trans-4-(Phenoxy­meth­yl)cyclo­hexane­carboxylic acid

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.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.018 Å
• R factor = 0.073
• wR factor = 0.150
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT340_ALERT_3_B Low Bond Precision on C-C Bonds (x 1000) Ang ...         18

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C14
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.14

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Computing details

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

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

trans-4-(Phenoxymethyl)cyclohexanecarboxylic acid

Crystal data

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) Å^3	Block, colourless
Z = 4	0.45 × 0.25 × 0.24 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.001
Radiation source: fine-focus sealed tube	θmax = 25.5°, θmin = 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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0395P)^2] where P = (Fo^2 + 2Fc^2)/3
2330 reflections	(Δ/σ)max < 0.001
156 parameters	Δρmax = 0.17 e Å^−3
9 restraints	Δρmin = −0.17 e Å^−3

Special details

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 (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3^i	0.82	1.83	2.626 (10)	164

Symmetry code: (i) −x+2, −y+2, −z+2.