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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1443.
Published online 2010 May 26. doi:  10.1107/S1600536810018544
PMCID: PMC2979377

4-(3-Methoxy­phen­yl)-2,6-dimethyl­cyclo­hex-3-enecarboxylic acid

Abstract

The racemic title compound, C16H20O3, was synthesized to study the hydrogen-bonding inter­action of the two enanti­o­mers in the solid state. In the crystal structure, R and S pairs of the racemate are linked by pairs of inter­molecular O—H(...)O hydrogen bonds, producing centrosymmetric R 2 2(8) rings.

Related literature

For similar compounds in which the racemates also consist of carboxylic acid RS dimers, see: Xie et al. (2002 [triangle], 2007a [triangle], 2008a [triangle],b [triangle]). For the structure of the precursor of the title compound, which is achiral and forms hydrogen-bonded dimers, see: Xie et al. (2007b [triangle]). The chirality of the title compound is solely generated by the presence of the double bond in the cyclo­hexene ring, see: Xie et al. (2004 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]).

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Object name is e-66-o1443-scheme1.jpg

Experimental

Crystal data

  • C16H20O3
  • M r = 260.32
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1443-efi1.jpg
  • a = 11.032 (2) Å
  • b = 7.8423 (17) Å
  • c = 32.140 (8) Å
  • V = 2780.7 (11) Å3
  • Z = 8
  • Synchrotron radiation
  • λ = 0.44280 Å
  • μ = 0.05 mm−1
  • T = 100 K
  • 0.02 × 0.01 × 0.01 mm

Data collection

  • Bruker Platform goniometer diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2007 [triangle]; Blessing, 1995 [triangle]) T min = 0.999, T max = 1.000
  • 8586 measured reflections
  • 2173 independent reflections
  • 1755 reflections with I > 2σ(I)
  • R int = 0.050

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.119
  • S = 1.11
  • 2173 reflections
  • 179 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SIR2004 (Burla et al., 2005 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018544/fj2304sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018544/fj2304Isup2.hkl

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

Acknowledgments

SX, DN, and HS are grateful for the Grant-in-aid for Faculty Research from Indiana University Kokomo, as well as the Senior Research Grant from Indiana Academy of Science. ChemMatCARS Sector 15 is principally supported by the National Science Foundation/Department of Energy under grant No. CHE-0535644. Use of the advanced Photon Source was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract No. DE—AC02-06CH11357. The authors also want to thank the beamline for synchrotron radiation at the Advanced Photon Source, Argonne National Laboratory.

supplementary crystallographic information

Comment

The title carboxylic acid was prepared to study the interaction of the two enantiomers in the solid state. We have previously reported the structure of its precursor, which is achiral and forms hydrogen-bonded dimers (Xie et al., 2007b). The chirality of the title compound is solely generated by the presence of the double bond in the cyclohexene ring (Xie et al., 2004). The resultant racemate is made up of carboxylic acid RS dimers (Xie et al., 2002, 2007a, 2008a,b). The structure and atom numbering are shown in Fig. 1, which illustrates the half-chair conformation of the cyclohexene ring. The torsion angles involving atoms C4, C5, C6, C1, and C2 are near 180°. The carboxyl group is almost perpendicular to the cyclohexene ring with an angle of 85.3° between the O1—C14—O2—C3 plane and the C1—C6 ring. The double bond between C5—C6 is not fully conjugated with the aromatic ring as shown by the C1—C6—C5 plane to benzene ring angle of 38.7°. Unlike other previously reported para substituted analogs and like other previously reported meta substituted analogs (Xie et al., 2008b), the molecule also has a chiral axis due to the meta methoxy substituent on the aromatic ring.

Fig. 2 shows the hydrogen bonding scheme. Atom O2 acts as a donor in an intermolecular hydrogen bond to atom O1, producing an R22(8) ring (Bernstein et al., 1995), thus creating a hydrogen- bonded dimer. There is no evidence to suggest that weak directional interactions interconnect the dimers. Hydrogen bond geometry is given in Table 1.

Experimental

The title carboxylic acid was synthesized following the similar method reported by Xie et al., 2002. Purified compound was recrystallized from hexane- dichloromethane as colorless plates (m.p. 415-417 K).

Refinement

The data collection was carried out using synchrotron radiation (λ= 0.44280, diamond 111 monochromator, two mirrors to exclude higher harmonics) with a frame time of 2 second and a detector distance of 6.0 cm. A randomly oriented region of reciprocal space was surveyed to the extent of a hemisphere. Two major sections of frames were collected with 0.50° steps in [var phi] and a detector position of -20° in 2θ. Data to a resolution of 0.84 Å were considered in the reduction. Final cell constants were calculated from the xyz centroids of 2804 strong reflections from the actual data collection after integration (SAINT, Bruker Analytical X-Ray Systems, Madison, WI, 2008). The intensity data were corrected for absorption (SADABS) (Blessing, 1995).

The space group Pbca was determined based on intensity statistics and systematic absences. The structure was solved using SIR-2004 (Burla et al., 2005) and refined with SHELXL-97 (Sheldrick, 2008). A direct-methods solution was calculated, which provided most non-hydrogen atoms from the E-map. Full-matrix least squares / difference Fourier cycles were performed, which located the remaining non-hydrogen atoms. All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydrogen atoms were placed in ideal positions and refined as riding atoms with relative isotropic displacement parameters with the exception of the hydroxyl hydrogen atom, which was refined for all parameters. The final full matrix least squares refinement converged to R1 = 0.0368 and wR2 = 0.1190 (F2, all data). The structure was found as proposed. The remaining electron density is minuscule and located on bonds.

Figures

Fig. 1.
The molecular structure and atom numbering scheme.
Fig. 2.
Hydrogen bonded dimer. Dashed lines represent hydrogen bonds. [Symmetry code: #1 -x,-y,-z+1.]

Crystal data

C16H20O3F(000) = 1120
Mr = 260.32Dx = 1.244 Mg m3
Orthorhombic, PbcaSynchrotron radiation, λ = 0.44280 Å
Hall symbol: -P 2ac 2abCell parameters from 2804 reflections
a = 11.032 (2) Åθ = 2.3–15.3°
b = 7.8423 (17) ŵ = 0.05 mm1
c = 32.140 (8) ÅT = 100 K
V = 2780.7 (11) Å3Plate, colorless
Z = 80.02 × 0.01 × 0.01 mm

Data collection

Bruker Platform goniometer diffractometer2173 independent reflections
Radiation source: synchrotron1755 reflections with I > 2σ(I)
diamond 1 1 1Rint = 0.050
Detector resolution: 83.33 pixels mm-1θmax = 15.3°, θmin = 0.8°
ω and phi scansh = −11→13
Absorption correction: multi-scan (SADABS; Bruker, 2007; Blessing, 1995)k = −8→6
Tmin = 0.999, Tmax = 1.000l = −38→26
8586 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H atoms treated by a mixture of independent and constrained refinement
S = 1.11w = 1/[σ2(Fo2) + (0.0707P)2 + 0.0727P] where P = (Fo2 + 2Fc2)/3
2173 reflections(Δ/σ)max = 0.001
179 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = −0.23 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O1−0.01213 (10)0.06346 (16)0.54893 (3)0.0182 (3)
O20.02685 (11)0.22640 (18)0.49329 (4)0.0209 (3)
H2O0.018 (2)0.122 (4)0.4790 (8)0.049 (7)*
O30.19151 (12)0.77788 (18)0.76439 (3)0.0250 (4)
C1−0.07178 (15)0.5720 (2)0.60649 (5)0.0173 (4)
H1A−0.07300.66500.58570.021*
H1B−0.14030.59090.62580.021*
C2−0.09016 (14)0.4018 (2)0.58418 (5)0.0152 (4)
H2−0.10310.31080.60550.018*
C30.02669 (14)0.3611 (2)0.55976 (5)0.0141 (4)
H30.04460.45920.54090.017*
C40.13603 (14)0.3370 (2)0.58944 (5)0.0148 (4)
H40.12880.22270.60300.018*
C50.13641 (15)0.4715 (2)0.62290 (5)0.0161 (4)
H50.20660.47960.63990.019*
C60.04532 (15)0.5812 (2)0.63059 (5)0.0152 (4)
C70.05757 (14)0.7208 (2)0.66193 (5)0.0157 (4)
C80.11780 (15)0.6918 (2)0.69955 (5)0.0167 (4)
H80.15000.58200.70540.020*
C90.13098 (15)0.8233 (2)0.72858 (5)0.0181 (4)
C100.08441 (15)0.9845 (2)0.72076 (5)0.0202 (4)
H100.09301.07360.74060.024*
C110.02467 (16)1.0126 (3)0.68315 (5)0.0209 (4)
H11−0.00671.12280.67720.025*
C120.01008 (15)0.8828 (2)0.65423 (5)0.0189 (4)
H12−0.03240.90420.62910.023*
C13−0.20110 (15)0.4090 (2)0.55581 (5)0.0194 (4)
H13A−0.21530.29620.54360.029*
H13B−0.18700.49200.53350.029*
H13C−0.27220.44330.57210.029*
C140.01185 (14)0.2031 (2)0.53354 (5)0.0137 (4)
C150.25486 (15)0.3418 (2)0.56468 (5)0.0183 (4)
H15A0.32350.32770.58370.027*
H15B0.26180.45150.55030.027*
H15C0.25520.24920.54420.027*
C160.19283 (18)0.8987 (3)0.79772 (5)0.0244 (5)
H16A0.23280.84830.82200.037*
H16B0.10940.92970.80500.037*
H16C0.23711.00100.78900.037*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0202 (7)0.0155 (9)0.0188 (7)−0.0023 (5)0.0004 (5)−0.0007 (5)
O20.0300 (7)0.0176 (10)0.0153 (7)−0.0046 (5)0.0012 (5)−0.0023 (5)
O30.0342 (8)0.0229 (10)0.0177 (7)0.0040 (5)−0.0082 (5)−0.0049 (5)
C10.0154 (9)0.0176 (13)0.0190 (9)0.0023 (7)0.0011 (7)−0.0024 (7)
C20.0133 (9)0.0163 (12)0.0161 (8)0.0002 (6)0.0005 (6)0.0001 (6)
C30.0147 (9)0.0130 (12)0.0148 (8)−0.0001 (6)−0.0009 (6)0.0004 (7)
C40.0126 (9)0.0149 (12)0.0169 (8)0.0003 (6)−0.0016 (6)0.0007 (7)
C50.0159 (9)0.0165 (12)0.0159 (8)−0.0020 (7)−0.0018 (6)−0.0007 (7)
C60.0162 (9)0.0151 (12)0.0142 (8)−0.0016 (7)0.0014 (7)0.0018 (6)
C70.0119 (9)0.0179 (13)0.0171 (9)−0.0020 (7)0.0038 (6)−0.0007 (7)
C80.0182 (9)0.0138 (12)0.0181 (9)0.0009 (6)0.0022 (6)−0.0004 (6)
C90.0175 (9)0.0198 (13)0.0170 (8)−0.0018 (7)0.0005 (7)0.0002 (7)
C100.0197 (10)0.0204 (13)0.0205 (9)−0.0017 (7)0.0028 (7)−0.0063 (7)
C110.0228 (10)0.0161 (13)0.0239 (10)0.0045 (7)0.0012 (7)−0.0020 (7)
C120.0172 (9)0.0206 (14)0.0189 (9)0.0025 (7)−0.0013 (7)−0.0012 (7)
C130.0145 (9)0.0199 (13)0.0238 (9)0.0016 (7)−0.0021 (7)−0.0031 (7)
C140.0074 (8)0.0156 (13)0.0181 (9)0.0008 (6)−0.0011 (6)0.0011 (7)
C150.0151 (9)0.0173 (12)0.0225 (8)0.0000 (7)−0.0005 (7)−0.0029 (7)
C160.0330 (11)0.0235 (14)0.0168 (9)−0.0040 (8)−0.0029 (8)−0.0055 (7)

Geometric parameters (Å, °)

O1—C141.230 (2)C6—C71.493 (2)
O2—C141.317 (2)C7—C121.396 (3)
O2—H2O0.94 (3)C7—C81.398 (2)
O3—C91.378 (2)C8—C91.399 (2)
O3—C161.430 (2)C8—H80.9500
C1—C61.508 (2)C9—C101.387 (3)
C1—C21.528 (2)C10—C111.394 (2)
C1—H1A0.9900C10—H100.9500
C1—H1B0.9900C11—C121.388 (3)
C2—C131.527 (2)C11—H110.9500
C2—C31.543 (2)C12—H120.9500
C2—H21.0000C13—H13A0.9800
C3—C141.508 (2)C13—H13B0.9800
C3—C41.549 (2)C13—H13C0.9800
C3—H31.0000C15—H15A0.9800
C4—C51.507 (2)C15—H15B0.9800
C4—C151.534 (2)C15—H15C0.9800
C4—H41.0000C16—H16A0.9800
C5—C61.346 (3)C16—H16B0.9800
C5—H50.9500C16—H16C0.9800
C14—O2—H2O110.1 (16)C7—C8—H8119.8
C9—O3—C16117.34 (15)C9—C8—H8119.8
C6—C1—C2113.35 (14)O3—C9—C10124.50 (15)
C6—C1—H1A108.9O3—C9—C8114.65 (16)
C2—C1—H1A108.9C10—C9—C8120.85 (16)
C6—C1—H1B108.9C9—C10—C11118.43 (16)
C2—C1—H1B108.9C9—C10—H10120.8
H1A—C1—H1B107.7C11—C10—H10120.8
C13—C2—C1110.76 (14)C12—C11—C10121.27 (18)
C13—C2—C3111.93 (13)C12—C11—H11119.4
C1—C2—C3107.97 (13)C10—C11—H11119.4
C13—C2—H2108.7C11—C12—C7120.36 (16)
C1—C2—H2108.7C11—C12—H12119.8
C3—C2—H2108.7C7—C12—H12119.8
C14—C3—C2111.34 (13)C2—C13—H13A109.5
C14—C3—C4109.16 (14)C2—C13—H13B109.5
C2—C3—C4111.26 (13)H13A—C13—H13B109.5
C14—C3—H3108.3C2—C13—H13C109.5
C2—C3—H3108.3H13A—C13—H13C109.5
C4—C3—H3108.3H13B—C13—H13C109.5
C5—C4—C15110.53 (14)O1—C14—O2123.06 (15)
C5—C4—C3110.86 (14)O1—C14—C3122.03 (14)
C15—C4—C3110.06 (13)O2—C14—C3114.91 (15)
C5—C4—H4108.4C4—C15—H15A109.5
C15—C4—H4108.4C4—C15—H15B109.5
C3—C4—H4108.4H15A—C15—H15B109.5
C6—C5—C4125.23 (15)C4—C15—H15C109.5
C6—C5—H5117.4H15A—C15—H15C109.5
C4—C5—H5117.4H15B—C15—H15C109.5
C5—C6—C7121.65 (15)O3—C16—H16A109.5
C5—C6—C1120.98 (16)O3—C16—H16B109.5
C7—C6—C1117.32 (14)H16A—C16—H16B109.5
C12—C7—C8118.65 (15)O3—C16—H16C109.5
C12—C7—C6120.89 (15)H16A—C16—H16C109.5
C8—C7—C6120.46 (16)H16B—C16—H16C109.5
C7—C8—C9120.42 (17)
C6—C1—C2—C13−172.40 (14)C5—C6—C7—C8−39.5 (2)
C6—C1—C2—C3−49.53 (18)C1—C6—C7—C8142.90 (16)
C13—C2—C3—C14−52.46 (19)C12—C7—C8—C9−0.6 (2)
C1—C2—C3—C14−174.62 (13)C6—C7—C8—C9178.94 (15)
C13—C2—C3—C4−174.47 (15)C16—O3—C9—C108.2 (2)
C1—C2—C3—C463.37 (17)C16—O3—C9—C8−171.22 (15)
C14—C3—C4—C5−166.45 (14)C7—C8—C9—O3179.71 (14)
C2—C3—C4—C5−43.19 (19)C7—C8—C9—C100.2 (2)
C14—C3—C4—C1570.95 (17)O3—C9—C10—C11−179.78 (16)
C2—C3—C4—C15−165.78 (14)C8—C9—C10—C11−0.4 (2)
C15—C4—C5—C6132.37 (18)C9—C10—C11—C120.9 (3)
C3—C4—C5—C610.1 (2)C10—C11—C12—C7−1.3 (3)
C4—C5—C6—C7−174.49 (16)C8—C7—C12—C111.2 (2)
C4—C5—C6—C13.0 (3)C6—C7—C12—C11−178.39 (15)
C2—C1—C6—C517.8 (2)C2—C3—C14—O1−60.2 (2)
C2—C1—C6—C7−164.57 (14)C4—C3—C14—O163.06 (19)
C5—C6—C7—C12140.02 (18)C2—C3—C14—O2120.03 (15)
C1—C6—C7—C12−37.5 (2)C4—C3—C14—O2−116.76 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2O···O1i0.94 (3)1.71 (3)2.6523 (19)175 (2)

Symmetry codes: (i) −x, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2304).

References

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