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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1516.
Published online 2010 May 29. doi:  10.1107/S1600536810019732
PMCID: PMC2979589

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

Abstract

The title compound, C16H20O3, was synthesized to study the hydrogen-bonding inter­actions of the two enanti­omers in the solid state. Inter­molecular O—H(...)O hydrogen bonds produce centrosymmetric R 2 2(8) rings which dimerize the two chiral enanti­omers together through their carboxyl groups.

Related literature

In similar compounds previously reported (Xie et al., 2002 [triangle], 2007a [triangle], 2008a [triangle],b [triangle]), the racemates also consist of carb­oxy­lic acid RS dimers. For the structure of the precursor, 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]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1516-scheme1.jpg

Experimental

Crystal data

  • C16H20O3
  • M r = 260.32
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1516-efi1.jpg
  • a = 14.2283 (9) Å
  • b = 7.1202 (5) Å
  • c = 14.9517 (10) Å
  • β = 106.069 (2)°
  • V = 1455.55 (17) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 150 K
  • 0.25 × 0.23 × 0.07 mm

Data collection

  • Bruker APEXII Kappa Duo diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.980, T max = 0.994
  • 11165 measured reflections
  • 2964 independent reflections
  • 2296 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.138
  • S = 1.04
  • 2964 reflections
  • 179 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.56 e Å−3
  • Δρmin = −0.34 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: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810019732/om2342sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810019732/om2342Isup2.hkl

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

Acknowledgments

SX, BF, and SD 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.

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 0°. The carboxyl group is almost perpendicular to the cyclohexene ring with an angle of 82.2° 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 52.6°. 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 ortho 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 asimilar method reported by Xie et al., 2002. Purified compound was recrystallized from hexane- dichloromethane as colorless plates (m.p. 417-418 K).

Refinement

All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydrogen atoms not involved in hydrogen bonding were placed in ideal positions and refined as riding atoms with relative isotropic displacement parameters. H1 was freely refined.

Figures

Fig. 1.
The molecular structure showing thermal ellipsoids at the 50% probability level and the atom numbering scheme.
Fig. 2.
Hydrogen bonded dimer. Dashed lines represent hydrogen bonds (symmetry code: #1 -x+2,-y+3,-z).

Crystal data

C16H20O3F(000) = 560
Mr = 260.32Dx = 1.188 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4026 reflections
a = 14.2283 (9) Åθ = 2.8–26.3°
b = 7.1202 (5) ŵ = 0.08 mm1
c = 14.9517 (10) ÅT = 150 K
β = 106.069 (2)°Plate, colorless
V = 1455.55 (17) Å30.25 × 0.23 × 0.07 mm
Z = 4

Data collection

Bruker APEXII Kappa Duo diffractometer2964 independent reflections
Radiation source: fine-focus sealed tube2296 reflections with I > 2σ(I)
graphiteRint = 0.022
Detector resolution: 83.33 pixels mm-1θmax = 26.4°, θmin = 1.5°
ω and [var phi] scansh = −16→17
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)k = −7→8
Tmin = 0.980, Tmax = 0.994l = −13→18
11165 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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138H atoms treated by a mixture of independent and constrained refinement
S = 1.04w = 1/[σ2(Fo2) + (0.0653P)2 + 0.6215P] where P = (Fo2 + 2Fc2)/3
2964 reflections(Δ/σ)max = 0.001
179 parametersΔρmax = 0.56 e Å3
0 restraintsΔρmin = −0.34 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
O10.88885 (9)0.4779 (2)0.00968 (10)0.0602 (5)
O21.02302 (9)0.3518 (2)0.10376 (10)0.0531 (4)
H2O1.051 (2)0.411 (4)0.0670 (18)0.082 (8)*
O30.55725 (8)−0.14999 (17)0.09567 (7)0.0342 (3)
C10.76051 (16)−0.0149 (3)0.11315 (14)0.0478 (5)
H1A0.7060−0.08030.06830.057*
H1B0.8079−0.11220.14460.057*
C20.81042 (14)0.1106 (3)0.05858 (12)0.0418 (5)
H20.75850.17710.01000.050*
C30.87036 (12)0.2591 (3)0.12493 (12)0.0366 (4)
H30.91750.19270.17750.044*
C40.80346 (14)0.3809 (3)0.16515 (13)0.0409 (4)
H40.76100.45590.11290.049*
C50.73751 (16)0.2583 (3)0.20376 (14)0.0479 (5)
H50.70530.31370.24500.057*
C60.72161 (11)0.0741 (2)0.18303 (11)0.0300 (4)
C70.66838 (11)−0.0451 (2)0.23497 (10)0.0279 (4)
C80.69907 (12)−0.0459 (2)0.33172 (11)0.0322 (4)
H80.75150.03370.36290.039*
C90.65520 (14)−0.1596 (2)0.38384 (11)0.0377 (4)
H90.6772−0.15700.44990.045*
C100.57966 (14)−0.2762 (3)0.33929 (12)0.0392 (4)
H100.5501−0.35570.37480.047*
C110.54636 (13)−0.2784 (2)0.24267 (12)0.0343 (4)
H110.4942−0.35920.21220.041*
C120.58967 (11)−0.1624 (2)0.19099 (11)0.0279 (4)
C130.87078 (18)−0.0056 (4)0.00957 (17)0.0680 (7)
H13A0.89840.0766−0.02920.102*
H13B0.8290−0.1004−0.02970.102*
H13C0.9239−0.06800.05600.102*
C140.92794 (13)0.3744 (3)0.07423 (12)0.0409 (5)
C150.86046 (19)0.5186 (3)0.23835 (16)0.0615 (6)
H15A0.81460.59430.26150.092*
H15B0.89970.60130.21050.092*
H15C0.90370.44880.29010.092*
C160.47037 (14)−0.2506 (3)0.05064 (12)0.0441 (5)
H16A0.4516−0.2223−0.01610.066*
H16B0.4175−0.21290.07720.066*
H16C0.4822−0.38570.05990.066*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0321 (7)0.0899 (12)0.0542 (8)−0.0105 (7)0.0048 (6)0.0408 (8)
O20.0299 (7)0.0756 (11)0.0510 (8)−0.0106 (7)0.0066 (6)0.0317 (7)
O30.0347 (6)0.0422 (7)0.0275 (6)−0.0110 (5)0.0115 (5)−0.0011 (5)
C10.0570 (12)0.0433 (11)0.0542 (11)−0.0197 (9)0.0341 (10)−0.0117 (9)
C20.0365 (9)0.0554 (12)0.0387 (9)−0.0140 (9)0.0190 (8)−0.0047 (8)
C30.0303 (9)0.0444 (10)0.0336 (8)−0.0108 (8)0.0066 (7)0.0099 (7)
C40.0461 (11)0.0374 (10)0.0397 (9)−0.0125 (8)0.0124 (8)0.0025 (8)
C50.0604 (13)0.0390 (11)0.0554 (11)−0.0104 (9)0.0346 (10)−0.0058 (9)
C60.0270 (8)0.0360 (9)0.0285 (8)−0.0060 (7)0.0100 (6)−0.0011 (7)
C70.0277 (8)0.0292 (8)0.0294 (8)0.0019 (7)0.0121 (6)0.0008 (6)
C80.0318 (9)0.0335 (9)0.0315 (8)0.0020 (7)0.0091 (7)−0.0001 (7)
C90.0475 (10)0.0398 (10)0.0274 (8)0.0071 (8)0.0129 (7)0.0056 (7)
C100.0515 (11)0.0355 (9)0.0374 (9)−0.0013 (8)0.0236 (8)0.0088 (8)
C110.0382 (9)0.0314 (9)0.0374 (9)−0.0046 (7)0.0173 (7)0.0010 (7)
C120.0301 (8)0.0279 (8)0.0291 (8)0.0011 (7)0.0138 (6)0.0007 (6)
C130.0605 (14)0.0884 (18)0.0704 (15)−0.0219 (13)0.0437 (12)−0.0283 (13)
C140.0299 (9)0.0529 (11)0.0365 (9)−0.0122 (8)0.0036 (7)0.0126 (8)
C150.0778 (16)0.0467 (12)0.0576 (13)−0.0251 (12)0.0148 (12)−0.0074 (10)
C160.0473 (11)0.0508 (11)0.0334 (9)−0.0185 (9)0.0098 (8)−0.0066 (8)

Geometric parameters (Å, °)

O1—C141.219 (2)C6—C71.491 (2)
O2—C141.312 (2)C7—C81.391 (2)
O2—H2O0.88 (3)C7—C121.406 (2)
O3—C121.3740 (19)C8—C91.386 (2)
O3—C161.426 (2)C8—H80.9500
C1—C61.456 (2)C9—C101.376 (3)
C1—C21.513 (2)C9—H90.9500
C1—H1A0.9900C10—C111.390 (2)
C1—H1B0.9900C10—H100.9500
C2—C131.519 (3)C11—C121.387 (2)
C2—C31.537 (2)C11—H110.9500
C2—H21.0000C13—H13A0.9800
C3—C141.504 (2)C13—H13B0.9800
C3—C41.528 (3)C13—H13C0.9800
C3—H31.0000C15—H15A0.9800
C4—C51.508 (2)C15—H15B0.9800
C4—C151.525 (3)C15—H15C0.9800
C4—H41.0000C16—H16A0.9800
C5—C61.352 (3)C16—H16B0.9800
C5—H50.9500C16—H16C0.9800
C14—O2—H2O110.0 (18)C9—C8—H8119.1
C12—O3—C16117.10 (12)C7—C8—H8119.1
C6—C1—C2117.26 (16)C10—C9—C8119.56 (15)
C6—C1—H1A108.0C10—C9—H9120.2
C2—C1—H1A108.0C8—C9—H9120.2
C6—C1—H1B108.0C9—C10—C11120.40 (16)
C2—C1—H1B108.0C9—C10—H10119.8
H1A—C1—H1B107.2C11—C10—H10119.8
C1—C2—C13110.54 (18)C12—C11—C10119.74 (16)
C1—C2—C3108.53 (14)C12—C11—H11120.1
C13—C2—C3113.54 (16)C10—C11—H11120.1
C1—C2—H2108.0O3—C12—C11122.89 (15)
C13—C2—H2108.0O3—C12—C7116.24 (13)
C3—C2—H2108.0C11—C12—C7120.84 (15)
C14—C3—C4111.98 (15)C2—C13—H13A109.5
C14—C3—C2109.42 (14)C2—C13—H13B109.5
C4—C3—C2110.45 (14)H13A—C13—H13B109.5
C14—C3—H3108.3C2—C13—H13C109.5
C4—C3—H3108.3H13A—C13—H13C109.5
C2—C3—H3108.3H13B—C13—H13C109.5
C5—C4—C15111.17 (16)O1—C14—O2122.86 (16)
C5—C4—C3110.10 (15)O1—C14—C3122.40 (16)
C15—C4—C3112.43 (17)O2—C14—C3114.73 (15)
C5—C4—H4107.6C4—C15—H15A109.5
C15—C4—H4107.6C4—C15—H15B109.5
C3—C4—H4107.6H15A—C15—H15B109.5
C6—C5—C4123.77 (17)C4—C15—H15C109.5
C6—C5—H5118.1H15A—C15—H15C109.5
C4—C5—H5118.1H15B—C15—H15C109.5
C5—C6—C1120.94 (16)O3—C16—H16A109.5
C5—C6—C7120.64 (15)O3—C16—H16B109.5
C1—C6—C7118.33 (15)H16A—C16—H16B109.5
C8—C7—C12117.67 (14)O3—C16—H16C109.5
C8—C7—C6119.05 (14)H16A—C16—H16C109.5
C12—C7—C6123.25 (14)H16B—C16—H16C109.5
C9—C8—C7121.77 (16)
C6—C1—C2—C13164.10 (19)C1—C6—C7—C12−53.0 (2)
C6—C1—C2—C339.0 (2)C12—C7—C8—C90.9 (2)
C1—C2—C3—C14174.85 (16)C6—C7—C8—C9−177.28 (15)
C13—C2—C3—C1451.5 (2)C7—C8—C9—C100.4 (3)
C1—C2—C3—C4−61.4 (2)C8—C9—C10—C11−0.9 (3)
C13—C2—C3—C4175.22 (18)C9—C10—C11—C120.0 (3)
C14—C3—C4—C5172.34 (15)C16—O3—C12—C115.2 (2)
C2—C3—C4—C550.1 (2)C16—O3—C12—C7−172.68 (15)
C14—C3—C4—C15−63.1 (2)C10—C11—C12—O3−176.46 (16)
C2—C3—C4—C15174.67 (15)C10—C11—C12—C71.4 (2)
C15—C4—C5—C6−141.8 (2)C8—C7—C12—O3176.16 (14)
C3—C4—C5—C6−16.6 (3)C6—C7—C12—O3−5.7 (2)
C4—C5—C6—C1−6.3 (3)C8—C7—C12—C11−1.8 (2)
C4—C5—C6—C7170.29 (17)C6—C7—C12—C11176.29 (15)
C2—C1—C6—C5−5.8 (3)C4—C3—C14—O1−56.8 (3)
C2—C1—C6—C7177.46 (16)C2—C3—C14—O166.0 (3)
C5—C6—C7—C8−51.6 (2)C4—C3—C14—O2124.50 (18)
C1—C6—C7—C8125.06 (18)C2—C3—C14—O2−112.68 (19)
C5—C6—C7—C12130.28 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2O···O1i0.88 (3)1.79 (3)2.6640 (18)177 (3)

Symmetry codes: (i) −x+2, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2342).

References

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