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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2576–o2577.
Published online 2010 September 18. doi:  10.1107/S1600536810036652
PMCID: PMC2983244

4-Oxocyclo­hexa­neacetic acid: catemeric hydrogen bonding and spontaneous resolution of a single conformational enanti­omer in an achiral [sm epsilon]-keto acid

Abstract

The asymmetric unit of the title compound, C8H12O3, consists of a single conformational enanti­omer, which aggregates in the catemeric acid-to-ketone hydrogen-bonding mode [O(...)O = 2.682 (4) Å and O—H(...)O = 172 (6)°]. Four hydrogen-bonding chains of translationally related mol­ecules pass through the cell orthogonal to the 43 screw axis along c, alternating in the 110 and the An external file that holds a picture, illustration, etc.
Object name is e-66-o2576-efi1.jpg10 direction, with alignment with respect to this axis of + + − −. Successive chains are rotated by 90° around the c axis. One C—H(...)O=C close contact, involving the carboxyl group, exists.

Related literature

For a discussion of highly ordered carboxyl bond distances and angles, see: Borthwick (1980 [triangle]). For close contact information, see: Steiner (1997 [triangle]). For related structures, see: Abell et al. (1991 [triangle]); Chen et al. (2000 [triangle]); Desiraju (1989 [triangle]); Halfpenny (1990 [triangle]); Jacques et al. (1981 [triangle]); Kawai et al. (1985 [triangle]); McGuire et al. (1995 [triangle]). For background information regarding the crystallization of a single chiral conformer from a racemic solution, see: Kondepudi et al. (1990 [triangle]). For anti-isoketopinic acid, see: Lalancette et al. (1997 [triangle]). For a description of the Cambridge Structural Database, see: Allen (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2576-scheme1.jpg

Experimental

Crystal data

  • C8H12O3
  • M r = 156.18
  • Tetragonal, An external file that holds a picture, illustration, etc.
Object name is e-66-o2576-efi2.jpg
  • a = 6.8531 (12) Å
  • c = 17.372 (3) Å
  • V = 815.9 (3) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 0.80 mm−1
  • T = 100 K
  • 0.28 × 0.20 × 0.16 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2008a [triangle]) T min = 0.806, T max = 0.882
  • 6963 measured reflections
  • 1310 independent reflections
  • 1274 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.113
  • S = 1.18
  • 1310 reflections
  • 105 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.20 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 559 Friedel pairs
  • Flack parameter: 0.0 (4)

Data collection: APEX2 (Bruker, 2006 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008b [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810036652/sj5037sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036652/sj5037Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge support by NSF-CRIF grant No. 0443538. This paper is dedicated to the memory of HWT: he was a wonderful mentor, teacher and friend at Rutgers University-Newark for 44 years; he will surely be missed.

supplementary crystallographic information

Comment

The similar carbonyl basicities of carboxylic acids and ketones allow the two to compete as hydrogen-bond acceptors. Hence, simple keto acids display three known solid-state H-bonding modes beyond those seen in functionally unelaborated acids. The commonest, acid-to-ketone catemerization, constitutes a sizable minority of cases. The title compound aggregates as a catemer and crystallizes with only a single chiral conformer present.

Fig. 1 offers a view of the asymmetric unit. The expected staggering of substituents at C1 and C7 minimizes interactions with the axial H atoms at C2 and C6 by rotating the carboxyl away from the central O1—C4—C1—C7 plane, thus producing a chiral conformation. The C2—C1—C7—C8 torsion angle is -66.9 (4)° and the C1—C7—C8—O2 torsion angle is -9.9 (6)°.

The averaging of C—O bond lengths and C—C—O angles by disorder, common in carboxyl dimers, is not observed in catemers whose geometry cannot support the underlying averaging mechanisms involved. Here, these lengths and angles are typical of those for highly ordered dimeric carboxyls and catemers (Borthwick, 1980).

Fig. 2 shows the packing of the cell, with extracellular molecules to illustrate the H-bonding aggregation as translational carboxyl-to-ketone catemers around the 43 screw axis coinciding with the c cell edge [O···O = 2.682 (4) Å, O—H···O = 172 (6)°]. Successive molecules in a given H-bonding chain advance alternately along the 110 and the -110 directions, with alignment with respect to the c axis of + + - -. Successive chains around the c axis are rotated by 90°. The structure therefore is comprised of stacked sheets in four orientations, each layer consisting of parallel H-bonding chains laid side-by-side. The arrangement is nearly identical with that we have previously reported for anti-isoketopinic acid (Lalancette et al., 1997).

We characterize the geometry of H bonding to carbonyls using a combination of H···O=C angle and H···O=C—C torsion angle. These describe the approach of the acid H atom to the receptor O in terms of its deviation from, respectively, C=O axiality (ideal = 120°) and coplanarity with the carbonyl (ideal = 0°). Here, these two angles are 128.6 (16) and -1.2 (19)°.

Within the 2.6 Å range we survey for non-bonded C—H···O packing interactions (Steiner, 1997), only one close contact was found (see Table 2).

Although crystallization in space group P43 is itself quite unusual (ca 0.12% of compounds in the Cambridge database), an equally unusual aspect of the packing is the presence of only a single chiral conformer. Preferential crystallization of one chiral conformer from solutions of an inherently achiral molecule is very rare but far from unknown (Jacques et al., 1981; Desiraju, 1989). Among keto acids, five cases are known of this phenomenon: [Cambridge Structural Database (CSD, Version 5.28, update of Nov., 2006; Allen, 2002) refcodes CUHCUD (Kawai et al., 1985), JISVAI (Abell et al., 1991), KICRIX (Halfpenny, 1990) & ZEMJIK (McGuire et al., 1995)], plus the case of mesitylglyoxylic acid (Chen et al., 2000). The particular antipode crystallizing from such a solution may depend merely on which one chances to crystallize first, and it has been shown in a similar case that stirring seeds the solution and may largely or entirely prevent the enantiomeric species from crystallizing (Kondepudi et al., 1990). In the present instance, the Flack parameter allows us to assign a specific hand to (I), so the antipode actually illustrated is the correct one. Also, the octant rule predicts that the conformer should have (-) rotation.

Experimental

The solid-state (KBr) infrared spectrum of (I) has C=O stretching absorptions at 1726 and 1685 cm-1, consistent with known shifts produced when H-bonding is removed from carboxyl C=O and added to a ketone, respectively. In CHCl3 solution, these bands coalesce to a single absorption at 1707 cm-1, with a typical carboxyl-dilution shoulder around 1755 cm-1.

The title compound was prepared by Jones oxidation of the product obtained by catalytic hydrogenation of p-hydroxyphenylacetic acid over a Rh/C catalyst. The crystal used was obtained from Et2O/cyclohexane (60:40 v/v) by evaporation, mp 345 K.

Refinement

All H atoms for (I) were found in electron density difference maps. The hydroxyl H was fully refined. The methylene and methine Hs were placed in geometrically idealized positions and constrained to ride on their parent C atoms with C—H distances of 0.99 and 1.00 Å, respectively, and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
A view of the asymmetric unit with its numbering. Displacement ellipsoids are set at the 40% probability level.
Fig. 2.
A packing diagram, with extracellular molecules, showing the four catemers created by acid-to-ketone H bonds proceeding along chains of translationally related molecules, advancing alternately along the 110 and the -110 directions. These chains have alignment ...

Crystal data

C8H12O3Dx = 1.271 Mg m3
Mr = 156.18Melting point: 345 K
Tetragonal, P43Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 4cwCell parameters from 6759 reflections
a = 6.8531 (12) Åθ = 5.1–70.5°
c = 17.372 (3) ŵ = 0.80 mm1
V = 815.9 (3) Å3T = 100 K
Z = 4Block, colourless
F(000) = 3360.28 × 0.20 × 0.16 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer1310 independent reflections
Radiation source: fine-focus sealed tube1274 reflections with I > 2σ(I)
graphiteRint = 0.029
[var phi] and ω scansθmax = 70.8°, θmin = 6.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)h = −7→7
Tmin = 0.806, Tmax = 0.882k = −8→7
6963 measured reflectionsl = −20→18

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.039w = 1/[σ2(Fo2) + (0.0369P)2 + 0.671P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.113(Δ/σ)max < 0.001
S = 1.18Δρmax = 0.17 e Å3
1310 reflectionsΔρmin = −0.20 e Å3
105 parametersExtinction correction: SHELXTL (Sheldrick, 2008b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0023 (5)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 559 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.0 (4)

Special details

Experimental. crystal mounted on a Cryoloop using Paratone-N
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)

xyzUiso*/Ueq
O10.9958 (3)1.2372 (3)0.08526 (13)0.0341 (5)
O20.2472 (4)0.6544 (3)0.03744 (14)0.0460 (6)
O30.1245 (4)0.5683 (4)0.15016 (13)0.0421 (6)
H30.083 (6)0.482 (6)0.130 (2)0.036 (11)*
C10.4571 (4)0.9768 (4)0.10334 (18)0.0275 (6)
H10.39561.01550.05340.033*
C20.6441 (4)0.8617 (4)0.08592 (17)0.0289 (7)
H2A0.70560.82080.13490.035*
H2B0.61050.74260.05650.035*
C30.7890 (4)0.9841 (4)0.03955 (19)0.0299 (6)
H3A0.91280.91090.03420.036*
H3B0.73581.0064−0.01270.036*
C40.8297 (4)1.1764 (4)0.07670 (18)0.0294 (7)
C50.6532 (5)1.2912 (4)0.10375 (19)0.0340 (7)
H5A0.58671.34940.05870.041*
H5B0.69671.39900.13760.041*
C60.5086 (4)1.1616 (4)0.14778 (18)0.0309 (7)
H6A0.56621.12490.19800.037*
H6B0.38791.23650.15800.037*
C70.3105 (4)0.8534 (4)0.14873 (17)0.0284 (6)
H7A0.37570.80310.19560.034*
H7B0.20190.93860.16560.034*
C80.2272 (4)0.6841 (4)0.10499 (17)0.0285 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0344 (12)0.0356 (12)0.0322 (12)−0.0107 (9)−0.0004 (9)0.0009 (9)
O20.0644 (16)0.0488 (14)0.0248 (12)−0.0289 (12)0.0023 (12)−0.0052 (10)
O30.0544 (15)0.0413 (14)0.0305 (12)−0.0195 (12)0.0077 (11)−0.0039 (11)
C10.0327 (15)0.0281 (15)0.0217 (14)−0.0034 (12)−0.0037 (12)0.0028 (12)
C20.0366 (16)0.0244 (15)0.0258 (16)−0.0003 (12)−0.0009 (13)−0.0002 (12)
C30.0321 (16)0.0318 (15)0.0257 (15)0.0002 (12)−0.0033 (13)0.0002 (13)
C40.0353 (16)0.0308 (15)0.0222 (14)−0.0054 (13)−0.0014 (13)0.0070 (12)
C50.0407 (18)0.0254 (16)0.0358 (18)−0.0041 (13)−0.0004 (14)−0.0018 (13)
C60.0282 (15)0.0294 (16)0.0352 (17)0.0007 (11)−0.0004 (13)−0.0025 (14)
C70.0311 (15)0.0299 (15)0.0244 (15)−0.0004 (11)−0.0004 (12)0.0015 (12)
C80.0270 (15)0.0351 (16)0.0234 (16)0.0001 (12)−0.0016 (12)0.0002 (12)

Geometric parameters (Å, °)

O1—C41.222 (4)C3—H3A0.9900
O2—C81.199 (4)C3—H3B0.9900
O3—C81.319 (4)C4—C51.518 (4)
O3—H30.74 (4)C5—C61.535 (4)
C1—C61.524 (4)C5—H5A0.9900
C1—C71.532 (4)C5—H5B0.9900
C1—C21.535 (4)C6—H6A0.9900
C1—H11.0000C6—H6B0.9900
C2—C31.529 (4)C7—C81.500 (4)
C2—H2A0.9900C7—H7A0.9900
C2—H2B0.9900C7—H7B0.9900
C3—C41.494 (4)
C8—O3—H3114 (3)C4—C5—C6111.6 (2)
C6—C1—C7110.5 (2)C4—C5—H5A109.3
C6—C1—C2109.5 (2)C6—C5—H5A109.3
C7—C1—C2111.4 (2)C4—C5—H5B109.3
C6—C1—H1108.5C6—C5—H5B109.3
C7—C1—H1108.5H5A—C5—H5B108.0
C2—C1—H1108.5C1—C6—C5112.2 (2)
C3—C2—C1111.4 (2)C1—C6—H6A109.2
C3—C2—H2A109.4C5—C6—H6A109.2
C1—C2—H2A109.4C1—C6—H6B109.2
C3—C2—H2B109.4C5—C6—H6B109.2
C1—C2—H2B109.4H6A—C6—H6B107.9
H2A—C2—H2B108.0C8—C7—C1114.6 (2)
C4—C3—C2112.2 (3)C8—C7—H7A108.6
C4—C3—H3A109.2C1—C7—H7A108.6
C2—C3—H3A109.2C8—C7—H7B108.6
C4—C3—H3B109.2C1—C7—H7B108.6
C2—C3—H3B109.2H7A—C7—H7B107.6
H3A—C3—H3B107.9O2—C8—O3122.8 (3)
O1—C4—C3121.8 (3)O2—C8—C7125.7 (3)
O1—C4—C5121.9 (3)O3—C8—C7111.5 (3)
C3—C4—C5116.3 (3)
C6—C1—C2—C3−58.4 (3)C7—C1—C6—C5−179.2 (2)
C7—C1—C2—C3179.1 (2)C2—C1—C6—C557.8 (3)
C1—C2—C3—C452.9 (3)C4—C5—C6—C1−51.0 (3)
C2—C3—C4—O1132.3 (3)C6—C1—C7—C8171.1 (2)
C2—C3—C4—C5−47.3 (4)C2—C1—C7—C8−67.0 (3)
O1—C4—C5—C6−133.5 (3)C1—C7—C8—O2−9.6 (4)
C3—C4—C5—C646.0 (4)C1—C7—C8—O3171.0 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3···O1i0.75 (6)1.94 (6)2.682 (4)172 (6)
C7—H7A···O2ii0.992.513.439 (5)156

Symmetry codes: (i) x−1, y−1, z; (ii) y, −x+1, z+1/4.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ5037).

References

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