2-(o-Tol­yloxy)benzoic acid

Xu, J.-Y.; Cheng, W.-H.; Zhu, X.; Gu, D.

doi:10.1107/S1600536811017119

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1394

doi:10.1107/S1600536811017119

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2-(o-Tolyloxy)benzoic acid

Jia-Ying Xu,^a ^* Wei-Hua Cheng,^b Xun Zhu ^b and Dong-ya Gu ^b

^aCollege of Chemical and Biological Engineering, Yancheng Institute of Technology, Yinbing Road No.9 Yancheng, Yancheng 224051, People's Republic of China, and ^bDepartment of Chemical Engineering, Yancheng College of Textile Technology, Yancheng 224005, People's Republic of China
^*Correspondence e-mail: xujiaying-1984@163.com

(Received 28 April 2011; accepted 6 May 2011; online 14 May 2011)

In the crystal structure of the title compound, C₁₄H₁₂O₃, molecules are linked via intermolecular O—H⋯O hydrogen bonds, resulting in dimer formation. The dihedral angle between the two phenyl rings is 76.2 (2)°.

Related literature

For the synthesis, see: Glorius et al. (2009 ); For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₂O₃
M_r = 228.24
Triclinic, $[P \overline 1]$
a = 7.0900 (14) Å
b = 7.4820 (15) Å
c = 12.680 (3) Å
α = 95.34 (3)°
β = 96.36 (3)°
γ = 115.76 (3)°
V = 594.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.974, T_max = 0.991
2382 measured reflections
2190 independent reflections
1437 reflections with I > 2σ(I)
R_int = 0.020
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.178
S = 1.00
2190 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.23 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—H2A⋯O3ⁱ	0.82	1.81	2.624 (3)	172
Symmetry code: (i) -x, -y, -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/S1600536811017119/vm2093sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811017119/vm2093Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811017119/vm2093Isup3.cml

checkCIF report

Comment top

The title compound, 2-(o-tolyloxy)benzoic acid, is an important intermediate in the synthesis of the biaryl moiety, an ubiquitous motif of polymeric materials, ligands, and biologically active compounds (Glorius et al., 2009).

The molecular structure of (I) is shown in Fig. 1, and the hydrogen-bond geometry is given in Table 1. The bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angle between the two phenyl rings C8—C13 and C2—C7 is 76.2 (2) °.

The crystal packing shows dimer formation via O—H···O intermolecular hydrogen bonds, which seems to be very effective in the stabilization of the crystal structure. The molecules are stacked parallel to the b axis direction.

Related literature top

For the synthetis, see: Glorius et al. (2009); For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I) was prepared by a method reported in literature (Glorius et al., 2009). The crystals were obtained by dissolving (I) (0.2 g, 0.87 mmol) in ethanol (25 ml) and evaporating the solvent slowly at room temperature for about 6 d.

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), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram for (I). O—H···O hydrogen bonds are shown by dashed lines.

2-(o-Tolyloxy)benzoic acid top

Crystal data top

C₁₄H₁₂O₃	Z = 2
M_r = 228.24	F(000) = 240
Triclinic, P1	D_x = 1.275 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0900 (14) Å	Cell parameters from 25 reflections
b = 7.4820 (15) Å	θ = 9–14°
c = 12.680 (3) Å	µ = 0.09 mm⁻¹
α = 95.34 (3)°	T = 293 K
β = 96.36 (3)°	Block, colorless
γ = 115.76 (3)°	0.30 × 0.20 × 0.10 mm
V = 594.5 (2) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1437 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
Graphite monochromator	θ_max = 25.4°, θ_min = 1.6°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = −9→8
T_min = 0.974, T_max = 0.991	l = −15→15
2382 measured reflections	3 standard reflections every 200 reflections
2190 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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1P)² + 0.094P] where P = (F_o² + 2F_c²)/3
2190 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₄H₁₂O₃	γ = 115.76 (3)°
M_r = 228.24	V = 594.5 (2) Å³
Triclinic, P1	Z = 2
a = 7.0900 (14) Å	Mo Kα radiation
b = 7.4820 (15) Å	µ = 0.09 mm⁻¹
c = 12.680 (3) Å	T = 293 K
α = 95.34 (3)°	0.30 × 0.20 × 0.10 mm
β = 96.36 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1437 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.020
T_min = 0.974, T_max = 0.991	3 standard reflections every 200 reflections
2382 measured reflections	intensity decay: 1%
2190 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 1.00	Δρ_max = 0.23 e Å⁻³
2190 reflections	Δρ_min = −0.17 e Å⁻³
154 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	0.4820 (3)	0.1177 (2)	0.80889 (14)	0.0712 (5)
C1	0.2152 (6)	0.0560 (7)	0.6153 (4)	0.1589 (19)
H1A	0.1796	−0.0054	0.6782	0.238*
H1B	0.1718	−0.0467	0.5539	0.238*
H1C	0.1434	0.1376	0.6043	0.238*
O2	0.0651 (3)	−0.2020 (3)	0.99961 (15)	0.0772 (6)
H2A	−0.0042	−0.1483	1.0230	0.116*
C2	0.4515 (5)	0.1851 (4)	0.6302 (2)	0.0833 (8)
O3	0.1733 (3)	0.0598 (3)	0.91609 (17)	0.0833 (6)
C3	0.5551 (8)	0.2950 (7)	0.5531 (3)	0.1137 (13)
H3A	0.4763	0.2862	0.4874	0.136*
C4	0.7687 (8)	0.4147 (6)	0.5719 (3)	0.1119 (13)
H4A	0.8334	0.4873	0.5196	0.134*
C5	0.8863 (5)	0.4283 (5)	0.6654 (3)	0.0904 (9)
H5A	1.0323	0.5095	0.6776	0.108*
C6	0.7915 (4)	0.3231 (4)	0.7426 (2)	0.0666 (7)
H6A	0.8727	0.3321	0.8075	0.080*
C7	0.5773 (4)	0.2046 (3)	0.72433 (19)	0.0570 (6)
C8	0.4571 (3)	−0.0695 (3)	0.82224 (18)	0.0533 (6)
C9	0.5732 (4)	−0.1542 (3)	0.7750 (2)	0.0654 (7)
H9A	0.6639	−0.0868	0.7289	0.078*
C10	0.5543 (5)	−0.3372 (4)	0.7963 (2)	0.0735 (7)
H10A	0.6318	−0.3935	0.7642	0.088*
C11	0.4216 (4)	−0.4382 (4)	0.8646 (2)	0.0722 (7)
H11A	0.4096	−0.5619	0.8791	0.087*
C12	0.3066 (4)	−0.3541 (3)	0.91134 (19)	0.0605 (6)
H12A	0.2185	−0.4218	0.9583	0.073*
C13	0.3188 (3)	−0.1708 (3)	0.89020 (17)	0.0497 (5)
C14	0.1800 (3)	−0.0953 (3)	0.93742 (18)	0.0522 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0866 (12)	0.0514 (9)	0.0985 (13)	0.0410 (9)	0.0489 (10)	0.0272 (9)
C1	0.102 (3)	0.141 (4)	0.193 (5)	0.043 (3)	−0.048 (3)	−0.014 (3)
O2	0.0842 (12)	0.0730 (11)	0.1051 (14)	0.0510 (10)	0.0480 (11)	0.0389 (10)
C2	0.092 (2)	0.0775 (18)	0.0812 (19)	0.0452 (16)	−0.0036 (16)	0.0006 (15)
O3	0.0924 (14)	0.0684 (11)	0.1259 (16)	0.0542 (10)	0.0591 (12)	0.0458 (11)
C3	0.174 (4)	0.131 (3)	0.064 (2)	0.099 (3)	−0.001 (2)	0.015 (2)
C4	0.161 (4)	0.127 (3)	0.093 (3)	0.089 (3)	0.065 (3)	0.053 (2)
C5	0.095 (2)	0.083 (2)	0.110 (2)	0.0428 (17)	0.0529 (19)	0.0361 (18)
C6	0.0678 (16)	0.0677 (15)	0.0724 (16)	0.0338 (13)	0.0220 (13)	0.0191 (12)
C7	0.0694 (15)	0.0468 (11)	0.0687 (15)	0.0350 (11)	0.0240 (12)	0.0141 (10)
C8	0.0582 (13)	0.0420 (11)	0.0655 (14)	0.0267 (10)	0.0141 (11)	0.0091 (10)
C9	0.0781 (16)	0.0549 (13)	0.0775 (16)	0.0382 (12)	0.0308 (13)	0.0132 (12)
C10	0.0914 (19)	0.0580 (14)	0.0921 (19)	0.0486 (14)	0.0324 (15)	0.0121 (13)
C11	0.0890 (18)	0.0517 (13)	0.0904 (19)	0.0415 (13)	0.0252 (15)	0.0169 (13)
C12	0.0660 (14)	0.0481 (12)	0.0724 (15)	0.0286 (11)	0.0168 (12)	0.0120 (11)
C13	0.0482 (11)	0.0419 (11)	0.0590 (13)	0.0213 (9)	0.0064 (10)	0.0052 (9)
C14	0.0496 (12)	0.0450 (11)	0.0649 (14)	0.0220 (9)	0.0132 (10)	0.0141 (10)

Geometric parameters (Å, º) top

O1—C8	1.363 (2)	C5—C6	1.363 (4)
O1—C7	1.392 (3)	C5—H5A	0.9300
C1—C2	1.505 (5)	C6—C7	1.364 (3)
C1—H1A	0.9600	C6—H6A	0.9300
C1—H1B	0.9600	C8—C9	1.390 (3)
C1—H1C	0.9600	C8—C13	1.393 (3)
O2—C14	1.272 (2)	C9—C10	1.372 (3)
O2—H2A	0.8200	C9—H9A	0.9300
C2—C7	1.364 (4)	C10—C11	1.375 (4)
C2—C3	1.398 (5)	C10—H10A	0.9300
O3—C14	1.235 (2)	C11—C12	1.376 (3)
C3—C4	1.361 (5)	C11—H11A	0.9300
C3—H3A	0.9300	C12—C13	1.390 (3)
C4—C5	1.340 (5)	C12—H12A	0.9300
C4—H4A	0.9300	C13—C14	1.482 (3)

C8—O1—C7	119.48 (17)	C2—C7—O1	118.9 (2)
C2—C1—H1A	109.5	C6—C7—O1	118.4 (2)
C2—C1—H1B	109.5	O1—C8—C9	121.8 (2)
H1A—C1—H1B	109.5	O1—C8—C13	117.77 (18)
C2—C1—H1C	109.5	C9—C8—C13	120.32 (19)
H1A—C1—H1C	109.5	C10—C9—C8	120.0 (2)
H1B—C1—H1C	109.5	C10—C9—H9A	120.0
C14—O2—H2A	109.5	C8—C9—H9A	120.0
C7—C2—C3	116.0 (3)	C9—C10—C11	120.6 (2)
C7—C2—C1	120.1 (3)	C9—C10—H10A	119.7
C3—C2—C1	123.9 (3)	C11—C10—H10A	119.7
C4—C3—C2	121.5 (3)	C10—C11—C12	119.3 (2)
C4—C3—H3A	119.2	C10—C11—H11A	120.4
C2—C3—H3A	119.2	C12—C11—H11A	120.4
C5—C4—C3	120.4 (3)	C11—C12—C13	121.7 (2)
C5—C4—H4A	119.8	C11—C12—H12A	119.1
C3—C4—H4A	119.8	C13—C12—H12A	119.1
C4—C5—C6	119.9 (3)	C12—C13—C8	118.0 (2)
C4—C5—H5A	120.1	C12—C13—C14	118.97 (19)
C6—C5—H5A	120.1	C8—C13—C14	123.02 (18)
C5—C6—C7	119.8 (3)	O3—C14—O2	122.0 (2)
C5—C6—H6A	120.1	O3—C14—C13	122.05 (19)
C7—C6—H6A	120.1	O2—C14—C13	115.94 (18)
C2—C7—C6	122.3 (2)

C7—C2—C3—C4	−0.3 (5)	O1—C8—C9—C10	175.6 (2)
C1—C2—C3—C4	177.9 (4)	C13—C8—C9—C10	−0.9 (4)
C2—C3—C4—C5	0.7 (6)	C8—C9—C10—C11	−0.3 (4)
C3—C4—C5—C6	−0.5 (5)	C9—C10—C11—C12	0.3 (4)
C4—C5—C6—C7	−0.1 (4)	C10—C11—C12—C13	0.9 (4)
C3—C2—C7—C6	−0.3 (4)	C11—C12—C13—C8	−2.0 (4)
C1—C2—C7—C6	−178.6 (3)	C11—C12—C13—C14	175.9 (2)
C3—C2—C7—O1	172.8 (2)	O1—C8—C13—C12	−174.58 (19)
C1—C2—C7—O1	−5.5 (4)	C9—C8—C13—C12	2.0 (3)
C5—C6—C7—C2	0.5 (4)	O1—C8—C13—C14	7.6 (3)
C5—C6—C7—O1	−172.7 (2)	C9—C8—C13—C14	−175.9 (2)
C8—O1—C7—C2	94.5 (3)	C12—C13—C14—O3	−175.2 (2)
C8—O1—C7—C6	−92.1 (3)	C8—C13—C14—O3	2.6 (4)
C7—O1—C8—C9	18.4 (3)	C12—C13—C14—O2	3.5 (3)
C7—O1—C8—C13	−165.1 (2)	C8—C13—C14—O2	−178.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O3ⁱ	0.82	1.81	2.624 (3)	172

Symmetry code: (i) −x, −y, −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)	7.0900 (14), 7.4820 (15), 12.680 (3)
α, β, γ (°)	95.34 (3), 96.36 (3), 115.76 (3)
V (Å³)	594.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.974, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2382, 2190, 1437
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.178, 1.00
No. of reflections	2190
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.17

Computer programs: CAD-4 Software (Enraf–Nonius,1985), 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
O2—H2A···O3ⁱ	0.82	1.81	2.624 (3)	172

Symmetry code: (i) −x, −y, −z+2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Glorius, F., Piel, I. & Wang, C. Y. (2009). J. Am. Chem. Soc. 131, 4194–4195. Web of Science PubMed Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar