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The two δ-keto carboxylic acids of the title, both C10H14O3, are epimeric at the site of carboxyl attachment. The endo (3α) epimer, (I), has its keto-acid ring in a boat conformation, with the tilt of the carboxyl group creating conformational chirality. The mol­ecules form hydrogen bonds by centrosymmetric pairing of carboxyl groups across the corners of the chosen cell [O...O = 2.671 (2) Å and O—H...O = 179 (2)°]. Two close intermolecular C—H...O contacts exist for the ketone. The exo (3β) epimer exists in the closed ring–chain tautomeric form as the lactol, 8-hydroxy-9-oxatri­cyclo­[5.3.1.03,8]­undecan-10-one, (II). The mol­ecules have conformational chirality, and the hydrogen-bonding scheme involves intermolecular hydroxyl-to-carbonyl chains of mol­ecules screw-related in b [O...O = 2.741 (2) Å and O—H...O = 177 (2)°].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103001495/fr1406sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103001495/fr1406Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103001495/fr1406IIsup3.hkl
Contains datablock II

CCDC references: 208033; 208034

Comment top

Keto carboxylic acids, with two hydrogen-bonding receptors and a single donor, constitute a class in which five solid-state hydrogen-bonding modes are known. Three of these engage the ketone function, while the remainder correspond to the common pairing and rare chain modes of simple acids. In our continuing study of factors governing the choice of hydrogen-bonding mode, we have examined the title compounds, (I) and (II), which belong to the category of δ-keto acids, one generally rich in hydrogen-bonding types. \sch

Fig. 1 shows the asymmetric unit for the 3-α or `endo' acid (I), the methyl ester of which was the kinetic but less thermodynamically stable product of our synthesis. Of the four chair-boat permutations available to (I), those having a boat conformation for the ring bearing the carboxyl avoid placing that group on an axial bond and are clearly favored. Thus, the conformation found in the crystal is also the one energetically favored in solution (McEuen et al., 1970), with one boat and one chair. Given that preference, the molecule has no significant conformational flexibility, and the only available rotation involves the bond to the carboxyl group. That group is tilted so that the C2—C3—C10—O2 torsional angle is −8.3 (2)°, producing a net conformational chirality in this otherwise inherently symmetric molecule.

Fig. 2 is a packing diagram showing that the hydrogen bonding in (I) is of the relatively common carboxyl-pairing type, with centrosymmetric dimers across the corners of the chosen cell. Although not seen in catemeric hydrogen bonding, complete or partial averaging of C—O bond lengths and C—C—O angles by disorder is frequent in carboxyl dimers (Leiserowitz, 1976), but is not significantly present in (I). Here, these lengths are 1.222 (2) and 1.320 (2) Å, with angles of 123.67 (18) and 113.94 (17)°. Our own survey of 56 keto acid structures which are not acid dimers gives average values of 1.20 (1) and 1.32 (2) Å, and 124.5 (14) and 112.7 (17)°, respectively, for these lengths and angles, in accord with the typical values of 1.21 and 1.31 Å, and 123 and 112°, cited for highly ordered dimeric carboxyls (Borthwick, 1980).

Within the 2.7 Å range we employ as our standard criterion (Steiner, 1997), two non-bonded intermolecular C—H···O packing interactions were found in (I), both involving the ketone (2.68 Å to atom H3A and 2.68 Å to atom H8A in two different centrosymmetrically related neighbors). Using compiled data for a large number of C—H···O contacts, Steiner & Desiraju (1998) have found 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.

Fig. 3 shows the asymmetric unit of the 3-β `exo' diastereomer, (II), obtained via base-catalyzed epimerization of the endo ester. This material is identical by melting point with that originally identified as the exo keto acid by Peters et al. (1974), but is found here to exist in the closed lactol form, (II). Based on NMR evidence, the existence of a ring-chain tautomerism for solutions of this compound was later recognized by van Oosterhout et al. (1978), but no structural assignment was made for the crystalline form of the compound. Note that the bicyclo[3.3.1] numbering of the exo keto acid is retained in the following discussion of (II), rather than the more complex tricyclo[5.3.1.03,8] alternative, which obscures the parentage of (II) and its relationship to (I).

Such ring-chain tautomerism is relatively common in β- and γ-carboxy ketones and carboxy aldehydes (Chadwick & Dunitz, 1979; Thompson et al., 1985; Dobson & Gerkin, 1996; Valente et al., 1998; Tsao et al., 2003). Although there appears to be some preference for γ- over δ-lactones (Soffer et al., 1950; Jones, 1963), examples of the latter are not lacking. In either case, the open and closed forms often lie so close energetically that small changes in structure or the medium can shift the equilibria appreciably (Valters & Flitsch, 1985), and for (II), the specific source of stability for the δ-lactol form is not obvious. With the carboxyl group in the exo position, both rings would appear to be free to adopt chair conformations with no very serious stereochemical disadvantage, as seen in the case of 9-oxobicyclo[3.3.1]nonane-1-carboxylic acid (Thompson et al., 1992). However, in general, incorporating significant rotational constraints and/or substitution on the chain atoms usually shifts equilibria toward the closed form (Valters & Flitsch, 1985), and both of these features are present in (II). The 13C NMR peaks (in C5D5N and CDCl3) for both forms of (II) were identified by van Oosterhout et al. (1978) and some data on the rates of equilibration were reported, but none on the position of the equilibrium involved. It seems probable that the isolation of (II) represents displacement of the solution equilibrium by selective precipitation.

Both the open and closed forms of (II) lack chiral centers and are inherently symmetric. However, while (II) is skeletally symmetrical, like (I) it adopts a chiral conformation arising principally from the only free rotation available, in this case that of the hydroxyl. It is well recognized that simple bicyclo[2.2.2]octane systems are not entirely rigid, and the nominally parallel ethylene bridges are often significantly skewed, presumably to relieve eclipsing strain (Deutsch, 1972; Blackstock et al., 1987; Zimmerman et al., 1992). In (II), this tendency is severely curtailed by the presence of the additional ring, which imparts extra rigidity to the bicyclo[2.2.2]octane portion of the molecule. As a result, the three torsional angles involving the [2.2.2] bridgeheads all lie very close to 0°; these are C9—C1—C2—C3 [−0.08 (16)°], C9—O3—C10—C3 [−1.13 (16)°] and C9—C5—C4—C3 [−1.43 (16)°].

Fig. 4 is a packing diagram showing the hydrogen-bonding scheme for (II). As is seen in other simple lactols, the hydrogen bonding is catemeric, proceeding in the bc plane from the hydroxyl of one molecule to the carbonyl of a neighbor, in this case one screw-related in b. A second chain, centrosymmetric to the first, runs counterdirectionally. No intermolecular C—H···O contacts were found within 2.7 Å.

The solid-state (KBr) IR spectrum of (I) displays CO peaks at 1719 and 1702 cm−1. In CHCl3 solution, these bands coalesce and appear at 1712 cm−1. For compound (II), the KBr spectrum displays sharp peaks at 3265 (O—H) and 1714 cm−1 (hydrogen-bonded CO). In CHCl3 solution, peaks appear for both unassociated and associated O—H (3576 and 3323 cm−1), as well as at 1748 cm−1 for the lactone CO, with a shoulder at 1730 cm−1.

Experimental top

Compound (I) was synthesized by the procedure of McEuen et al. (1970), as modified by Peters et al. (1974), and was recrystallized from methyl acetate/hexane to give crystals suitable for X-ray analysis (m.p. 404 K). The methyl ester of (I) was epimerized with sodium methoxide and saponified to give (II), which was sublimed and recrystallized from ethyl acetate (m.p. 422 K).

Refinement top

All H atoms of (I) and (II) were found in electron-density difference maps but C-bound H atoms were placed in calculated positions [0.97 Å for methylene H, 0.98 Å for methine H] and allowed to refine as riding models on their respective C atoms, with their displacement parameters fixed at 120% of those of their respective C atoms. The positional parameters of the O-bound H atoms were allowed to refine, but their displacement parameters were held at 0.08 Å2.

Computing details top

For both compounds, data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 in SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 in SHELXTL; molecular graphics: SHELXP97 in SHELXTL; software used to prepare material for publication: SHELXL97 in SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit of (I). Displacement ellipsoids are set at the 20% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A packing diagram for (I), with an extracellular molecule included to illustrate the centrosymmetric carboxyl pairing across the corners of the chosen cell. Displacement ellipsoids are set at the 20% probability level.
[Figure 3] Fig. 3. A view of the asymmetric unit of (II); the atom-numbering scheme follows that of the parent keto acid and (I). Displacement ellipsoids are set at the 20% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. A partial packing diagram for (II) with extracellular molecules, illustrating the hydroxyl-to-carbonyl hydrogen-bonding catemers among molecules screw-related in b. All C-bound H atoms have been removed for clarity. Displacement ellipsoids are set at the 20% probability level.
(I) 9-oxobicyclo[3.3.1]nonane-3α-carboxylic acid top
Crystal data top
C10H14O3Z = 2
Mr = 182.21F(000) = 196
Triclinic, P1Dx = 1.333 Mg m3
Hall symbol: -P 1Melting point: 404 K
a = 6.617 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.316 (1) ÅCell parameters from 23 reflections
c = 10.421 (2) Åθ = 3.3–9.9°
α = 71.47 (1)°µ = 0.10 mm1
β = 73.44 (2)°T = 296 K
γ = 77.29 (1)°Pentagonal rod, colorless
V = 453.81 (13) Å30.50 × 0.22 × 0.08 mm
Data collection top
Siemens P4
diffractometer
1141 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.020
Graphite monochromatorθmax = 25.0°, θmin = 2.1°
2θ/θ scansh = 17
Absorption correction: analytical
(SHELXTL; Sheldrick, 1997)
k = 88
Tmin = 0.940, Tmax = 0.980l = 1212
2040 measured reflections3 standard reflections every 97 reflections
1588 independent reflections intensity decay: variation < 1.1%
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) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.048P)2 + 0.0479P]
where P = (Fo2 + 2Fc2)/3
1588 reflections(Δ/σ)max < 0.001
121 parametersΔρmax = 0.13 e Å3
0 restraintsΔρmin = 0.17 e Å3
Crystal data top
C10H14O3γ = 77.29 (1)°
Mr = 182.21V = 453.81 (13) Å3
Triclinic, P1Z = 2
a = 6.617 (1) ÅMo Kα radiation
b = 7.316 (1) ŵ = 0.10 mm1
c = 10.421 (2) ÅT = 296 K
α = 71.47 (1)°0.50 × 0.22 × 0.08 mm
β = 73.44 (2)°
Data collection top
Siemens P4
diffractometer
1141 reflections with I > 2σ(I)
Absorption correction: analytical
(SHELXTL; Sheldrick, 1997)
Rint = 0.020
Tmin = 0.940, Tmax = 0.9803 standard reflections every 97 reflections
2040 measured reflections intensity decay: variation < 1.1%
1588 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.13 e Å3
1588 reflectionsΔρmin = 0.17 e Å3
121 parameters
Special details top

Experimental. 'crystal mounted on glass fiber using cyanoacrylate cement'

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R- factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.8706 (2)0.8265 (2)0.46312 (14)0.0561 (4)
O20.8195 (2)0.10089 (19)0.90893 (15)0.0554 (4)
O31.0978 (2)0.2324 (2)0.90087 (18)0.0607 (4)
C10.6182 (3)0.6068 (3)0.59638 (19)0.0400 (5)
C20.6791 (3)0.4122 (3)0.7012 (2)0.0431 (5)
C30.8636 (3)0.4217 (3)0.75880 (19)0.0394 (5)
C40.8174 (3)0.5993 (3)0.81780 (19)0.0415 (5)
C50.7591 (3)0.7915 (3)0.70982 (19)0.0391 (5)
C60.5307 (3)0.8922 (3)0.7583 (2)0.0457 (5)
C70.3613 (3)0.7696 (3)0.7749 (2)0.0470 (5)
C80.3889 (3)0.7034 (3)0.6455 (2)0.0455 (5)
C90.7651 (3)0.7493 (3)0.57578 (19)0.0386 (4)
C100.9228 (3)0.2367 (3)0.8624 (2)0.0423 (5)
H31.125 (4)0.115 (4)0.967 (3)0.080*
H10.63180.58240.50690.048*
H2A0.55640.38170.77750.052*
H2B0.71920.30860.65550.052*
H3A0.98780.44110.68010.047*
H4A0.94210.60810.84570.050*
H4B0.70080.58110.89980.050*
H50.86140.88040.69180.047*
H6A0.51750.91710.84650.055*
H6B0.50641.01660.69090.055*
H7A0.36890.65610.85390.056*
H7B0.22150.84520.79400.056*
H8A0.35300.81500.57120.055*
H8B0.29100.61150.66550.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0579 (9)0.0587 (9)0.0442 (8)0.0183 (7)0.0080 (7)0.0145 (7)
O20.0549 (9)0.0459 (8)0.0662 (10)0.0143 (7)0.0196 (8)0.0065 (7)
O30.0521 (10)0.0502 (9)0.0822 (11)0.0088 (7)0.0307 (8)0.0071 (8)
C10.0418 (11)0.0447 (10)0.0387 (10)0.0071 (8)0.0074 (8)0.0196 (8)
C20.0428 (11)0.0381 (10)0.0538 (11)0.0075 (9)0.0108 (9)0.0191 (9)
C30.0359 (11)0.0382 (10)0.0449 (11)0.0056 (8)0.0044 (8)0.0165 (9)
C40.0405 (11)0.0449 (11)0.0440 (11)0.0071 (9)0.0081 (9)0.0198 (9)
C50.0402 (11)0.0374 (10)0.0435 (10)0.0114 (8)0.0049 (8)0.0166 (8)
C60.0502 (12)0.0418 (11)0.0477 (11)0.0028 (9)0.0072 (9)0.0220 (9)
C70.0374 (11)0.0503 (12)0.0532 (12)0.0019 (9)0.0035 (9)0.0232 (10)
C80.0414 (11)0.0457 (11)0.0526 (12)0.0077 (9)0.0112 (9)0.0163 (9)
C90.0358 (10)0.0360 (10)0.0406 (11)0.0031 (8)0.0028 (9)0.0126 (8)
C100.0362 (11)0.0427 (11)0.0497 (11)0.0016 (9)0.0066 (9)0.0206 (9)
Geometric parameters (Å, º) top
O1—C91.212 (2)O3—H30.93 (3)
O2—C101.222 (2)C1—H10.9800
O3—C101.320 (2)C2—H2A0.9700
C1—C91.504 (2)C2—H2B0.9700
C1—C81.542 (3)C3—H3A0.9800
C1—C21.547 (3)C4—H4A0.9700
C2—C31.528 (3)C4—H4B0.9700
C3—C101.493 (3)C5—H50.9800
C3—C41.545 (2)C6—H6A0.9700
C4—C51.548 (3)C6—H6B0.9700
C5—C91.511 (2)C7—H7A0.9700
C5—C61.547 (3)C7—H7B0.9700
C6—C71.524 (3)C8—H8A0.9700
C7—C81.523 (3)C8—H8B0.9700
C9—C1—C8107.26 (14)H2A—C2—H2B107.9
C9—C1—C2110.15 (15)C10—C3—H3A106.9
C8—C1—C2112.69 (16)C2—C3—H3A106.9
C3—C2—C1111.72 (15)C4—C3—H3A106.9
C10—C3—C2112.79 (15)C3—C4—H4A109.3
C10—C3—C4111.75 (15)C5—C4—H4A109.3
C2—C3—C4111.18 (15)C3—C4—H4B109.3
C3—C4—C5111.82 (15)C5—C4—H4B109.3
C9—C5—C6106.21 (15)H4A—C4—H4B107.9
C9—C5—C4109.70 (14)C9—C5—H5109.5
C6—C5—C4112.40 (15)C6—C5—H5109.5
C7—C6—C5112.37 (14)C4—C5—H5109.5
C8—C7—C6112.17 (16)C7—C6—H6A109.1
C7—C8—C1112.31 (16)C5—C6—H6A109.1
O1—C9—C1123.43 (17)C7—C6—H6B109.1
O1—C9—C5124.00 (17)C5—C6—H6B109.1
C1—C9—C5112.52 (15)H6A—C6—H6B107.9
O2—C10—O3122.38 (19)C8—C7—H7A109.2
O2—C10—C3123.67 (18)C6—C7—H7A109.2
O3—C10—C3113.94 (17)C8—C7—H7B109.2
C10—O3—H3110.4 (16)C6—C7—H7B109.2
C9—C1—H1108.9H7A—C7—H7B107.9
C8—C1—H1108.9C7—C8—H8A109.1
C2—C1—H1108.9C1—C8—H8A109.1
C3—C2—H2A109.3C7—C8—H8B109.1
C1—C2—H2A109.3C1—C8—H8B109.1
C3—C2—H2B109.3H8A—C8—H8B107.9
C1—C2—H2B109.3
C9—C1—C2—C32.4 (2)C2—C1—C8—C766.2 (2)
C8—C1—C2—C3117.33 (16)C8—C1—C9—O1113.6 (2)
C1—C2—C3—C10178.88 (14)C2—C1—C9—O1123.4 (2)
C1—C2—C3—C452.4 (2)C8—C1—C9—C563.92 (19)
C10—C3—C4—C5179.21 (15)C2—C1—C9—C559.06 (19)
C2—C3—C4—C553.8 (2)C6—C5—C9—O1113.3 (2)
C3—C4—C5—C90.2 (2)C4—C5—C9—O1125.0 (2)
C3—C4—C5—C6117.70 (17)C6—C5—C9—C164.21 (19)
C9—C5—C6—C756.4 (2)C4—C5—C9—C157.5 (2)
C4—C5—C6—C763.6 (2)C2—C3—C10—O28.3 (2)
C5—C6—C7—C851.8 (2)C4—C3—C10—O2117.8 (2)
C6—C7—C8—C150.9 (2)C2—C3—C10—O3172.09 (15)
C9—C1—C8—C755.2 (2)C4—C3—C10—O361.8 (2)
(II) 8-hydroxy-9-oxatricyclo[5.3.1.03,8]undecan-10-one' top
Crystal data top
C10H14O3F(000) = 392
Mr = 182.21Dx = 1.404 Mg m3
Monoclinic, P21/cMelting point: 422 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 7.331 (4) ÅCell parameters from 30 reflections
b = 9.288 (7) Åθ = 2.8–11.9°
c = 12.669 (7) ŵ = 0.10 mm1
β = 92.64 (2)°T = 296 K
V = 861.7 (9) Å3Parallelepiped, colorless
Z = 40.44 × 0.28 × 0.24 mm
Data collection top
Siemens P4
diffractometer
Rint = 0.025
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.7°
Graphite monochromatorh = 80
2θ/θ scansk = 1111
2946 measured reflectionsl = 1415
1512 independent reflections3 standard reflections every 97 reflections
1239 reflections with I > 2σ(I) intensity decay: variation < 1.0%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.084 w = 1/[σ2(Fo2) + (0.0326P)2 + 0.1747P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
1512 reflectionsΔρmax = 0.16 e Å3
122 parametersΔρmin = 0.15 e Å3
0 restraintsExtinction correction: SHELXL97 in SHELXTL (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.044 (3)
Crystal data top
C10H14O3V = 861.7 (9) Å3
Mr = 182.21Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.331 (4) ŵ = 0.10 mm1
b = 9.288 (7) ÅT = 296 K
c = 12.669 (7) Å0.44 × 0.28 × 0.24 mm
β = 92.64 (2)°
Data collection top
Siemens P4
diffractometer
Rint = 0.025
2946 measured reflections3 standard reflections every 97 reflections
1512 independent reflections intensity decay: variation < 1.0%
1239 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.084H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.16 e Å3
1512 reflectionsΔρmin = 0.15 e Å3
122 parameters
Special details top

Experimental. crystal mounted on glass fiber using cyanoacrylate cement

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R- factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.35127 (14)0.06409 (11)0.71666 (8)0.0429 (3)
O20.13911 (15)0.32101 (12)0.79250 (8)0.0480 (3)
O30.10111 (13)0.19328 (10)0.75595 (7)0.0364 (3)
C10.14628 (18)0.14322 (15)0.57177 (10)0.0342 (3)
C20.0128 (2)0.26741 (16)0.54614 (11)0.0402 (4)
C30.0237 (2)0.37789 (16)0.63548 (11)0.0400 (4)
C40.2183 (2)0.43584 (16)0.64863 (13)0.0461 (4)
C50.3523 (2)0.31150 (15)0.67261 (12)0.0392 (4)
C60.4967 (2)0.29299 (18)0.59060 (13)0.0475 (4)
C70.4154 (2)0.25132 (18)0.48297 (13)0.0495 (4)
C80.2886 (2)0.12282 (17)0.48902 (12)0.0437 (4)
C90.24365 (18)0.17374 (14)0.67771 (10)0.0325 (3)
C100.0165 (2)0.29918 (14)0.73416 (11)0.0359 (3)
H10.282 (3)0.020 (2)0.7123 (17)0.080*
H1A0.07640.05380.57730.041*
H2B0.04350.31290.48040.048*
H2A0.11070.23020.53770.048*
H3A0.06380.45630.62200.048*
H4B0.22590.50510.70600.055*
H4A0.25070.48450.58440.055*
H5A0.41400.32840.74180.047*
H6B0.56350.38250.58450.057*
H6A0.58270.21940.61470.057*
H7B0.51310.22840.43670.059*
H7A0.34810.33250.45270.059*
H8B0.36010.03740.50610.052*
H8A0.22700.10790.42050.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0378 (6)0.0403 (6)0.0501 (6)0.0054 (5)0.0051 (5)0.0091 (5)
O20.0510 (6)0.0466 (7)0.0478 (6)0.0049 (5)0.0156 (5)0.0033 (5)
O30.0402 (6)0.0362 (6)0.0331 (5)0.0014 (4)0.0043 (4)0.0043 (4)
C10.0324 (7)0.0335 (7)0.0365 (8)0.0013 (6)0.0006 (6)0.0024 (6)
C20.0369 (8)0.0487 (9)0.0349 (7)0.0061 (7)0.0001 (6)0.0024 (6)
C30.0450 (8)0.0331 (8)0.0421 (8)0.0095 (6)0.0040 (6)0.0046 (6)
C40.0572 (10)0.0333 (8)0.0484 (9)0.0048 (7)0.0091 (7)0.0007 (7)
C50.0394 (8)0.0398 (8)0.0378 (8)0.0082 (6)0.0031 (6)0.0014 (6)
C60.0369 (8)0.0519 (9)0.0538 (9)0.0098 (7)0.0057 (7)0.0034 (8)
C70.0435 (9)0.0618 (11)0.0441 (9)0.0002 (8)0.0117 (7)0.0022 (8)
C80.0407 (8)0.0521 (9)0.0383 (8)0.0064 (7)0.0026 (6)0.0080 (7)
C90.0316 (7)0.0339 (7)0.0320 (7)0.0023 (6)0.0009 (5)0.0025 (6)
C100.0396 (8)0.0313 (7)0.0369 (8)0.0000 (6)0.0016 (6)0.0046 (6)
Geometric parameters (Å, º) top
O1—C91.3665 (17)O1—H10.93 (2)
O2—C101.2067 (18)C1—H1A0.9800
O3—C101.3287 (18)C2—H2B0.9700
O3—C91.4842 (17)C2—H2A0.9700
C1—C91.518 (2)C3—H3A0.9800
C1—C81.524 (2)C4—H4B0.9700
C1—C21.538 (2)C4—H4A0.9700
C2—C31.527 (2)C5—H5A0.9800
C3—C101.489 (2)C6—H6B0.9700
C3—C41.527 (2)C6—H6A0.9700
C4—C51.537 (2)C7—H7B0.9700
C5—C91.510 (2)C7—H7A0.9700
C5—C61.527 (2)C8—H8B0.9700
C6—C71.513 (2)C8—H8A0.9700
C7—C81.517 (2)
C10—O3—C9114.96 (10)C3—C2—H2A109.7
C9—C1—C8108.82 (12)C1—C2—H2A109.7
C9—C1—C2108.39 (11)H2B—C2—H2A108.2
C8—C1—C2113.39 (12)C10—C3—H3A111.0
C3—C2—C1109.67 (12)C4—C3—H3A111.0
C10—C3—C4107.55 (13)C2—C3—H3A111.0
C10—C3—C2106.66 (13)C3—C4—H4B109.7
C4—C3—C2109.54 (12)C5—C4—H4B109.7
C3—C4—C5110.00 (12)C3—C4—H4A109.7
C9—C5—C6108.50 (12)C5—C4—H4A109.7
C9—C5—C4108.15 (12)H4B—C4—H4A108.2
C6—C5—C4114.01 (13)C9—C5—H5A108.7
C7—C6—C5112.67 (13)C6—C5—H5A108.7
C6—C7—C8111.88 (13)C4—C5—H5A108.7
C7—C8—C1112.17 (13)C7—C6—H6B109.1
O1—C9—O3105.22 (10)C5—C6—H6B109.1
O1—C9—C5110.49 (12)C7—C6—H6A109.1
O3—C9—C5108.30 (11)C5—C6—H6A109.1
O1—C9—C1114.86 (12)H6B—C6—H6A107.8
O3—C9—C1107.25 (11)C6—C7—H7B109.2
C5—C9—C1110.36 (11)C8—C7—H7B109.2
O2—C10—O3119.45 (13)C6—C7—H7A109.2
O2—C10—C3127.84 (13)C8—C7—H7A109.2
O3—C10—C3112.71 (12)H7B—C7—H7A107.9
C9—O1—H1107.6 (13)C7—C8—H8B109.2
C9—C1—H1A108.7C1—C8—H8B109.2
C8—C1—H1A108.7C7—C8—H8A109.2
C2—C1—H1A108.7C1—C8—H8A109.2
C3—C2—H2B109.7H8B—C8—H8A107.9
C1—C2—H2B109.7
C9—C1—C2—C30.08 (16)C4—C5—C9—O1169.50 (11)
C8—C1—C2—C3121.03 (14)C6—C5—C9—O3178.88 (11)
C1—C2—C3—C1056.86 (16)C4—C5—C9—O354.74 (14)
C1—C2—C3—C459.26 (15)C6—C5—C9—C161.76 (15)
C10—C3—C4—C556.97 (15)C4—C5—C9—C162.38 (14)
C2—C3—C4—C558.58 (16)C8—C1—C9—O163.60 (15)
C3—C4—C5—C91.43 (16)C2—C1—C9—O1172.67 (11)
C3—C4—C5—C6119.34 (14)C8—C1—C9—O3179.86 (11)
C9—C5—C6—C756.18 (17)C2—C1—C9—O356.13 (14)
C4—C5—C6—C764.40 (18)C8—C1—C9—C562.09 (15)
C5—C6—C7—C851.31 (18)C2—C1—C9—C561.64 (15)
C6—C7—C8—C151.18 (18)C9—O3—C10—O2178.61 (12)
C9—C1—C8—C756.13 (16)C9—O3—C10—C31.13 (16)
C2—C1—C8—C764.57 (17)C4—C3—C10—O2122.77 (16)
C10—O3—C9—O1178.20 (10)C2—C3—C10—O2119.79 (16)
C10—O3—C9—C560.03 (14)C4—C3—C10—O357.51 (15)
C10—O3—C9—C159.08 (14)C2—C3—C10—O359.93 (15)
C6—C5—C9—O166.36 (15)

Experimental details

(I)(II)
Crystal data
Chemical formulaC10H14O3C10H14O3
Mr182.21182.21
Crystal system, space groupTriclinic, P1Monoclinic, P21/c
Temperature (K)296296
a, b, c (Å)6.617 (1), 7.316 (1), 10.421 (2)7.331 (4), 9.288 (7), 12.669 (7)
α, β, γ (°)71.47 (1), 73.44 (2), 77.29 (1)90, 92.64 (2), 90
V3)453.81 (13)861.7 (9)
Z24
Radiation typeMo KαMo Kα
µ (mm1)0.100.10
Crystal size (mm)0.50 × 0.22 × 0.080.44 × 0.28 × 0.24
Data collection
DiffractometerSiemens P4
diffractometer
Siemens P4
diffractometer
Absorption correctionAnalytical
(SHELXTL; Sheldrick, 1997)
Tmin, Tmax0.940, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
2040, 1588, 1141 2946, 1512, 1239
Rint0.0200.025
(sin θ/λ)max1)0.5940.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.108, 1.04 0.033, 0.084, 1.03
No. of reflections15881512
No. of parameters121122
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.13, 0.170.16, 0.15

Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 in SHELXTL (Sheldrick, 1997), SHELXL97 in SHELXTL, SHELXP97 in SHELXTL.

Selected geometric parameters (Å, º) for (I) top
O2—C101.222 (2)O3—C101.320 (2)
O2—C10—C3123.67 (18)O3—C10—C3113.94 (17)
 

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