Acta Cryst. (2008). E64, o741 [ doi:10.1107/S1600536808007381 ]
The title compound, C14H18O3, is an important model compound in the synthesis of phenolic ethers. The cyclohexane ring adopts a chair conformation. In the crystal structure, adjacent molecules are linked by O-H
O hydrogen bonds.
Methyl trans-4-(tosylmethyl)cyclohexanecarboxylate(3.26 g, 10 mmol), phenol(2.82 g, 30 mmol) and potassium phosphate(10.6 g, 50 mmol) were suspended in dry DMF(20 mL) and heated at 368 K for 6 h, then 30 mL water and 30 mL toluene were added to the mixture. The water layer separated was washed twice with toluene and the organic layer combined was washed with water and then dried with sodium sulfate. After filtration and concentration, the crude product was obtained which was further purified by silica gel column chromatography to give pure methyl ester. The ester was hydrolyzed in a mixed solution of 10 mL e thanol and 15 mL 1 N NaOH solution for 5 h at 313 K, after cooling and acidification with hydrochloride the white solid precipitated was collected. Colorless crystals were obtained by slow evaporation in a ethanol-water(4:1) solution at room temperature.
H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C).
Data collection: DIFRAC (Gabe et al., 1993); cell refinement: DIFRAC (Gabe et al., 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./bv2092fig1thm.gif)
| Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. |
| C14H18O3 | F(000) = 504 |
| Mr = 234.28 | Dx = 1.205 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 6.178 (3) Å | Cell parameters from 30 reflections |
| b = 35.042 (8) Å | θ = 4.5–9.5° |
| c = 6.526 (3) Å | µ = 0.08 mm−1 |
| β = 113.93 (4)° | T = 292 K |
| V = 1291.4 (9) Å3 | Block, colourless |
| Z = 4 | 0.45 × 0.25 × 0.24 mm |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.001 |
| Radiation source: fine-focus sealed tube | θmax = 25.5°, θmin = 3.5° |
| graphite | h = −7→6 |
| ω/2–θ scans | k = 0→42 |
| 2657 measured reflections | l = −1→7 |
| 2330 independent reflections | 3 standard reflections every 250 reflections |
| 1301 reflections with I > 2σ(I) | intensity decay: 1.8% |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.072 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.149 | H-atom parameters constrained |
| S = 0.97 | w = 1/[σ2(Fo2) + (0.0395P)2] where P = (Fo2 + 2Fc2)/3 |
| 2330 reflections | (Δ/σ)max < 0.001 |
| 156 parameters | Δρmax = 0.17 e Å−3 |
| 9 restraints | Δρmin = −0.17 e Å−3 |
| C14H18O3 | V = 1291.4 (9) Å3 |
| Mr = 234.28 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 6.178 (3) Å | µ = 0.08 mm−1 |
| b = 35.042 (8) Å | T = 292 K |
| c = 6.526 (3) Å | 0.45 × 0.25 × 0.24 mm |
| β = 113.93 (4)° |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.001 |
| 2657 measured reflections | θmax = 25.5° |
| 2330 independent reflections | 3 standard reflections every 250 reflections |
| 1301 reflections with I > 2σ(I) | intensity decay: 1.8% |
| R[F2 > 2σ(F2)] = 0.072 | H-atom parameters constrained |
| wR(F2) = 0.149 | Δρmax = 0.17 e Å−3 |
| S = 0.97 | Δρmin = −0.17 e Å−3 |
| 2330 reflections | Absolute structure: ? |
| 156 parameters | Flack parameter: ? |
| 9 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.5351 (13) | 0.8410 (2) | −0.0641 (11) | 0.084 (2) | |
| O2 | 1.0653 (15) | 0.9709 (3) | 0.8119 (13) | 0.110 (3) | |
| H2 | 1.1166 | 0.9870 | 0.9115 | 0.132* | |
| O3 | 0.7287 (14) | 0.9889 (2) | 0.8198 (11) | 0.104 (3) | |
| C1 | 0.584 (2) | 0.8016 (3) | −0.328 (2) | 0.087 (4) | |
| H1 | 0.7444 | 0.8012 | −0.2354 | 0.105* | |
| C2 | 0.494 (4) | 0.7816 (4) | −0.531 (3) | 0.112 (6) | |
| H2A | 0.5971 | 0.7680 | −0.5758 | 0.134* | |
| C3 | 0.260 (4) | 0.7818 (4) | −0.662 (3) | 0.117 (6) | |
| H3 | 0.2030 | 0.7679 | −0.7951 | 0.141* | |
| C4 | 0.103 (3) | 0.8026 (4) | −0.6030 (19) | 0.102 (5) | |
| H4 | −0.0571 | 0.8032 | −0.6962 | 0.123* | |
| C5 | 0.192 (3) | 0.8225 (3) | −0.3991 (19) | 0.085 (4) | |
| H5 | 0.0893 | 0.8360 | −0.3543 | 0.102* | |
| C6 | 0.425 (3) | 0.8221 (3) | −0.268 (2) | 0.074 (4) | |
| C7 | 0.3845 (19) | 0.8640 (3) | 0.0058 (16) | 0.080 (4) | |
| H7A | 0.2653 | 0.8483 | 0.0257 | 0.096* | |
| H7B | 0.3052 | 0.8834 | −0.1060 | 0.096* | |
| C8 | 0.5426 (19) | 0.8826 (3) | 0.2262 (15) | 0.062 (3) | |
| H8 | 0.6310 | 0.8625 | 0.3314 | 0.074* | |
| C9 | 0.3865 (17) | 0.9033 (3) | 0.3227 (15) | 0.076 (4) | |
| H9A | 0.2912 | 0.9223 | 0.2163 | 0.092* | |
| H9B | 0.2802 | 0.8852 | 0.3460 | 0.092* | |
| C10 | 0.5351 (19) | 0.9225 (3) | 0.5425 (15) | 0.076 (4) | |
| H10A | 0.4323 | 0.9360 | 0.5975 | 0.092* | |
| H10B | 0.6210 | 0.9033 | 0.6524 | 0.092* | |
| C11 | 0.7078 (19) | 0.9501 (3) | 0.5158 (16) | 0.066 (3) | |
| H11 | 0.6143 | 0.9689 | 0.4037 | 0.079* | |
| C12 | 0.8661 (18) | 0.9296 (3) | 0.4193 (15) | 0.075 (3) | |
| H12A | 0.9704 | 0.9480 | 0.3942 | 0.091* | |
| H12B | 0.9635 | 0.9108 | 0.5261 | 0.091* | |
| C13 | 0.7164 (19) | 0.9100 (3) | 0.2005 (16) | 0.077 (3) | |
| H13A | 0.6310 | 0.9292 | 0.0898 | 0.092* | |
| H13B | 0.8191 | 0.8964 | 0.1460 | 0.092* | |
| C14 | 0.842 (2) | 0.9717 (4) | 0.7277 (17) | 0.073 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.102 (6) | 0.090 (6) | 0.065 (5) | −0.001 (5) | 0.040 (5) | −0.021 (5) |
| O2 | 0.103 (7) | 0.143 (9) | 0.085 (6) | 0.002 (7) | 0.040 (6) | −0.046 (5) |
| O3 | 0.109 (7) | 0.127 (8) | 0.083 (6) | 0.020 (6) | 0.046 (5) | −0.031 (5) |
| C1 | 0.120 (12) | 0.073 (9) | 0.093 (9) | 0.000 (8) | 0.068 (9) | −0.004 (8) |
| C2 | 0.179 (18) | 0.097 (12) | 0.102 (12) | −0.012 (13) | 0.100 (13) | −0.017 (10) |
| C3 | 0.20 (2) | 0.099 (12) | 0.078 (11) | −0.008 (14) | 0.078 (13) | −0.007 (9) |
| C4 | 0.152 (14) | 0.093 (11) | 0.070 (9) | −0.011 (10) | 0.052 (10) | −0.013 (8) |
| C5 | 0.114 (12) | 0.088 (10) | 0.058 (8) | 0.000 (9) | 0.038 (8) | −0.009 (8) |
| C6 | 0.108 (12) | 0.063 (9) | 0.063 (8) | 0.000 (9) | 0.045 (9) | 0.002 (7) |
| C7 | 0.098 (9) | 0.090 (9) | 0.066 (7) | −0.006 (8) | 0.049 (7) | −0.010 (7) |
| C8 | 0.080 (8) | 0.056 (8) | 0.051 (6) | 0.001 (7) | 0.029 (6) | −0.004 (6) |
| C9 | 0.088 (9) | 0.095 (10) | 0.061 (7) | −0.013 (7) | 0.045 (7) | −0.013 (7) |
| C10 | 0.096 (9) | 0.090 (9) | 0.062 (7) | −0.025 (8) | 0.052 (7) | −0.021 (7) |
| C11 | 0.084 (9) | 0.065 (8) | 0.050 (6) | 0.005 (7) | 0.030 (6) | −0.010 (6) |
| C12 | 0.088 (9) | 0.079 (9) | 0.067 (7) | −0.012 (7) | 0.039 (7) | −0.011 (7) |
| C13 | 0.089 (9) | 0.098 (10) | 0.059 (7) | −0.013 (8) | 0.044 (7) | −0.017 (7) |
| C14 | 0.068 (9) | 0.102 (10) | 0.055 (7) | 0.013 (9) | 0.030 (7) | 0.004 (7) |
| O1—C6 | 1.394 (12) | C7—H7B | 0.9700 |
| O1—C7 | 1.438 (10) | C8—C13 | 1.501 (12) |
| O2—C14 | 1.261 (11) | C8—C9 | 1.532 (11) |
| O2—H2 | 0.8200 | C8—H8 | 0.9800 |
| O3—C14 | 1.248 (11) | C9—C10 | 1.512 (12) |
| C1—C6 | 1.392 (14) | C9—H9A | 0.9700 |
| C1—C2 | 1.401 (16) | C9—H9B | 0.9700 |
| C1—H1 | 0.9300 | C10—C11 | 1.501 (12) |
| C2—C3 | 1.350 (18) | C10—H10A | 0.9700 |
| C2—H2A | 0.9300 | C10—H10B | 0.9700 |
| C3—C4 | 1.386 (17) | C11—C14 | 1.497 (13) |
| C3—H3 | 0.9300 | C11—C12 | 1.540 (12) |
| C4—C5 | 1.402 (13) | C11—H11 | 0.9800 |
| C4—H4 | 0.9300 | C12—C13 | 1.514 (12) |
| C5—C6 | 1.341 (14) | C12—H12A | 0.9700 |
| C5—H5 | 0.9300 | C12—H12B | 0.9700 |
| C7—C8 | 1.519 (12) | C13—H13A | 0.9700 |
| C7—H7A | 0.9700 | C13—H13B | 0.9700 |
| C6—O1—C7 | 116.2 (9) | C10—C9—H9A | 109.4 |
| C14—O2—H2 | 109.5 | C8—C9—H9A | 109.4 |
| C6—C1—C2 | 118.1 (14) | C10—C9—H9B | 109.4 |
| C6—C1—H1 | 120.9 | C8—C9—H9B | 109.4 |
| C2—C1—H1 | 120.9 | H9A—C9—H9B | 108.0 |
| C3—C2—C1 | 120.5 (16) | C11—C10—C9 | 111.3 (8) |
| C3—C2—H2A | 119.8 | C11—C10—H10A | 109.4 |
| C1—C2—H2A | 119.8 | C9—C10—H10A | 109.4 |
| C2—C3—C4 | 121.1 (16) | C11—C10—H10B | 109.4 |
| C2—C3—H3 | 119.5 | C9—C10—H10B | 109.4 |
| C4—C3—H3 | 119.5 | H10A—C10—H10B | 108.0 |
| C3—C4—C5 | 118.5 (14) | C14—C11—C10 | 111.9 (8) |
| C3—C4—H4 | 120.7 | C14—C11—C12 | 114.1 (10) |
| C5—C4—H4 | 120.7 | C10—C11—C12 | 110.2 (8) |
| C6—C5—C4 | 120.3 (12) | C14—C11—H11 | 106.7 |
| C6—C5—H5 | 119.8 | C10—C11—H11 | 106.7 |
| C4—C5—H5 | 119.8 | C12—C11—H11 | 106.7 |
| C5—C6—C1 | 121.5 (12) | C13—C12—C11 | 110.5 (9) |
| C5—C6—O1 | 125.9 (11) | C13—C12—H12A | 109.5 |
| C1—C6—O1 | 112.7 (13) | C11—C12—H12A | 109.5 |
| O1—C7—C8 | 106.9 (9) | C13—C12—H12B | 109.5 |
| O1—C7—H7A | 110.3 | C11—C12—H12B | 109.5 |
| C8—C7—H7A | 110.3 | H12A—C12—H12B | 108.1 |
| O1—C7—H7B | 110.3 | C8—C13—C12 | 112.1 (7) |
| C8—C7—H7B | 110.3 | C8—C13—H13A | 109.2 |
| H7A—C7—H7B | 108.6 | C12—C13—H13A | 109.2 |
| C13—C8—C7 | 112.5 (8) | C8—C13—H13B | 109.2 |
| C13—C8—C9 | 109.9 (8) | C12—C13—H13B | 109.2 |
| C7—C8—C9 | 108.8 (9) | H13A—C13—H13B | 107.9 |
| C13—C8—H8 | 108.5 | O3—C14—O2 | 122.0 (11) |
| C7—C8—H8 | 108.5 | O3—C14—C11 | 118.6 (11) |
| C9—C8—H8 | 108.5 | O2—C14—C11 | 119.4 (11) |
| C10—C9—C8 | 111.1 (8) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O3i | 0.82 | 1.83 | 2.626 (10) | 164. |
| Symmetry codes: (i) −x+2, −y+2, −z+2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O3i | 0.82 | 1.83 | 2.626 (10) | 164. |
| Symmetry codes: (i) −x+2, −y+2, −z+2. |
Dunitz, J. D. & Strickler, P. (1966). Helv. Chim. Acta, 49, 290–291.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387.
Gabe, E. J., White, P. S. & Enright, G. D. (1993). DIFRAC. Pittsburgh Meeting Abstract, PA 104. American Crystallographic Association, Buffalo, New York, USA.
Luger, P., Plieth, K. & Ruban, G. (1972). Acta Cryst. B28, 706–710.
Sekera, V. C. & Marvel, C. S. (1933). J. Am. Chem. Soc. B55, 345–349.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
To compare the activity of 4-chloromethyl cyclohexane and 4-(tosyloxymethyl)cyclohexane, some cyclohexane derivatives were designed to be linked to substituted phenol. Thus the title compound, a trans-4-(phenoxymethyl)cyclohexanecarboxylic acid was synthesized (Sekera & Marvel,1933). We report here the crystal structure of the title compound. The cyclohexane ring of the title compound adopts a chair conformation. The average C—C bond length of the cyclohexane ring is 1.517 (12) Å, is similar to that of trans-1,4-cyclohexanedicarboxylic acid (1.523 (3) Å, Luger et al., 1972). The mean endocyclic angle of the cyclohexane is 110.9 (8)°, which is in the range observed for cyclohexane rings (111.4 (4)°, Dunitz & Strickler, 1966).