organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

2-(m-Tol­yl­oxy)benzoic acid

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[Shi, L., Zhang, Q., Xiao, Q., Wu, T. & Zhu, H.-J. (2011). Acta Cryst. E67, o748.]); Raghunathan et al. (1982[Raghunathan, S., Chandrasekhar, K. & Pattabhi, V. (1982). Acta Cryst. B38, 2536-2538.]); Zhang (2011[Zhang, Z.-F. (2011). Acta Cryst. E67, o1078.]). For the synthesis of the title compound, see: Pellon et al. (1995[Pellon, R. F., Carrasco, R., Millian, V. & Rodes, L. (1995). Synth. Commun. 25, 1077-1083.]). For bond-length data, see: Allen et al. (1987[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.]).

[Scheme 1]

Experimental

Crystal data
  • C14H12O3

  • Mr = 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[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.982, Tmax = 0.991

  • 2387 measured reflections

  • 2132 independent reflections

  • 1132 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.12 e Å−3

  • Δρmin = −0.12 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Enraf-Nonius (1985). CAD-4 Software. Enraf-Nonius, Delft, The Netherlands.]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995[Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

H atoms were positioned geometrically and refined as riding groups, with O—H = 0.82 and C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.2 for aromatic H, and x = 1.5 for other H.

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
[Figure 1] Fig. 1. The molecular structure of (I) (thermal ellipsoids are shown at 30% probability levels).
[Figure 2] Fig. 2. The structure of a dimer of (I).
2-(m-Tolyloxy)benzoic acid top
Crystal data top
C14H12O3Z = 2
Mr = 228.24F(000) = 240
Triclinic, P1Dx = 1.308 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.193 (1) ÅCell parameters from 25 reflections
b = 7.8000 (16) Åθ = 9–12°
c = 14.868 (3) ŵ = 0.09 mm1
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 tubeRint = 0.030
Graphite monochromatorθmax = 25.4°, θmin = 1.4°
ω/2θ scansh = 06
Absorption correction: ψ scan
(North et al., 1968)
k = 99
Tmin = 0.982, Tmax = 0.991l = 1717
2387 measured reflections3 standard reflections every 200 reflections
2132 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.040P)2]
where P = (Fo2 + 2Fc2)/3
2132 reflections(Δ/σ)max < 0.001
155 parametersΔρmax = 0.12 e Å3
0 restraintsΔρmin = 0.12 e Å3
Crystal data top
C14H12O3γ = 102.54 (3)°
Mr = 228.24V = 579.5 (2) Å3
Triclinic, P1Z = 2
a = 5.193 (1) ÅMo Kα radiation
b = 7.8000 (16) ŵ = 0.09 mm1
c = 14.868 (3) ÅT = 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)
Rint = 0.030
Tmin = 0.982, Tmax = 0.9913 standard reflections every 200 reflections
2387 measured reflections intensity decay: 1%
2132 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.00Δρmax = 0.12 e Å3
2132 reflectionsΔρmin = 0.12 e Å3
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
xyzUiso*/Ueq
O10.3075 (4)0.93730 (19)0.80140 (11)0.0780 (6)
C10.1740 (8)0.8008 (4)0.4694 (2)0.1111 (12)
H1A0.36130.80390.47580.167*
H1B0.14290.90870.44790.167*
H1C0.07780.70270.42640.167*
O20.7293 (3)0.95411 (19)0.92424 (11)0.0683 (6)
C20.0798 (7)0.7808 (3)0.56045 (19)0.0694 (8)
O30.9363 (3)1.21756 (19)0.99325 (11)0.0706 (6)
H3B1.03551.15981.01720.106*
C30.2341 (6)0.8720 (3)0.63921 (19)0.0660 (8)
H3A0.39940.94550.63660.079*
C40.1428 (6)0.8542 (3)0.72192 (19)0.0617 (8)
C50.0968 (6)0.7484 (3)0.7283 (2)0.0720 (8)
H5A0.15680.73960.78440.086*
C60.2495 (6)0.6544 (4)0.6507 (2)0.0856 (10)
H6A0.41260.57890.65390.103*
C70.1597 (7)0.6725 (4)0.5675 (2)0.0826 (10)
H7A0.26520.60920.51510.099*
C80.3485 (5)1.1181 (3)0.81945 (15)0.0519 (7)
C90.1781 (5)1.2089 (3)0.77587 (16)0.0640 (8)
H9A0.03521.14900.73240.077*
C100.2199 (6)1.3888 (3)0.79684 (17)0.0673 (8)
H10A0.10491.45000.76720.081*
C110.4270 (6)1.4776 (3)0.86027 (17)0.0671 (8)
H11A0.45441.59920.87370.081*
C120.5958 (5)1.3877 (3)0.90456 (16)0.0580 (7)
H12A0.73661.44950.94820.070*
C130.5610 (5)1.2048 (3)0.88546 (14)0.0459 (6)
C140.7462 (5)1.1132 (3)0.93547 (15)0.0488 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.1006 (15)0.0443 (9)0.0743 (12)0.0174 (10)0.0369 (12)0.0027 (9)
C10.168 (4)0.092 (2)0.081 (2)0.049 (2)0.014 (2)0.0103 (19)
O20.0736 (13)0.0455 (9)0.0766 (12)0.0160 (9)0.0205 (10)0.0042 (8)
C20.089 (2)0.0538 (16)0.0635 (19)0.0329 (17)0.0149 (18)0.0047 (14)
O30.0756 (13)0.0522 (10)0.0735 (12)0.0157 (10)0.0223 (11)0.0048 (9)
C30.070 (2)0.0504 (15)0.0723 (19)0.0160 (14)0.0116 (17)0.0070 (14)
C40.0639 (19)0.0383 (13)0.0723 (19)0.0136 (13)0.0245 (16)0.0067 (13)
C50.070 (2)0.0588 (16)0.084 (2)0.0207 (16)0.0002 (18)0.0067 (15)
C60.066 (2)0.0715 (19)0.108 (3)0.0098 (17)0.007 (2)0.014 (2)
C70.081 (2)0.0577 (17)0.095 (3)0.0232 (18)0.036 (2)0.0216 (17)
C80.0642 (17)0.0412 (12)0.0474 (14)0.0131 (13)0.0009 (13)0.0003 (11)
C90.0706 (19)0.0557 (15)0.0618 (17)0.0210 (14)0.0129 (15)0.0011 (13)
C100.081 (2)0.0549 (16)0.0689 (18)0.0288 (15)0.0007 (17)0.0041 (14)
C110.083 (2)0.0448 (14)0.0751 (19)0.0217 (15)0.0086 (17)0.0025 (14)
C120.0656 (18)0.0453 (13)0.0589 (16)0.0100 (13)0.0028 (14)0.0012 (12)
C130.0534 (15)0.0438 (13)0.0387 (13)0.0108 (12)0.0019 (12)0.0040 (10)
C140.0523 (16)0.0449 (13)0.0446 (14)0.0053 (13)0.0035 (12)0.0012 (11)
Geometric parameters (Å, º) top
O1—C81.380 (2)C5—H5A0.9300
O1—C41.389 (3)C6—C71.384 (4)
C1—C21.506 (4)C6—H6A0.9300
C1—H1A0.9600C7—H7A0.9300
C1—H1B0.9600C8—C91.377 (3)
C1—H1C0.9600C8—C131.390 (3)
O2—C141.222 (2)C9—C101.378 (3)
C2—C71.365 (4)C9—H9A0.9300
C2—C31.380 (3)C10—C111.357 (3)
O3—C141.304 (2)C10—H10A0.9300
O3—H3B0.8200C11—C121.371 (3)
C3—C41.380 (3)C11—H11A0.9300
C3—H3A0.9300C12—C131.401 (3)
C4—C51.355 (4)C12—H12A0.9300
C5—C61.371 (3)C13—C141.476 (3)
C8—O1—C4118.75 (17)C2—C7—H7A119.2
C2—C1—H1A109.5C6—C7—H7A119.2
C2—C1—H1B109.5C9—C8—O1121.0 (2)
H1A—C1—H1B109.5C9—C8—C13121.0 (2)
C2—C1—H1C109.5O1—C8—C13118.0 (2)
H1A—C1—H1C109.5C8—C9—C10119.8 (2)
H1B—C1—H1C109.5C8—C9—H9A120.1
C7—C2—C3118.2 (3)C10—C9—H9A120.1
C7—C2—C1121.2 (3)C11—C10—C9120.7 (2)
C3—C2—C1120.7 (3)C11—C10—H10A119.7
C14—O3—H3B109.5C9—C10—H10A119.7
C2—C3—C4119.9 (3)C10—C11—C12119.9 (2)
C2—C3—H3A120.1C10—C11—H11A120.1
C4—C3—H3A120.1C12—C11—H11A120.1
C5—C4—C3121.6 (3)C11—C12—C13121.4 (2)
C5—C4—O1118.9 (3)C11—C12—H12A119.3
C3—C4—O1119.3 (3)C13—C12—H12A119.3
C4—C5—C6118.9 (3)C8—C13—C12117.2 (2)
C4—C5—H5A120.5C8—C13—C14123.17 (19)
C6—C5—H5A120.5C12—C13—C14119.6 (2)
C5—C6—C7119.7 (3)O2—C14—O3121.7 (2)
C5—C6—H6A120.2O2—C14—C13124.1 (2)
C7—C6—H6A120.2O3—C14—C13114.12 (19)
C2—C7—C6121.7 (3)
C7—C2—C3—C40.9 (4)C13—C8—C9—C100.9 (4)
C1—C2—C3—C4179.0 (2)C8—C9—C10—C110.2 (4)
C2—C3—C4—C50.0 (4)C9—C10—C11—C120.4 (4)
C2—C3—C4—O1175.7 (2)C10—C11—C12—C130.4 (4)
C8—O1—C4—C5110.5 (3)C9—C8—C13—C120.9 (3)
C8—O1—C4—C373.7 (3)O1—C8—C13—C12178.5 (2)
C3—C4—C5—C61.3 (4)C9—C8—C13—C14178.8 (2)
O1—C4—C5—C6174.5 (2)O1—C8—C13—C141.2 (3)
C4—C5—C6—C71.6 (4)C11—C12—C13—C80.2 (4)
C3—C2—C7—C60.6 (4)C11—C12—C13—C14179.4 (2)
C1—C2—C7—C6179.3 (3)C8—C13—C14—O20.6 (4)
C5—C6—C7—C20.7 (4)C12—C13—C14—O2179.0 (2)
C4—O1—C8—C918.2 (4)C8—C13—C14—O3178.6 (2)
C4—O1—C8—C13164.2 (2)C12—C13—C14—O31.8 (3)
O1—C8—C9—C10178.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3B···O2i0.821.832.648 (2)176
Symmetry code: (i) x+2, y+2, z+2.

Experimental details

Crystal data
Chemical formulaC14H12O3
Mr228.24
Crystal system, space groupTriclinic, 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)
V3)579.5 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.20 × 0.20 × 0.10
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.982, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
2387, 2132, 1132
Rint0.030
(sin θ/λ)max1)0.603
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.116, 1.00
No. of reflections2132
No. of parameters155
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O3—H3B···O2i0.821.832.648 (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

First citationAllen, 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
First citationEnraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.  Google Scholar
First citationHarms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.  Google Scholar
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science Google Scholar
First citationPellon, R. F., Carrasco, R., Millian, V. & Rodes, L. (1995). Synth. Commun. 25, 1077–1083.  CAS Google Scholar
First citationRaghunathan, S., Chandrasekhar, K. & Pattabhi, V. (1982). Acta Cryst. B38, 2536–2538.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationShi, L., Zhang, Q., Xiao, Q., Wu, T. & Zhu, H.-J. (2011). Acta Cryst. E67, o748.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationZhang, Z.-F. (2011). Acta Cryst. E67, o1078.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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