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The crystal structure of (±)-4-oxo-1,2,3,4-tetra­hydro­naph­thalene-2-carboxylic acid (C11H10O3) involves projection of the carboxyl group nearly orthogonal to the aromatic plane and hydrogen bonding of the acid groups by centrosymmetric pairing across the a edge and the center of the chosen cell [O...O = 2.705 (2) Å]. Intermolecular C—H...O=C close contacts to translationally related mol­ecules are found for both the ketone (2.55 Å) and the acid (2.67 Å). In (±)-1-oxo-1,2,3,4-tetra­hydro­naph­thalene-2-acetic acid (C12H12O3), the aggregation involves centrosymmetric carboxyl dimers mutually hydrogen bonded across the bc face and the a edge of the chosen cell [O...O = 2.674 (2) Å]. A 2.60 Å close C—H...O=C contact is found to the carboxyl group of centrosymmetrically related mol­ecule.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100020783/fr1312sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100020783/fr1312Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100020783/fr1312IIsup3.hkl
Contains datablock II

CCDC references: 162586; 162587

Comment top

Beyond the dimerization that dominates the hydrogen bonding in functionally unadorned carboxylic acids lies a range of alternative hydrogen-bonding modes that expands as other functional groups are added. Our continuing study of the crystal structures of keto acids explores the molecular characteristics that control their five known hydrogen-bonding modes (Lalancette, Thompson & Brunskill, 1999). Two of these, including carboxyl dimerization, lack ketone involvement, but acid-to-ketone catemers constitute a sizable minority of cases, while intramolecular hydrogen bonds and acid-to-ketone dimers are rarely observed. In addition, more than a dozen hydrates are known, having more complex hydrogen-bonding patterns.

We report here the structures and hydrogen-bonding behavior of the two tetralone acids of the title. The category of γ-keto acids is especially rich in hydrogen-bonding types, embracing internal hydrogen bonds and catemers of the helical, translational and glide types, as well as dimers and hydrated patterns. The two compounds presented here are part of a series of indanone and tetralone acids we have examined, in which the indanone species have been found to be predominantly catemers (Lalancette et al., 1997; Lalancette, Brunskill & Thompson, 1999; Thompson, Brunskill & Lalancette, 1998; Thompson, Lalancette & Brunskill, 1998).

Fig. 1 shows the asymmetric unit of (±)-1-tetralone-3-carboxylic acid [(±)-4-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid, C11H10O3, (I)] with its numbering. The ketone ring adopts a conformation resembling a folded envelope, in which the dihedral angle for C1—C2—C3 versus the tetralone ring system excluding C2 is 49.92 (14)°, placing C2 above the average aromatic plane by 0.703 (3) Å, while C3 lies 0.059 (3) Å above it. This allows the ketone to lie nearly coplanar with the aromatic ring [torsion angle O1—C4—C4A—C5 = -3.4 (3)°], while the carboxyl group is positioned pseudo-axially and turned so that it is nearly coplanar with the C2—C3 bond, with its carbonyl toward the ketone. Torsion angle O2—C9—C2—C3 is -1.7 (3)° and the vector angle for C2—C9 versus the tetralone ring system without C2 is 80.22 (8)°. The ketone–carboxyl dihedral angle (C3/C4/C4A/O1 versus C9/O2/O3) is 82.3 (2)°.

This angular carboxyl conformation seems surprising, but its resemblance to the usual axial arrangements is both superficial and deceptive. Even apart from the flattening of the ketone ring, the H atoms responsible for unfavorable 1,3-diaxial interactions in cyclohexane systems are absent in (I). The gauche arrangements created along the C1—C2 and C2—C3 bonds by the pseudo-axial carboxyl are C9—C2—C1—C8A and C9—C2—C3—C4, but the terminal atoms, C9, C8A and C4, are all trigonal. These atoms therefore lack much of the three-dimensional character that creates the steric strain in alkylcyclohexanes, a situation also seen with halo- and cyano-substituted cyclohexanes (Hirsch, 1967). The result is that the pseudo-axial and pseudo-equatorial conformations for (I) are energetically closer than in systems fully populated by tetrahedral C atoms. Although semi-empirical molecular (AM1) modeling (Wavefunction, 1995; Dewar et al., 1985) indicated the pseudo-equatorial conformation to be slightly more stable, any such advantage is obviously overbalanced by other forces in the crystal.

The disorder commonly detected in carboxyl dimers as an averaging of C—O distances and C—C—O angles (Leiserowitz, 1976) is not seen in (I), where these values are 1.214 (3)/1.313 (3) Å and 123.3 (2)/114.3 (2)°, respectively. Values cited as typical for highly ordered dimeric carboxyls are 1.21/1.31 Å and 123/112°, respectively (Borthwick, 1980).

Fig. 2 shows the packing arrangement for (I), involving centrosymmetric dimers centered on the a edge of the chosen cell and at 1/2, 1/2, 1/2 [O···O = 2.705 (2) Å and O—H···O = 173 (3)°]. Translationally related molecules stack with an interplanar distance of 3.48 Å, but the aromatic portions do not stack directly together, and the overlap between stacked aromatic and ketone rings involves only about half of each ring. Close C—H···OC contacts are found to separate translational neighbors between the ketone and H7 (2.55 Å) and between the acid and H1B (2.67 Å). These distances lie within the 2.7 Å range we often employ for non-bonded H···O packing interactions (Steiner, 1997). 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.

Fig. 3 shows the asymmetric unit for (±)-1-oxo-1,2,3,4-tetrahydronaphthalene-2-acetic acid, (II), with its numbering. The flexible ketone ring adopts a significantly more twisted conformation than in (I), placing C2 0.358 (3) Å above the average aromatic plane, while C3 lies 0.440 (3) Å below it. The ketone is significantly less coplanar with the aromatic ring than in the case of (I) [torsion angle O1—C1—C8A—C8 = -14.3 (3)°]. Free rotation is possible about only two bonds, and the conformational arrangement at C2—C9 is staggered, with C9 occupying a pseudo-equatorial bond so that torsion angle C9—C2—C3—C4 is 171.3 (2)°. Bond C9—C10 is rotated so that the O2—C10—C9—C2 torsion angle is 23.4 (3)°, placing the two carboxyl O atoms at similar distances from the ketone O atom [O1···O2 = 3.173 (2) Å and O1···O3 = 3.670 (2) Å]. The ketone–carboxyl dihedral angle (C2/C1/C8A/O1 versus C10/O2/O3) is 79.1 (1)°. No carboxyl disorder was detected in (II), where the C—O distances are 1.216 (2)/1.311 (2) Å and the C—C—O angles 123.7 (2)/114.1 (2)°.

Fig. 4 shows the packing arrangement, involving centrosymmetric dimers centered on the bc face and the a edge of the chosen cell [O···O = 2.674 (2) Å and O—H···O = 176°]. Centrosymmetrically related molecules stack with their aromatic rings significantly overlapped, at an interplanar distance of 3.65 Å, and a 2.60 Å close C—H···OC contact is found between the acid and H6 in a centrosymmetrically related neighbor (to which it is not hydrogen bonded).

Compound (I) in KBr has a single IR peak at 1691 cm-1 for both CO groups. In CHCl3 solution, where dimers are known to predominate, the presence of two peaks, at 1687 and 1713 cm-1, suggests the presence in solution of either a different conformation or more than one. The KBr spectrum of (II) has discrete CO absorptions at 1692 (ketone) and 1704 cm-1 (acid). In CHCl3 solution, only slight shifts occur, and these peaks appear at 1683 and 1712 cm-1, with a typical carboxyl-dilution shoulder ca 1740 cm-1.

Related literature top

For related literature, see: Bachman & Johnson (1949); Borthwick (1980); Dewar et al. (1985); Hirsch (1967); Horning & Walker (1952); Lalancette et al. (1997); Lalancette, Brunskill & Thompson (1999); Lalancette, Thompson & Brunskill (1999); Leiserowitz (1976); Steiner (1997); Steiner & Desiraju (1998); Thompson, Brunskill & Lalancette (1998); Thompson, Lalancette & Brunskill (1998); Wavefunction (1995).

Experimental top

Compound (I) was prepared from the Stobbe-condensation product of benzaldehyde with diethyl succinate by sequential saponification, hydrogenation (Pd/C) and acid-catalyzed cyclization (Horning & Walker, 1952). Crystals of (I) (m.p. 420 K) were obtained from ethyl acetate/cyclohexane. For compound (II), 2-carbomethoxy-1-tetralone was alkylated with ethyl bromoacetate and the product was hydrolyzed and decarboxylated under acidic conditions, as described by Bachman & Johnson (1949). After sublimation of the crude product, crystals of (II) (m.p. 383 K) were obtained from diethyl ether.

Refinement top

For both (I) and (II), all H atoms were found in electron-density difference maps but were placed in calculated positions and allowed to refine as riding models, with C—H distances of 0.97 Å for CH2, 0.98 Å for methine and 0.93 Å for aromatic C atoms. All Uiso values for H atoms were refined. The carboxyl H atoms was also found in difference maps, but their positional and isotropic displacement parameters were allowed to fully refine.

Computing details top

For both compounds, 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: SHELXL97; software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), with the atomic numbering. Displacement ellipsoids are drawn at the 20% probability level.
[Figure 2] Fig. 2. A partial packing diagram for (I), with extracellular molecules, showing acid dimers centered on the a edge and at 1/2, 1/2, 1/2. Close contacts found between O1 and H7 (2.55 Å) and between O2 and H1B (2.67 Å) of separate translationally related molecules are indicated by dotted lines. Displacement ellipsoids are drawn at the 20% probability level and carbon-bound H atoms have been removed for clarity.
[Figure 3] Fig. 3. The asymmetric unit of (II), with the atomic numbering. Displacement ellipsoids are drawn at the 20% probability level.
[Figure 4] Fig. 4. A partial packing diagram for (II), with extracellular molecules, showing acid dimers centered on the a edge and the bc face. A reciprocal close contact found between the acid carbonyl and the H6 atom in a centrosymmetrically related neighbor is indicated by dotted lines. Displacement ellipsoids are set at the 20% probability level and carbon-bound H atoms have been removed for clarity.
(I) (±)-4-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid top
Crystal data top
C11H10O3Dx = 1.416 Mg m3
Mr = 190.19Melting point: 420 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 6.2645 (7) ÅCell parameters from 52 reflections
b = 5.4440 (12) Åθ = 4.5–20.2°
c = 26.170 (3) ŵ = 0.10 mm1
β = 91.339 (11)°T = 293 K
V = 892.2 (2) Å3Trapezoid, colourless
Z = 40.56 × 0.52 × 0.10 mm
F(000) = 400
Data collection top
Siemens P4
diffractometer
1118 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.036
Graphite monochromatorθmax = 25.0°, θmin = 3.1°
2θ/θ scansh = 77
Absorption correction: numerical
(XPREP; Sheldrick, 1997)
k = 06
Tmin = 0.952, Tmax = 0.990l = 030
2499 measured reflections3 standard reflections every 97 reflections
1582 independent reflections intensity decay: variation < 0.7%
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)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.106 w = 1/[σ2(Fo2) + (0.0365P)2 + 0.237P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.02
1582 reflectionsΔρmax = 0.16 e Å3
141 parametersΔρmin = 0.12 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.007 (2)
Crystal data top
C11H10O3V = 892.2 (2) Å3
Mr = 190.19Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.2645 (7) ŵ = 0.10 mm1
b = 5.4440 (12) ÅT = 293 K
c = 26.170 (3) Å0.56 × 0.52 × 0.10 mm
β = 91.339 (11)°
Data collection top
Siemens P4
diffractometer
1118 reflections with I > 2σ(I)
Absorption correction: numerical
(XPREP; Sheldrick, 1997)
Rint = 0.036
Tmin = 0.952, Tmax = 0.9903 standard reflections every 97 reflections
2499 measured reflections intensity decay: variation < 0.7%
1582 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.16 e Å3
1582 reflectionsΔρmin = 0.12 e Å3
141 parameters
Special details top

Experimental. crystal mounted on glass fiber using epoxy resin

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
O10.5737 (3)0.0132 (3)0.32935 (6)0.0593 (5)
O20.5317 (2)0.2851 (3)0.45790 (6)0.0520 (5)
O30.2324 (3)0.3497 (3)0.49923 (6)0.0578 (5)
C10.0254 (3)0.1111 (4)0.41247 (8)0.0395 (5)
C20.2319 (3)0.0229 (4)0.43933 (8)0.0381 (5)
C30.3735 (3)0.1033 (4)0.40087 (8)0.0412 (5)
C40.4159 (3)0.0512 (4)0.35437 (8)0.0379 (5)
C4A0.2603 (3)0.2459 (4)0.34021 (7)0.0325 (5)
C50.2993 (4)0.3989 (4)0.29891 (8)0.0424 (5)
C60.1558 (4)0.5779 (4)0.28460 (8)0.0473 (6)
C70.0296 (4)0.6070 (4)0.31142 (8)0.0479 (6)
C8A0.0723 (3)0.2750 (4)0.36776 (7)0.0319 (5)
C80.0702 (3)0.4573 (4)0.35246 (8)0.0407 (5)
C90.3473 (3)0.2316 (4)0.46586 (7)0.0377 (5)
H30.313 (5)0.483 (5)0.5117 (11)0.086 (10)*
H1A0.05630.03000.40060.059 (7)*
H1B0.06040.20030.43670.042 (6)*
H20.19360.09820.46530.045 (6)*
H3A0.50870.14450.41750.049 (6)*
H3B0.30610.25550.39000.046 (6)*
H50.42410.37950.28080.048 (6)*
H60.18340.67930.25690.062 (7)*
H70.12730.72790.30180.057 (7)*
H80.19560.47880.37030.049 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0442 (9)0.0674 (12)0.0670 (11)0.0143 (9)0.0161 (8)0.0044 (9)
O20.0411 (10)0.0612 (11)0.0538 (9)0.0011 (8)0.0044 (7)0.0221 (9)
O30.0502 (10)0.0656 (12)0.0580 (11)0.0011 (10)0.0104 (8)0.0236 (10)
C10.0335 (11)0.0454 (13)0.0399 (11)0.0025 (11)0.0034 (9)0.0002 (10)
C20.0430 (12)0.0364 (11)0.0349 (10)0.0000 (10)0.0000 (9)0.0040 (10)
C30.0431 (12)0.0330 (11)0.0469 (13)0.0062 (11)0.0084 (10)0.0056 (10)
C40.0340 (11)0.0386 (12)0.0412 (11)0.0008 (10)0.0002 (10)0.0119 (10)
C4A0.0340 (11)0.0338 (11)0.0296 (10)0.0012 (9)0.0008 (8)0.0056 (9)
C50.0440 (12)0.0485 (13)0.0351 (11)0.0028 (12)0.0060 (10)0.0037 (11)
C60.0642 (15)0.0447 (13)0.0328 (11)0.0019 (13)0.0026 (10)0.0034 (11)
C70.0589 (15)0.0423 (13)0.0420 (13)0.0133 (12)0.0111 (11)0.0024 (11)
C8A0.0298 (10)0.0343 (11)0.0313 (10)0.0014 (9)0.0046 (8)0.0056 (9)
C80.0347 (12)0.0471 (13)0.0401 (11)0.0066 (11)0.0028 (9)0.0048 (10)
C90.0413 (12)0.0425 (12)0.0291 (10)0.0124 (11)0.0022 (9)0.0031 (10)
Geometric parameters (Å, º) top
O1—C41.216 (2)C7—C81.377 (3)
O2—C91.214 (3)C8A—C81.388 (3)
O3—C91.313 (3)O3—H30.94 (3)
C1—C8A1.505 (3)C1—H1A0.9700
C1—C21.535 (3)C1—H1B0.9700
C2—C91.507 (3)C2—H20.9800
C2—C31.521 (3)C3—H3A0.9700
C3—C41.508 (3)C3—H3B0.9700
C4—C4A1.481 (3)C5—H50.9300
C4A—C51.391 (3)C6—H60.9300
C4A—C8A1.404 (3)C7—H70.9300
C5—C61.372 (3)C8—H80.9300
C6—C71.380 (3)
C8A—C1—C2111.32 (17)C8A—C1—H1A109.4
C9—C2—C3111.39 (18)C2—C1—H1A109.4
C9—C2—C1111.40 (17)C8A—C1—H1B109.4
C3—C2—C1109.67 (17)C2—C1—H1B109.4
C4—C3—C2113.48 (17)H1A—C1—H1B108.0
O1—C4—C4A121.7 (2)C9—C2—H2108.1
O1—C4—C3120.0 (2)C3—C2—H2108.1
C4A—C4—C3118.26 (17)C1—C2—H2108.1
C5—C4A—C8A119.76 (19)C4—C3—H3A108.9
C5—C4A—C4119.75 (18)C2—C3—H3A108.9
C8A—C4A—C4120.49 (18)C4—C3—H3B108.9
C6—C5—C4A120.8 (2)C2—C3—H3B108.9
C5—C6—C7119.7 (2)H3A—C3—H3B107.7
C8—C8A—C4A118.29 (19)C6—C5—H5119.6
C8—C8A—C1120.82 (18)C4A—C5—H5119.6
C8—C7—C6120.1 (2)C5—C6—H6120.1
C4A—C8A—C1120.89 (18)C7—C6—H6120.1
C7—C8—C8A121.3 (2)C8—C7—H7119.9
O2—C9—O3122.4 (2)C6—C7—H7119.9
O2—C9—C2123.3 (2)C7—C8—H8119.4
O3—C9—C2114.3 (2)C8A—C8—H8119.4
C9—O3—H3108.1 (18)
C8A—C1—C2—C968.3 (2)C5—C4A—C8A—C80.2 (3)
C8A—C1—C2—C355.5 (2)C4—C4A—C8A—C8178.92 (18)
C9—C2—C3—C470.5 (2)C5—C4A—C8A—C1179.69 (18)
C1—C2—C3—C453.3 (2)C4—C4A—C8A—C10.5 (3)
C2—C3—C4—O1156.4 (2)C2—C1—C8A—C8150.94 (19)
C2—C3—C4—C4A24.2 (3)C2—C1—C8A—C4A29.6 (3)
O1—C4—C4A—C53.4 (3)C6—C7—C8—C8A0.1 (3)
C3—C4—C4A—C5177.15 (18)C4A—C8A—C8—C70.1 (3)
O1—C4—C4A—C8A175.7 (2)C1—C8A—C8—C7179.56 (19)
C3—C4—C4A—C8A3.7 (3)C3—C2—C9—O21.7 (3)
C8A—C4A—C5—C60.2 (3)C1—C2—C9—O2124.5 (2)
C4—C4A—C5—C6178.98 (18)C3—C2—C9—O3179.34 (18)
C4A—C5—C6—C70.0 (3)C1—C2—C9—O356.5 (2)
C5—C6—C7—C80.2 (3)
(II) (±)-1-oxo-1,2,3,4-tetrahydronaphthalene-2-acetic acid top
Crystal data top
C12H12O3Dx = 1.312 Mg m3
Mr = 204.22Melting point: 383 K
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.0008 (10) ÅCell parameters from 21 reflections
b = 10.579 (2) Åθ = 4.6–15.0°
c = 12.6789 (13) ŵ = 0.09 mm1
β = 105.616 (8)°T = 293 K
V = 1033.5 (3) Å3Block, colorless
Z = 40.60 × 0.34 × 0.24 mm
F(000) = 432
Data collection top
Siemens P4
diffractometer
1305 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.022
Graphite monochromatorθmax = 25.0°, θmin = 2.6°
2θ/θ scansh = 99
Absorption correction: numerical
(XPREP; Sheldrick, 1997)
k = 012
Tmin = 0.981, Tmax = 0.997l = 015
2503 measured reflections3 standard reflections every 97 reflections
1822 independent reflections intensity decay: variation < 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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.033P)2 + 0.2742P]
where P = (Fo2 + 2Fc2)/3
1822 reflections(Δ/σ)max < 0.001
149 parametersΔρmax = 0.13 e Å3
0 restraintsΔρmin = 0.13 e Å3
Crystal data top
C12H12O3V = 1033.5 (3) Å3
Mr = 204.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.0008 (10) ŵ = 0.09 mm1
b = 10.579 (2) ÅT = 293 K
c = 12.6789 (13) Å0.60 × 0.34 × 0.24 mm
β = 105.616 (8)°
Data collection top
Siemens P4
diffractometer
1305 reflections with I > 2σ(I)
Absorption correction: numerical
(XPREP; Sheldrick, 1997)
Rint = 0.022
Tmin = 0.981, Tmax = 0.9973 standard reflections every 97 reflections
2503 measured reflections intensity decay: variation < 1%
1822 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.13 e Å3
1822 reflectionsΔρmin = 0.13 e Å3
149 parameters
Special details top

Experimental. Crystal mounted on glass fiber using epoxy resin

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
O10.7110 (2)0.55343 (15)0.68247 (13)0.0815 (5)
O21.03906 (18)0.56028 (13)0.88932 (11)0.0587 (4)
O30.8518 (2)0.63400 (15)0.97459 (12)0.0711 (5)
C10.7988 (3)0.62252 (18)0.64218 (16)0.0504 (5)
C20.9084 (2)0.72610 (16)0.70744 (14)0.0444 (4)
C30.8816 (3)0.84541 (18)0.63760 (17)0.0556 (5)
C40.9442 (3)0.8246 (2)0.53706 (18)0.0650 (6)
C4A0.8739 (2)0.7057 (2)0.47632 (16)0.0559 (5)
C50.8794 (3)0.6872 (3)0.36910 (19)0.0789 (8)
C60.8140 (4)0.5772 (3)0.3128 (2)0.0941 (10)
C70.7401 (4)0.4866 (3)0.3623 (2)0.0892 (9)
C80.7339 (3)0.5023 (2)0.46809 (19)0.0702 (7)
C8A0.8016 (3)0.61072 (18)0.52628 (15)0.0509 (5)
C90.8742 (3)0.74468 (18)0.81790 (16)0.0544 (5)
C100.9286 (3)0.63678 (18)0.89547 (15)0.0481 (5)
H30.8904 (13)0.567 (2)1.0182 (14)0.107 (10)*
H21.03010.70090.72040.050 (5)*
H3A0.75940.86740.61600.055 (6)*
H3B0.94500.91500.68000.077 (7)*
H4A0.91010.89620.48830.084 (7)*
H4B1.07000.82060.55850.072 (7)*
H50.92750.74930.33430.064 (7)*
H60.82080.56540.24140.113 (10)*
H70.69380.41420.32390.108 (10)*
H80.68400.44000.50160.097 (10)*
H9A0.93470.82020.85130.076 (7)*
H9B0.75100.75900.80700.071 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.1034 (13)0.0721 (10)0.0690 (10)0.0408 (10)0.0234 (9)0.0027 (9)
O20.0684 (9)0.0623 (9)0.0502 (8)0.0188 (8)0.0240 (7)0.0072 (7)
O30.0885 (12)0.0738 (10)0.0635 (9)0.0278 (9)0.0422 (9)0.0145 (8)
C10.0549 (12)0.0419 (10)0.0515 (11)0.0001 (9)0.0094 (9)0.0048 (9)
C20.0438 (10)0.0418 (10)0.0457 (10)0.0019 (9)0.0089 (8)0.0027 (8)
C30.0587 (13)0.0428 (11)0.0615 (12)0.0044 (10)0.0099 (10)0.0052 (10)
C40.0641 (15)0.0657 (14)0.0661 (14)0.0052 (11)0.0192 (11)0.0200 (12)
C4A0.0497 (12)0.0699 (14)0.0472 (11)0.0186 (11)0.0114 (9)0.0105 (10)
C50.0728 (16)0.113 (2)0.0540 (14)0.0371 (16)0.0217 (12)0.0222 (15)
C60.092 (2)0.139 (3)0.0459 (15)0.062 (2)0.0088 (14)0.0081 (17)
C70.092 (2)0.092 (2)0.0658 (17)0.0373 (17)0.0083 (15)0.0236 (16)
C80.0727 (15)0.0642 (14)0.0614 (14)0.0132 (13)0.0032 (12)0.0113 (12)
C8A0.0505 (11)0.0507 (11)0.0460 (11)0.0082 (9)0.0035 (9)0.0003 (9)
C90.0623 (13)0.0468 (11)0.0535 (12)0.0069 (10)0.0147 (10)0.0016 (10)
C100.0519 (11)0.0498 (11)0.0429 (10)0.0007 (10)0.0129 (9)0.0059 (9)
Geometric parameters (Å, º) top
O1—C11.217 (2)C8—C8A1.392 (3)
O2—C101.216 (2)C9—C101.493 (3)
O3—C101.311 (2)O3—H30.9026
C1—C8A1.481 (3)C2—H20.9800
C1—C21.505 (3)C3—H3A0.9700
C2—C91.510 (3)C3—H3B0.9700
C2—C31.523 (2)C4—H4A0.9700
C3—C41.506 (3)C4—H4B0.9700
C4—C4A1.503 (3)C5—H50.9300
C4A—C51.386 (3)C6—H60.9300
C4A—C8A1.393 (3)C7—H70.9300
C5—C61.392 (4)C8—H80.9300
C6—C71.365 (4)C9—H9A0.9700
C7—C81.365 (3)C9—H9B0.9700
O1—C1—C8A122.03 (19)C3—C2—H2107.5
O1—C1—C2121.55 (18)C4—C3—H3A109.6
C8A—C1—C2116.41 (17)C2—C3—H3A109.6
C1—C2—C9112.36 (16)C4—C3—H3B109.6
C1—C2—C3108.28 (15)C2—C3—H3B109.6
C9—C2—C3113.51 (16)H3A—C3—H3B108.2
C4—C3—C2110.12 (17)C4A—C4—H4A109.0
C4A—C4—C3113.08 (18)C3—C4—H4A109.0
C5—C4A—C8A118.1 (2)C4A—C4—H4B109.0
C5—C4A—C4120.9 (2)C3—C4—H4B109.0
C8A—C4A—C4120.96 (18)H4A—C4—H4B107.8
C4A—C5—C6120.9 (3)C4A—C5—H5119.5
C7—C6—C5120.0 (3)C6—C5—H5119.5
C6—C7—C8120.1 (3)C7—C6—H6120.0
C7—C8—C8A120.6 (3)C5—C6—H6120.0
C8—C8A—C4A120.2 (2)C6—C7—H7119.9
C8—C8A—C1119.2 (2)C8—C7—H7119.9
C4A—C8A—C1120.62 (18)C7—C8—H8119.7
C10—C9—C2114.69 (16)C8A—C8—H8119.7
O2—C10—O3122.20 (18)C10—C9—H9A108.6
O2—C10—C9123.69 (18)C2—C9—H9A108.6
O3—C10—C9114.05 (18)C10—C9—H9B108.6
C10—O3—H3109.5C2—C9—H9B108.6
C1—C2—H2107.5H9A—C9—H9B107.6
C9—C2—H2107.5
O1—C1—C2—C98.7 (3)C7—C8—C8A—C4A1.1 (3)
C8A—C1—C2—C9170.43 (16)C7—C8—C8A—C1177.7 (2)
O1—C1—C2—C3134.8 (2)C5—C4A—C8A—C81.4 (3)
C8A—C1—C2—C344.3 (2)C4—C4A—C8A—C8178.71 (19)
C1—C2—C3—C463.2 (2)C5—C4A—C8A—C1177.39 (18)
C9—C2—C3—C4171.34 (17)C4—C4A—C8A—C12.5 (3)
C2—C3—C4—C4A50.0 (2)O1—C1—C8A—C814.3 (3)
C3—C4—C4A—C5163.11 (19)C2—C1—C8A—C8166.59 (18)
C3—C4—C4A—C8A17.0 (3)O1—C1—C8A—C4A166.8 (2)
C8A—C4A—C5—C60.2 (3)C2—C1—C8A—C4A12.2 (3)
C4—C4A—C5—C6179.9 (2)C1—C2—C9—C1066.9 (2)
C4A—C5—C6—C71.3 (4)C3—C2—C9—C10169.83 (17)
C5—C6—C7—C81.6 (4)C2—C9—C10—O223.4 (3)
C6—C7—C8—C8A0.4 (4)C2—C9—C10—O3159.29 (17)

Experimental details

(I)(II)
Crystal data
Chemical formulaC11H10O3C12H12O3
Mr190.19204.22
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/n
Temperature (K)293293
a, b, c (Å)6.2645 (7), 5.4440 (12), 26.170 (3)8.0008 (10), 10.579 (2), 12.6789 (13)
β (°) 91.339 (11) 105.616 (8)
V3)892.2 (2)1033.5 (3)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.100.09
Crystal size (mm)0.56 × 0.52 × 0.100.60 × 0.34 × 0.24
Data collection
DiffractometerSiemens P4
diffractometer
Siemens P4
diffractometer
Absorption correctionNumerical
(XPREP; Sheldrick, 1997)
Numerical
(XPREP; Sheldrick, 1997)
Tmin, Tmax0.952, 0.9900.981, 0.997
No. of measured, independent and
observed [I > 2σ(I)] reflections
2499, 1582, 1118 2503, 1822, 1305
Rint0.0360.022
(sin θ/λ)max1)0.5950.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.106, 1.06 0.043, 0.109, 1.04
No. of reflections15821822
No. of parameters141149
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)0.16, 0.120.13, 0.13

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

Selected geometric parameters (Å, º) for (I) top
O2—C91.214 (3)O3—C91.313 (3)
O2—C9—C2123.3 (2)O3—C9—C2114.3 (2)
Selected geometric parameters (Å, º) for (II) top
O2—C101.216 (2)O3—C101.311 (2)
O2—C10—C9123.69 (18)O3—C10—C9114.05 (18)
 

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