trans-4-(Phenoxy­meth­yl)cyclo­hexane­carboxylic acid

Yang, J.; Qi, Q.-R.; Huang, W.-C.; Zheng, H.

doi:10.1107/S1600536808007381

organic compounds

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Volume 64| Part 4| April 2008| Page o741

doi:10.1107/S1600536808007381

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trans-4-(Phenoxymethyl)cyclohexanecarboxylic acid

Jun Yang,^a Qing-Rong Qi,^a Wen-Cai Huang ^b and Hu Zheng ^a ^*

^aDepartment of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, People's Republic of China, and ^bDepartment of Pharmaceuticals and Bioengineering, School of Chemical Engineering, Sichuan University, Chengdu 610065, People's Republic of China
^*Correspondence e-mail: wcums416@yahoo.com.cn

(Received 17 January 2008; accepted 18 March 2008; online 29 March 2008)

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.

Related literature

For related literature, see: Dunitz & Strickler (1966 ); Sekera & Marvel (1933 ); Luger et al. (1972 ).

Experimental

Crystal data

C₁₄H₁₈O₃
M_r = 234.28
Monoclinic, P 2₁ /c
a = 6.178 (3) Å
b = 35.042 (8) Å
c = 6.526 (3) Å
β = 113.93 (4)°
V = 1291.4 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 292 (2) K
0.45 × 0.25 × 0.24 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2657 measured reflections
2330 independent reflections
1301 reflections with I > 2σ(I)
R_int = 0.001
3 standard reflections every 250 reflections intensity decay: 1.8%

Refinement

R[F² > 2σ(F²)] = 0.072
wR(F²) = 0.149
S = 0.97
2330 reflections
156 parameters
9 restraints
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3ⁱ	0.82	1.83	2.626 (10)	164
Symmetry code: (i) -x+2, -y+2, -z+2.

Data collection: DIFRAC (Gabe et al., 1993 ); cell refinement: DIFRAC; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808007381/bv2092sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808007381/bv2092Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

For related literature, see: Dunitz & Strickler (1966); Sekera & Marvel (1933); Luger et al. (1972).

Experimental top

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.

Computing details top

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).

Figures top

Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level.

trans-4-(Phenoxymethyl)cyclohexanecarboxylic acid top

Crystal data top

C₁₄H₁₈O₃	F(000) = 504
M_r = 234.28	D_x = 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

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.001
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 3.5°
Graphite monochromator	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 top

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(F_o²) + (0.0395P)²] where P = (F_o² + 2F_c²)/3
2330 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.17 e Å⁻³
9 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₄H₁₈O₃	V = 1291.4 (9) Å³
M_r = 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)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.001
2657 measured reflections	3 standard reflections every 250 reflections
2330 independent reflections	intensity decay: 1.8%
1301 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.072	9 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 0.97	Δρ_max = 0.17 e Å⁻³
2330 reflections	Δρ_min = −0.17 e Å⁻³
156 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3ⁱ	0.82	1.83	2.626 (10)	164

Symmetry code: (i) −x+2, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₈O₃
M_r	234.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	292
a, b, c (Å)	6.178 (3), 35.042 (8), 6.526 (3)
β (°)	113.93 (4)
V (Å³)	1291.4 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.45 × 0.25 × 0.24

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2657, 2330, 1301
R_int	0.001
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.149, 0.97
No. of reflections	2330
No. of parameters	156
No. of restraints	9
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.17

Computer programs: DIFRAC (Gabe et al., 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3ⁱ	0.82	1.83	2.626 (10)	163.9

Symmetry code: (i) −x+2, −y+2, −z+2.

References

Dunitz, J. D. & Strickler, P. (1966). Helv. Chim. Acta, 49, 290–291. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387. CrossRef CAS Web of Science IUCr Journals Google Scholar
Gabe, E. J., White, P. S. & Enright, G. D. (1993). DIFRAC. Pittsburgh Meeting Abstract, PA 104. American Crystallographic Association, Buffalo, New York, USA. Google Scholar
Luger, P., Plieth, K. & Ruban, G. (1972). Acta Cryst. B28, 706–710. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Sekera, V. C. & Marvel, C. S. (1933). J. Am. Chem. Soc. B55, 345–349. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o741

doi:10.1107/S1600536808007381

Open

access