2-(m-Tol­yloxy)benzoic acid

Zhang, Z.-F.

doi:10.1107/S1600536811026171

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1935

doi:10.1107/S1600536811026171

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2-(m-Tolyloxy)benzoic acid

Zhi-Fang Zhang ^a ^*

^aSchool of Chemistry and Chemical Engineering, Yulin University, Yulin 719000, People's Republic of China
^*Correspondence e-mail: zhifang889@126.com

(Received 23 June 2011; accepted 1 July 2011; online 6 July 2011)

In the crystal structure of the title compound, C₁₄H₁₂O₃, the molecules form classical O—H⋯O hydrogen-bonded carboxylic acid dimers. The dihedral angle between the two rings is 80.9 (3)°.

Related literature

For related structures, see: Shi et al. (2011 ); Raghunathan et al. (1982 ); Zhang (2011 ). For the synthesis of the title compound, see: Pellon et al. (1995 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₂O₃
M_r = 228.24
Triclinic, $[P \overline 1]$
a = 5.193 (1) Å
b = 7.8000 (16) Å
c = 14.868 (3) Å
α = 94.28 (3)°
β = 97.50 (3)°
γ = 102.54 (3)°
V = 579.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.982, T_max = 0.991
2387 measured reflections
2132 independent reflections
1132 reflections with I > 2σ(I)
R_int = 0.030
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.116
S = 1.00
2132 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O2ⁱ	0.82	1.83	2.648 (2)	176
Symmetry code: (i) -x+2, -y+2, -z+2.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811026171/hg5059sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026171/hg5059Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811026171/hg5059Isup3.cml

checkCIF report

Comment top

Diphenylethers areuseful as herbicides, ignifuges, antiinflammatories and also as intermediatesin the synthesis of xanthones, p-dibenzo-furans, and p-dibenzo-dioxines (Pellon, et al., 1995). Knowledge of the crystal structure of such benzoic acid derivatives gives us not only information about nuclearity of the complex molecule, but is important in understanding the behaviour of these compounds with respect to the mechanisms of pharmacological activities and physiological activities. Therefore, we have synthesized the title compound, (I), and report its crystal structure here.

The molecular structure of (I) is shown in Fig. 1, and the intermolecular O—H···O hydrogen bond (Table 1) results in the formation of carboxylic acid dimers (Fig. 2). The bond lengths are within normal ranges (Allen et al., 1987). Similar crystal structure of some compounds have been reported (Shi et al., 2011; Raghunathan et al., 1982; Zhang et al.., 2011).

In the molecule of (I), the dihedral angle of the rings( C3—C6) and (C8—C13) is 80.9 (3)°, the molecules were connected together via O—H···O intermolecular hydrogen bonds to form dimers, which seems to be very effective in the stabilization of the crystal structure.

Related literature top

For related structures, see: Shi et al. (2011); Raghunathan et al. (1982); Zhang (2011). For the synthesis of the title compound, see: Pellon et al. (1995). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I), was prepared by the method of Ullmann condensation reaction reported in literature (Pellon et al., 1995). A mixture of 2-chlorobenzoic acid (6.26 g; 0.04 mol), m-cresol (8.65 g; 0.08 mol), anhydrous K₂CO₃ (11.04 g; 0.08 mol), pyridine (1.58 g; 0.02 mol), Cu powder (0.2 g) and cuprous iodide (0.2 g) in 25 ml water was kept at reflux for two hours. The mixture was then basified with Na₂CO₃ solution and extracted with diethyl ether. The aqueous solution was acidified with HCl, the precipitated solid was filtered off and disolved in NaOH; the basic solution was filtered (charcoal) and acidified with acetic acid. The 2-(3-tolyloxy)benzoic acid was crystalized from the mixture.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) (thermal ellipsoids are shown at 30% probability levels).
	Fig. 2. The structure of a dimer of (I).

2-(m-Tolyloxy)benzoic acid top

Crystal data top

C₁₄H₁₂O₃	Z = 2
M_r = 228.24	F(000) = 240
Triclinic, P1	D_x = 1.308 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.193 (1) Å	Cell parameters from 25 reflections
b = 7.8000 (16) Å	θ = 9–12°
c = 14.868 (3) Å	µ = 0.09 mm⁻¹
α = 94.28 (3)°	T = 293 K
β = 97.50 (3)°	Block, colourless
γ = 102.54 (3)°	0.20 × 0.20 × 0.10 mm
V = 579.5 (2) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1132 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 25.4°, θ_min = 1.4°
ω/2θ scans	h = 0→6
Absorption correction: ψ scan (North et al., 1968)	k = −9→9
T_min = 0.982, T_max = 0.991	l = −17→17
2387 measured reflections	3 standard reflections every 200 reflections
2132 independent reflections	intensity decay: 1%

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.040P)²] where P = (F_o² + 2F_c²)/3
2132 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₁₄H₁₂O₃	γ = 102.54 (3)°
M_r = 228.24	V = 579.5 (2) Å³
Triclinic, P1	Z = 2
a = 5.193 (1) Å	Mo Kα radiation
b = 7.8000 (16) Å	µ = 0.09 mm⁻¹
c = 14.868 (3) Å	T = 293 K
α = 94.28 (3)°	0.20 × 0.20 × 0.10 mm
β = 97.50 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1132 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.030
T_min = 0.982, T_max = 0.991	3 standard reflections every 200 reflections
2387 measured reflections	intensity decay: 1%
2132 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.00	Δρ_max = 0.12 e Å⁻³
2132 reflections	Δρ_min = −0.12 e Å⁻³
155 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	0.3075 (4)	0.93730 (19)	0.80140 (11)	0.0780 (6)
C1	0.1740 (8)	0.8008 (4)	0.4694 (2)	0.1111 (12)
H1A	0.3613	0.8039	0.4758	0.167*
H1B	0.1429	0.9087	0.4479	0.167*
H1C	0.0778	0.7027	0.4264	0.167*
O2	0.7293 (3)	0.95411 (19)	0.92424 (11)	0.0683 (6)
C2	0.0798 (7)	0.7808 (3)	0.56045 (19)	0.0694 (8)
O3	0.9363 (3)	1.21756 (19)	0.99325 (11)	0.0706 (6)
H3B	1.0355	1.1598	1.0172	0.106*
C3	0.2341 (6)	0.8720 (3)	0.63921 (19)	0.0660 (8)
H3A	0.3994	0.9455	0.6366	0.079*
C4	0.1428 (6)	0.8542 (3)	0.72192 (19)	0.0617 (8)
C5	−0.0968 (6)	0.7484 (3)	0.7283 (2)	0.0720 (8)
H5A	−0.1568	0.7396	0.7844	0.086*
C6	−0.2495 (6)	0.6544 (4)	0.6507 (2)	0.0856 (10)
H6A	−0.4126	0.5789	0.6539	0.103*
C7	−0.1597 (7)	0.6725 (4)	0.5675 (2)	0.0826 (10)
H7A	−0.2652	0.6092	0.5151	0.099*
C8	0.3485 (5)	1.1181 (3)	0.81945 (15)	0.0519 (7)
C9	0.1781 (5)	1.2089 (3)	0.77587 (16)	0.0640 (8)
H9A	0.0352	1.1490	0.7324	0.077*
C10	0.2199 (6)	1.3888 (3)	0.79684 (17)	0.0673 (8)
H10A	0.1049	1.4500	0.7672	0.081*
C11	0.4270 (6)	1.4776 (3)	0.86027 (17)	0.0671 (8)
H11A	0.4544	1.5992	0.8737	0.081*
C12	0.5958 (5)	1.3877 (3)	0.90456 (16)	0.0580 (7)
H12A	0.7366	1.4495	0.9482	0.070*
C13	0.5610 (5)	1.2048 (3)	0.88546 (14)	0.0459 (6)
C14	0.7462 (5)	1.1132 (3)	0.93547 (15)	0.0488 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1006 (15)	0.0443 (9)	0.0743 (12)	0.0174 (10)	−0.0369 (12)	−0.0027 (9)
C1	0.168 (4)	0.092 (2)	0.081 (2)	0.049 (2)	0.014 (2)	0.0103 (19)
O2	0.0736 (13)	0.0455 (9)	0.0766 (12)	0.0160 (9)	−0.0205 (10)	−0.0042 (8)
C2	0.089 (2)	0.0538 (16)	0.0635 (19)	0.0329 (17)	−0.0149 (18)	−0.0047 (14)
O3	0.0756 (13)	0.0522 (10)	0.0735 (12)	0.0157 (10)	−0.0223 (11)	−0.0048 (9)
C3	0.070 (2)	0.0504 (15)	0.0723 (19)	0.0160 (14)	−0.0116 (17)	0.0070 (14)
C4	0.0639 (19)	0.0383 (13)	0.0723 (19)	0.0136 (13)	−0.0245 (16)	−0.0067 (13)
C5	0.070 (2)	0.0588 (16)	0.084 (2)	0.0207 (16)	0.0002 (18)	−0.0067 (15)
C6	0.066 (2)	0.0715 (19)	0.108 (3)	0.0098 (17)	−0.007 (2)	−0.014 (2)
C7	0.081 (2)	0.0577 (17)	0.095 (3)	0.0232 (18)	−0.036 (2)	−0.0216 (17)
C8	0.0642 (17)	0.0412 (12)	0.0474 (14)	0.0131 (13)	−0.0009 (13)	−0.0003 (11)
C9	0.0706 (19)	0.0557 (15)	0.0618 (17)	0.0210 (14)	−0.0129 (15)	0.0011 (13)
C10	0.081 (2)	0.0549 (16)	0.0689 (18)	0.0288 (15)	0.0007 (17)	0.0041 (14)
C11	0.083 (2)	0.0448 (14)	0.0751 (19)	0.0217 (15)	0.0086 (17)	0.0025 (14)
C12	0.0656 (18)	0.0453 (13)	0.0589 (16)	0.0100 (13)	0.0028 (14)	−0.0012 (12)
C13	0.0534 (15)	0.0438 (13)	0.0387 (13)	0.0108 (12)	0.0019 (12)	0.0040 (10)
C14	0.0523 (16)	0.0449 (13)	0.0446 (14)	0.0053 (13)	0.0035 (12)	−0.0012 (11)

Geometric parameters (Å, º) top

O1—C8	1.380 (2)	C5—H5A	0.9300
O1—C4	1.389 (3)	C6—C7	1.384 (4)
C1—C2	1.506 (4)	C6—H6A	0.9300
C1—H1A	0.9600	C7—H7A	0.9300
C1—H1B	0.9600	C8—C9	1.377 (3)
C1—H1C	0.9600	C8—C13	1.390 (3)
O2—C14	1.222 (2)	C9—C10	1.378 (3)
C2—C7	1.365 (4)	C9—H9A	0.9300
C2—C3	1.380 (3)	C10—C11	1.357 (3)
O3—C14	1.304 (2)	C10—H10A	0.9300
O3—H3B	0.8200	C11—C12	1.371 (3)
C3—C4	1.380 (3)	C11—H11A	0.9300
C3—H3A	0.9300	C12—C13	1.401 (3)
C4—C5	1.355 (4)	C12—H12A	0.9300
C5—C6	1.371 (3)	C13—C14	1.476 (3)

C8—O1—C4	118.75 (17)	C2—C7—H7A	119.2
C2—C1—H1A	109.5	C6—C7—H7A	119.2
C2—C1—H1B	109.5	C9—C8—O1	121.0 (2)
H1A—C1—H1B	109.5	C9—C8—C13	121.0 (2)
C2—C1—H1C	109.5	O1—C8—C13	118.0 (2)
H1A—C1—H1C	109.5	C8—C9—C10	119.8 (2)
H1B—C1—H1C	109.5	C8—C9—H9A	120.1
C7—C2—C3	118.2 (3)	C10—C9—H9A	120.1
C7—C2—C1	121.2 (3)	C11—C10—C9	120.7 (2)
C3—C2—C1	120.7 (3)	C11—C10—H10A	119.7
C14—O3—H3B	109.5	C9—C10—H10A	119.7
C2—C3—C4	119.9 (3)	C10—C11—C12	119.9 (2)
C2—C3—H3A	120.1	C10—C11—H11A	120.1
C4—C3—H3A	120.1	C12—C11—H11A	120.1
C5—C4—C3	121.6 (3)	C11—C12—C13	121.4 (2)
C5—C4—O1	118.9 (3)	C11—C12—H12A	119.3
C3—C4—O1	119.3 (3)	C13—C12—H12A	119.3
C4—C5—C6	118.9 (3)	C8—C13—C12	117.2 (2)
C4—C5—H5A	120.5	C8—C13—C14	123.17 (19)
C6—C5—H5A	120.5	C12—C13—C14	119.6 (2)
C5—C6—C7	119.7 (3)	O2—C14—O3	121.7 (2)
C5—C6—H6A	120.2	O2—C14—C13	124.1 (2)
C7—C6—H6A	120.2	O3—C14—C13	114.12 (19)
C2—C7—C6	121.7 (3)

C7—C2—C3—C4	−0.9 (4)	C13—C8—C9—C10	0.9 (4)
C1—C2—C3—C4	179.0 (2)	C8—C9—C10—C11	−0.2 (4)
C2—C3—C4—C5	0.0 (4)	C9—C10—C11—C12	−0.4 (4)
C2—C3—C4—O1	175.7 (2)	C10—C11—C12—C13	0.4 (4)
C8—O1—C4—C5	−110.5 (3)	C9—C8—C13—C12	−0.9 (3)
C8—O1—C4—C3	73.7 (3)	O1—C8—C13—C12	−178.5 (2)
C3—C4—C5—C6	1.3 (4)	C9—C8—C13—C14	178.8 (2)
O1—C4—C5—C6	−174.5 (2)	O1—C8—C13—C14	1.2 (3)
C4—C5—C6—C7	−1.6 (4)	C11—C12—C13—C8	0.2 (4)
C3—C2—C7—C6	0.6 (4)	C11—C12—C13—C14	−179.4 (2)
C1—C2—C7—C6	−179.3 (3)	C8—C13—C14—O2	−0.6 (4)
C5—C6—C7—C2	0.7 (4)	C12—C13—C14—O2	179.0 (2)
C4—O1—C8—C9	18.2 (4)	C8—C13—C14—O3	178.6 (2)
C4—O1—C8—C13	−164.2 (2)	C12—C13—C14—O3	−1.8 (3)
O1—C8—C9—C10	178.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O2ⁱ	0.82	1.83	2.648 (2)	176

Symmetry code: (i) −x+2, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂O₃
M_r	228.24
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.193 (1), 7.8000 (16), 14.868 (3)
α, β, γ (°)	94.28 (3), 97.50 (3), 102.54 (3)
V (Å³)	579.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.982, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2387, 2132, 1132
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.116, 1.00
No. of reflections	2132
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.12

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O2ⁱ	0.82	1.83	2.648 (2)	176

Symmetry code: (i) −x+2, −y+2, −z+2.

Acknowledgements

The author gratefully acknowledges financial support from the Scientific Research Foundation for High-Level Personnel, Yulin University (11 GK03) and the Collaboration Programs of Yulin City and Universities and thanks Professor Hua-Qin Wang of the Analysis Center, Nanjing University, for providing the Enraf–Nonius CAD-4 diffractometer and data set for this research project.

References

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