (16)0.0056 (18)0.0216 (16)0.0011 (16)
C40.073 (2)0.055 (2)0.0444 (17)0.0016 (18)0.0167 (17)0.0069 (16)
C4A0.056 (2)0.0491 (19)0.0470 (17)0.0043 (16)0.0176 (16)0.0002 (15)
C50.076 (2)0.057 (2)0.059 (2)0.009 (2)0.0261 (19)0.0079 (18)
C60.082 (3)0.053 (2)0.066 (2)0.009 (2)0.037 (2)0.0009 (18)
C70.070 (2)0.057 (2)0.0475 (19)0.0027 (18)0.0262 (17)0.0013 (17)
C80.085 (2)0.053 (2)0.0492 (17)0.0079 (19)0.0324 (17)0.0046 (18)
C8A0.059 (2)0.0530 (19)0.0444 (17)0.0070 (17)0.0216 (16)0.0050 (16)
C90.060 (2)0.057 (2)0.0448 (17)0.0099 (17)0.0242 (16)0.0035 (16)
C100.072 (2)0.067 (2)0.0475 (19)0.001 (2)0.0318 (19)0.0062 (19)
C110.095 (3)0.072 (3)0.0512 (19)0.003 (2)0.036 (2)0.0036 (19)
C120.119 (3)0.062 (2)0.061 (2)0.014 (2)0.050 (2)0.0103 (19)
C130.080 (3)0.067 (2)0.071 (2)0.023 (2)0.032 (2)0.008 (2)
O1'0.153 (3)0.0549 (16)0.0711 (17)0.0089 (18)0.0613 (18)0.0008 (15)
O2'0.092 (2)0.095 (2)0.085 (2)0.0072 (19)0.0190 (18)0.0098 (19)
O3'0.142 (3)0.0634 (19)0.0619 (17)0.0302 (19)0.0327 (18)0.0016 (15)
C1'0.082 (2)0.0446 (19)0.059 (2)0.0144 (18)0.0347 (19)0.0021 (17)
C2'0.075 (2)0.0486 (19)0.0513 (19)0.0159 (18)0.0277 (17)0.0041 (16)
C3'0.102 (3)0.058 (2)0.062 (2)0.014 (2)0.042 (2)0.0025 (19)
C4'0.089 (3)0.048 (2)0.061 (2)0.0158 (19)0.028 (2)0.0053 (17)
C4A'0.063 (2)0.0426 (18)0.0482 (18)0.0084 (16)0.0139 (16)0.0043 (15)
C5'0.092 (3)0.0409 (18)0.056 (2)0.0051 (19)0.023 (2)0.0051 (16)
C6'0.087 (3)0.046 (2)0.067 (2)0.005 (2)0.030 (2)0.0002 (18)
C7'0.061 (2)0.049 (2)0.056 (2)0.0021 (17)0.0210 (16)0.0022 (17)
C8'0.065 (2)0.0426 (19)0.0529 (19)0.0038 (17)0.0232 (17)0.0021 (16)
C8A'0.055 (2)0.0423 (18)0.0552 (19)0.0084 (16)0.0198 (16)0.0032 (16)
C9'0.087 (3)0.057 (2)0.052 (2)0.016 (2)0.0341 (19)0.0072 (18)
C10'0.088 (3)0.058 (2)0.059 (2)0.011 (2)0.043 (2)0.0100 (19)
C11'0.157 (5)0.081 (3)0.092 (3)0.006 (3)0.086 (3)0.006 (3)
C12'0.091 (3)0.048 (2)0.064 (2)0.0030 (19)0.034 (2)0.0056 (17)
C13'0.081 (3)0.079 (3)0.068 (2)0.002 (2)0.001 (2)0.003 (2)
Geometric parameters (Å, º) top
O1—C71.223 (4)C2—H2A0.9800
O2—C101.193 (4)C3—H3A0.9700
O3—C101.316 (5)C3—H3B0.9700
C1—C8A1.509 (5)C4—H4A0.9700
C1—C21.538 (4)C4—H4B0.9700
C2—C31.516 (5)C5—H5A0.9700
C2—C91.549 (5)C5—H5B0.9700
C3—C41.517 (5)C6—H6A0.9700
C4—C4A1.531 (4)C6—H6B0.9700
C4A—C51.517 (5)C9—H9A0.9800
C4A—C8A1.521 (5)C11—H11A0.9600
C4A—C131.534 (5)C11—H11B0.9600
C5—C61.524 (5)C11—H11C0.9600
C6—C71.489 (5)C12—H12A0.9600
C7—C81.464 (5)C12—H12B0.9600
C8—C8A1.353 (5)C12—H12C0.9600
C8—C121.508 (5)C13—H13A0.9600
C9—C101.511 (5)C13—H13B0.9600
C9—C111.528 (4)C13—H13C0.9600
O1'—C7'1.215 (4)O3'—H3'0.82 (5)
O2'—C10'1.190 (5)C1'—H1'A0.9700
O3'—C10'1.320 (5)C1'—H1'B0.9700
C1'—C8A'1.506 (5)C2'—H2'A0.9800
C1'—C2'1.530 (5)C3'—H3'A0.9700
C2'—C3'1.526 (5)C3'—H3'B0.9700
C2'—C9'1.532 (5)C4'—H4'A0.9700
C3'—C4'1.515 (5)C4'—H4'B0.9700
C4'—C4A'1.534 (5)C5'—H5'A0.9700
C4A'—C8A'1.522 (4)C5'—H5'B0.9700
C4A'—C5'1.523 (5)C6'—H6'A0.9700
C4A'—C13'1.542 (5)C6'—H6'B0.9700
C5'—C6'1.503 (5)C9'—H9'A0.9800
C6'—C7'1.502 (5)C11'—H11D0.9600
C7'—C8'1.471 (5)C11'—H11E0.9600
C8'—C8A'1.342 (5)C11'—H11F0.9600
C8'—C12'1.513 (5)C12'—H12D0.9600
C9'—C10'1.506 (6)C12'—H12E0.9600
C9'—C11'1.524 (5)C12'—H12F0.9600
O3—H30.87 (4)C13'—H13D0.9600
C1—H1A0.9700C13'—H13E0.9600
C1—H1B0.9700C13'—H13F0.9600
C8A—C1—C2116.4 (3)C4A—C5—H5B109.2
C3—C2—C1110.0 (3)C6—C5—H5B109.2
C3—C2—C9112.3 (3)H5A—C5—H5B107.9
C1—C2—C9110.4 (3)C7—C6—H6A109.2
C2—C3—C4111.9 (3)C5—C6—H6A109.2
C3—C4—C4A114.4 (3)C7—C6—H6B109.2
C5—C4A—C8A109.9 (3)C5—C6—H6B109.2
C5—C4A—C4108.9 (3)H6A—C6—H6B107.9
C8A—C4A—C4108.6 (3)C10—C9—H9A107.1
C5—C4A—C13109.5 (3)C11—C9—H9A107.1
C8A—C4A—C13110.5 (3)C2—C9—H9A107.1
C4—C4A—C13109.4 (3)C9—C11—H11A109.5
C4A—C5—C6112.1 (3)C9—C11—H11B109.5
C7—C6—C5111.9 (3)H11A—C11—H11B109.5
O1—C7—C8121.0 (3)C9—C11—H11C109.5
O1—C7—C6120.2 (3)H11A—C11—H11C109.5
C8—C7—C6118.7 (3)H11B—C11—H11C109.5
C8A—C8—C7121.5 (3)C8—C12—H12A109.5
C8A—C8—C12123.1 (3)C8—C12—H12B109.5
C7—C8—C12115.3 (3)H12A—C12—H12B109.5
C8—C8A—C1121.5 (3)C8—C12—H12C109.5
C8—C8A—C4A122.3 (3)H12A—C12—H12C109.5
C1—C8A—C4A115.1 (3)H12B—C12—H12C109.5
C10—C9—C11110.6 (3)C4A—C13—H13A109.5
C10—C9—C2111.2 (3)C4A—C13—H13B109.5
C11—C9—C2113.4 (3)H13A—C13—H13B109.5
O2—C10—O3123.4 (4)C4A—C13—H13C109.5
O2—C10—C9124.5 (4)H13A—C13—H13C109.5
O3—C10—C9112.1 (3)H13B—C13—H13C109.5
C8A'—C1'—C2'115.0 (3)C10'—O3'—H3'111 (3)
C3'—C2'—C1'109.4 (3)C8A'—C1'—H1'A108.5
C3'—C2'—C9'113.2 (3)C2'—C1'—H1'A108.5
C1'—C2'—C9'111.4 (3)C8A'—C1'—H1'B108.5
C4'—C3'—C2'110.0 (3)C2'—C1'—H1'B108.5
C3'—C4'—C4A'115.4 (3)H1'A—C1'—H1'B107.5
C8A'—C4A'—C5'110.4 (3)C3'—C2'—H2'A107.5
C8A'—C4A'—C4'110.2 (3)C1'—C2'—H2'A107.5
C5'—C4A'—C4'108.3 (3)C9'—C2'—H2'A107.5
C8A'—C4A'—C13'108.1 (3)C4'—C3'—H3'A109.7
C5'—C4A'—C13'110.0 (3)C2'—C3'—H3'A109.7
C4'—C4A'—C13'109.9 (3)C4'—C3'—H3'B109.7
C6'—C5'—C4A'113.5 (3)C2'—C3'—H3'B109.7
C7'—C6'—C5'112.0 (3)H3'A—C3'—H3'B108.2
O1'—C7'—C8'120.4 (3)C3'—C4'—H4'A108.4
O1'—C7'—C6'121.3 (3)C4A'—C4'—H4'A108.4
C8'—C7'—C6'118.3 (3)C3'—C4'—H4'B108.4
C8A'—C8'—C7'121.6 (3)C4A'—C4'—H4'B108.4
C8A'—C8'—C12'123.9 (3)H4'A—C4'—H4'B107.5
C7'—C8'—C12'114.5 (3)C6'—C5'—H5'A108.9
C8'—C8A'—C1'122.1 (3)C4A'—C5'—H5'A108.9
C8'—C8A'—C4A'122.8 (3)C6'—C5'—H5'B108.9
C1'—C8A'—C4A'114.7 (3)C4A'—C5'—H5'B108.9
C10'—C9'—C11'109.0 (4)H5'A—C5'—H5'B107.7
C10'—C9'—C2'110.0 (3)C7'—C6'—H6'A109.2
C11'—C9'—C2'113.0 (3)C5'—C6'—H6'A109.2
O2'—C10'—O3'123.2 (4)C7'—C6'—H6'B109.2
O2'—C10'—C9'124.4 (4)C5'—C6'—H6'B109.2
O3'—C10'—C9'112.4 (4)H6'A—C6'—H6'B107.9
C10—O3—H3107 (3)C10'—C9'—H9'A108.2
C8A—C1—H1A108.2C11'—C9'—H9'A108.2
C2—C1—H1A108.2C2'—C9'—H9'A108.2
C8A—C1—H1B108.2C9'—C11'—H11D109.5
C2—C1—H1B108.2C9'—C11'—H11E109.5
H1A—C1—H1B107.4H11D—C11'—H11E109.5
C3—C2—H2A108.0C9'—C11'—H11F109.5
C1—C2—H2A108.0H11D—C11'—H11F109.5
C9—C2—H2A108.0H11E—C11'—H11F109.5
C2—C3—H3A109.2C8'—C12'—H12D109.5
C4—C3—H3A109.2C8'—C12'—H12E109.5
C2—C3—H3B109.2H12D—C12'—H12E109.5
C4—C3—H3B109.2C8'—C12'—H12F109.5
H3A—C3—H3B107.9H12D—C12'—H12F109.5
C3—C4—H4A108.6H12E—C12'—H12F109.5
C4A—C4—H4A108.6C4A'—C13'—H13D109.5
C3—C4—H4B108.6C4A'—C13'—H13E109.5
C4A—C4—H4B108.6H13D—C13'—H13E109.5
H4A—C4—H4B107.6C4A'—C13'—H13F109.5
C4A—C5—H5A109.2H13D—C13'—H13F109.5
C6—C5—H5A109.2H13E—C13'—H13F109.5
C8A—C1—C2—C346.7 (4)C8A'—C1'—C2'—C3'53.3 (4)
C8A—C1—C2—C9171.1 (3)C8A'—C1'—C2'—C9'179.2 (3)
C1—C2—C3—C451.1 (4)C1'—C2'—C3'—C4'55.7 (4)
C9—C2—C3—C4174.4 (3)C9'—C2'—C3'—C4'179.4 (3)
C2—C3—C4—C4A58.2 (4)C2'—C3'—C4'—C4A'57.1 (5)
C3—C4—C4A—C5173.7 (3)C3'—C4'—C4A'—C8A'50.1 (4)
C3—C4—C4A—C8A54.0 (4)C3'—C4'—C4A'—C5'170.9 (3)
C3—C4—C4A—C1366.7 (4)C3'—C4'—C4A'—C13'69.0 (4)
C8A—C4A—C5—C651.8 (4)C8A'—C4A'—C5'—C6'48.6 (4)
C4—C4A—C5—C6170.7 (3)C4'—C4A'—C5'—C6'169.3 (3)
C13—C4A—C5—C669.7 (4)C13'—C4A'—C5'—C6'70.6 (4)
C4A—C5—C6—C753.3 (4)C4A'—C5'—C6'—C7'52.0 (4)
C5—C6—C7—O1157.4 (4)C5'—C6'—C7'—O1'153.2 (4)
C5—C6—C7—C826.5 (5)C5'—C6'—C7'—C8'29.0 (5)
O1—C7—C8—C8A175.6 (4)O1'—C7'—C8'—C8A'178.2 (4)
C6—C7—C8—C8A0.4 (6)C6'—C7'—C8'—C8A'4.0 (5)
O1—C7—C8—C127.9 (6)O1'—C7'—C8'—C12'2.0 (5)
C6—C7—C8—C12176.0 (4)C6'—C7'—C8'—C12'175.8 (3)
C7—C8—C8A—C1166.3 (3)C7'—C8'—C8A'—C1'173.4 (3)
C12—C8—C8A—C117.5 (6)C12'—C8'—C8A'—C1'6.4 (5)
C7—C8—C8A—C4A0.9 (6)C7'—C8'—C8A'—C4A'1.5 (5)
C12—C8—C8A—C4A175.3 (4)C12'—C8'—C8A'—C4A'178.3 (3)
C2—C1—C8A—C8145.3 (3)C2'—C1'—C8A'—C8'138.9 (3)
C2—C1—C8A—C4A46.7 (4)C2'—C1'—C8A'—C4A'48.7 (4)
C5—C4A—C8A—C825.5 (5)C5'—C4A'—C8A'—C8'23.6 (5)
C4—C4A—C8A—C8144.6 (3)C4'—C4A'—C8A'—C8'143.2 (3)
C13—C4A—C8A—C895.4 (4)C13'—C4A'—C8A'—C8'96.7 (4)
C5—C4A—C8A—C1166.6 (3)C5'—C4A'—C8A'—C1'164.0 (3)
C4—C4A—C8A—C147.5 (4)C4'—C4A'—C8A'—C1'44.4 (4)
C13—C4A—C8A—C172.5 (4)C13'—C4A'—C8A'—C1'75.7 (4)
C3—C2—C9—C10179.8 (3)C3'—C2'—C9'—C10'178.3 (3)
C1—C2—C9—C1056.7 (4)C1'—C2'—C9'—C10'57.9 (4)
C3—C2—C9—C1154.9 (4)C3'—C2'—C9'—C11'56.3 (5)
C1—C2—C9—C11178.0 (3)C1'—C2'—C9'—C11'179.9 (3)
C11—C9—C10—O2129.2 (4)C11'—C9'—C10'—O2'69.0 (5)
C2—C9—C10—O2104.0 (4)C2'—C9'—C10'—O2'55.4 (5)
C11—C9—C10—O353.2 (4)C11'—C9'—C10'—O3'112.0 (4)
C2—C9—C10—O373.7 (4)C2'—C9'—C10'—O3'123.6 (4)

Experimental details

Crystal data
Chemical formulaC15H22O3
Mr250.33
Crystal system, space groupMonoclinic, P21
Temperature (K)296
a, b, c (Å)10.0225 (14), 14.862 (2), 10.0873 (14)
β (°) 110.758 (11)
V3)1405.0 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.44 × 0.30 × 0.22
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5441, 2579, 1977
Rint0.029
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.105, 1.03
No. of reflections2579
No. of parameters337
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.14, 0.10

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

Selected geometric parameters (Å, º) top
O2—C101.193 (4)O2'—C10'1.190 (5)
O3—C101.316 (5)O3'—C10'1.320 (5)
O2—C10—C9124.5 (4)O2'—C10'—C9'124.4 (4)
O3—C10—C9112.1 (3)O3'—C10'—C9'112.4 (4)
C1—C2—C9—C11178.0 (3)C1'—C2'—C9'—C11'179.9 (3)
C2—C9—C10—O373.7 (4)C2'—C9'—C10'—O3'123.6 (4)
 

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