2-(2-Chloro­phen­oxy)benzoic acid

Shi, L.; Zhang, Q.; Xiao, Q.; Wu, T.; Zhu, H.-J.

doi:10.1107/S1600536811006301

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o748

doi:10.1107/S1600536811006301

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2-(2-Chlorophenoxy)benzoic acid

Lu Shi,^a Qin Zhang,^a Qi Xiao,^a Tao Wu ^a and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhuhjnjut@hotmail.com

(Received 10 February 2011; accepted 19 February 2011; online 2 March 2011)

In the crystal structure of the title compound, C₁₃H₉ClO₃, the molecules form classical O—H⋯O hydrogen-bonded carboxylic acid dimers. These dimers are linked by C—H⋯π interactions into a three-dimensional network. The benzene rings are oriented at a dihedral angle of 77.8 (1)°.

Related literature

For applications of the title compound, see: Yang et al. (1972 ). For a related structure, see: Parkin et al. (2005 ). For the synthesis of the title compound, see: Rolando et al. (1995 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₃H₉ClO₃
M_r = 248.65
Monoclinic, P 2₁ /c
a = 6.9930 (14) Å
b = 24.986 (5) Å
c = 7.5140 (15) Å
β = 115.79 (3)°
V = 1182.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.32 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 = 0.912, T_max = 0.969
4651 measured reflections
2177 independent reflections
1061 reflections with I > 2σ(I)
R_int = 0.088
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.110
S = 1.01
2177 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2B⋯O3ⁱ	0.82	1.81	2.621 (3)	172
C11—H11A⋯Cg1ⁱⁱ	0.93	2.74	3.582 (4)	151
Symmetry codes: (i) -x, -y+2, -z; (ii) x, y, z-1.

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/S1600536811006301/bq2280sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811006301/bq2280Isup2.hkl

checkCIF report

Comment top

The tittle compound, 2-(2-chlorophenoxy)benzoic acid is an important intermediate (Yang et al., 1972). And we report here the crystal structure of the title compound, (I).

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 and angles are within normal ranges (Allen et al., 1987).

In the molecule of (I), the dihedral angle of the rings (C1—C6) and (C7—C12) is 77.8 (1)°. The O atom lies in the bonded benzene ring planes, and Cl atom is connected with the phenyl ring (C1—C6).

In the crystal of (I), the molecules were connected together via O—H···O intermolecular hydrogen bonds to form dimers. These dimers are linked by C—H···π interactions to give a three-dimensional network, which seems to be very effective in the stabilization of the crystal structure.

Related literature top

For applications of the title compound, see: Yang et al. (1972). For a related structure, see: Parkin et al. (2005). For the synthesis of the title compound, see: Rolando 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 (Rolando et al., 1995). The crystals were obtained by dissolving (I) (0.2 g, 0.8 mmol) in ethanol (25 ml) and evaporating the solvent slowly at room temperature for about 5 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. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

2-(2-Chlorophenoxy)benzoic acid top

Crystal data top

C₁₃H₉ClO₃	F(000) = 512
M_r = 248.65	D_x = 1.397 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 6.9930 (14) Å	θ = 9–14°
b = 24.986 (5) Å	µ = 0.32 mm⁻¹
c = 7.5140 (15) Å	T = 293 K
β = 115.79 (3)°	Block, colourless
V = 1182.1 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1061 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.088
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 = −30→30
T_min = 0.912, T_max = 0.969	l = −9→8
4651 measured reflections	3 standard reflections every 200 reflections
2177 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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.035P)²] where P = (F_o² + 2F_c²)/3
2177 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₃H₉ClO₃	V = 1182.1 (4) Å³
M_r = 248.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.9930 (14) Å	µ = 0.32 mm⁻¹
b = 24.986 (5) Å	T = 293 K
c = 7.5140 (15) Å	0.30 × 0.20 × 0.10 mm
β = 115.79 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1061 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.088
T_min = 0.912, T_max = 0.969	3 standard reflections every 200 reflections
4651 measured reflections	intensity decay: 1%
2177 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.01	Δρ_max = 0.20 e Å⁻³
2177 reflections	Δρ_min = −0.31 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
Cl	0.30495 (19)	0.80926 (6)	0.11968 (19)	0.1627 (6)
O1	0.5536 (3)	0.90532 (7)	0.1714 (2)	0.0654 (6)
C1	0.5689 (5)	0.81539 (15)	0.2793 (5)	0.0820 (9)
O2	0.0554 (3)	0.99730 (8)	−0.2082 (2)	0.0756 (6)
H2B	−0.0220	1.0088	−0.1606	0.113*
C2	0.6811 (8)	0.77525 (16)	0.4047 (6)	0.1038 (13)
H2A	0.6136	0.7432	0.4050	0.125*
O3	0.2120 (3)	0.96137 (9)	0.0872 (2)	0.0780 (7)
C3	0.8874 (8)	0.78149 (18)	0.5273 (6)	0.1116 (16)
H3A	0.9597	0.7542	0.6150	0.134*
C4	0.9925 (6)	0.82717 (19)	0.5254 (5)	0.0998 (13)
H4A	1.1367	0.8308	0.6076	0.120*
C5	0.8814 (5)	0.86787 (13)	0.3997 (4)	0.0701 (9)
H5A	0.9506	0.8994	0.3967	0.084*
C6	0.6706 (5)	0.86214 (12)	0.2799 (3)	0.0533 (7)
C7	0.5230 (4)	0.91164 (10)	−0.0195 (3)	0.0499 (7)
C8	0.3564 (4)	0.94517 (10)	−0.1407 (3)	0.0492 (7)
C9	0.3345 (4)	0.95491 (11)	−0.3322 (3)	0.0608 (8)
H9A	0.2275	0.9778	−0.4143	0.073*
C10	0.4647 (5)	0.93199 (13)	−0.4018 (4)	0.0755 (9)
H10A	0.4463	0.9388	−0.5299	0.091*
C11	0.6243 (5)	0.89853 (13)	−0.2802 (4)	0.0760 (10)
H11A	0.7140	0.8826	−0.3268	0.091*
C12	0.6529 (4)	0.88827 (11)	−0.0903 (3)	0.0619 (8)
H12A	0.7608	0.8654	−0.0099	0.074*
C13	0.2020 (4)	0.96877 (11)	−0.0801 (3)	0.0492 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.1046 (9)	0.1774 (14)	0.1807 (12)	−0.0608 (9)	0.0384 (8)	−0.0066 (9)
O1	0.0724 (13)	0.0844 (15)	0.0475 (10)	0.0307 (11)	0.0338 (10)	0.0141 (9)
C1	0.089 (3)	0.074 (2)	0.091 (2)	−0.002 (2)	0.046 (2)	0.0038 (19)
O2	0.0668 (14)	0.1086 (17)	0.0618 (11)	0.0366 (12)	0.0375 (11)	0.0274 (11)
C2	0.133 (4)	0.078 (3)	0.114 (3)	0.014 (3)	0.066 (3)	0.027 (2)
O3	0.0779 (14)	0.1155 (18)	0.0523 (11)	0.0450 (13)	0.0392 (10)	0.0240 (10)
C3	0.139 (4)	0.113 (4)	0.095 (3)	0.071 (3)	0.062 (3)	0.047 (3)
C4	0.073 (3)	0.146 (4)	0.076 (2)	0.045 (3)	0.028 (2)	0.018 (3)
C5	0.055 (2)	0.088 (3)	0.0663 (18)	0.0113 (18)	0.0260 (16)	0.0073 (17)
C6	0.0579 (18)	0.063 (2)	0.0439 (14)	0.0175 (17)	0.0267 (14)	0.0095 (13)
C7	0.0558 (17)	0.0591 (18)	0.0421 (14)	0.0042 (14)	0.0283 (13)	0.0022 (12)
C8	0.0453 (15)	0.0626 (19)	0.0420 (14)	0.0029 (14)	0.0210 (13)	0.0000 (12)
C9	0.0648 (19)	0.072 (2)	0.0479 (15)	0.0127 (16)	0.0267 (15)	0.0067 (13)
C10	0.091 (2)	0.096 (2)	0.0515 (17)	0.028 (2)	0.0423 (18)	0.0130 (16)
C11	0.088 (2)	0.100 (3)	0.0565 (17)	0.026 (2)	0.0459 (17)	−0.0012 (17)
C12	0.066 (2)	0.074 (2)	0.0525 (16)	0.0186 (16)	0.0320 (15)	0.0053 (14)
C13	0.0425 (15)	0.0625 (18)	0.0423 (14)	0.0026 (14)	0.0181 (12)	0.0064 (13)

Geometric parameters (Å, º) top

Cl—C1	1.716 (3)	C5—C6	1.360 (3)
O1—C7	1.364 (3)	C5—H5A	0.9300
O1—C6	1.385 (3)	C7—C12	1.367 (3)
C1—C2	1.366 (4)	C7—C8	1.402 (3)
C1—C6	1.367 (4)	C8—C9	1.401 (3)
O2—C13	1.276 (3)	C8—C13	1.466 (3)
O2—H2B	0.8200	C9—C10	1.358 (4)
C2—C3	1.341 (5)	C9—H9A	0.9300
C2—H2A	0.9300	C10—C11	1.376 (4)
O3—C13	1.242 (2)	C10—H10A	0.9300
C3—C4	1.361 (5)	C11—C12	1.376 (3)
C3—H3A	0.9300	C11—H11A	0.9300
C4—C5	1.375 (4)	C12—H12A	0.9300
C4—H4A	0.9300

C7—O1—C6	119.41 (19)	O1—C7—C8	117.3 (2)
C2—C1—C6	118.9 (3)	C12—C7—C8	120.5 (2)
C2—C1—Cl	122.5 (3)	C9—C8—C7	117.4 (2)
C6—C1—Cl	118.6 (3)	C9—C8—C13	118.9 (2)
C13—O2—H2B	109.5	C7—C8—C13	123.7 (2)
C3—C2—C1	120.8 (4)	C10—C9—C8	122.0 (3)
C3—C2—H2A	119.6	C10—C9—H9A	119.0
C1—C2—H2A	119.6	C8—C9—H9A	119.0
C2—C3—C4	121.0 (4)	C9—C10—C11	119.1 (2)
C2—C3—H3A	119.5	C9—C10—H10A	120.4
C4—C3—H3A	119.5	C11—C10—H10A	120.4
C3—C4—C5	118.8 (4)	C10—C11—C12	120.8 (3)
C3—C4—H4A	120.6	C10—C11—H11A	119.6
C5—C4—H4A	120.6	C12—C11—H11A	119.6
C6—C5—C4	120.2 (3)	C7—C12—C11	120.2 (2)
C6—C5—H5A	119.9	C7—C12—H12A	119.9
C4—C5—H5A	119.9	C11—C12—H12A	119.9
C5—C6—C1	120.3 (3)	O3—C13—O2	121.3 (2)
C5—C6—O1	120.0 (3)	O3—C13—C8	122.0 (2)
C1—C6—O1	119.4 (3)	O2—C13—C8	116.7 (2)
O1—C7—C12	122.2 (2)

C6—C1—C2—C3	0.3 (5)	O1—C7—C8—C9	175.4 (2)
Cl—C1—C2—C3	179.9 (3)	C12—C7—C8—C9	−2.2 (4)
C1—C2—C3—C4	−2.4 (6)	O1—C7—C8—C13	−6.7 (4)
C2—C3—C4—C5	2.2 (6)	C12—C7—C8—C13	175.8 (2)
C3—C4—C5—C6	−0.1 (5)	C7—C8—C9—C10	1.7 (4)
C4—C5—C6—C1	−1.8 (4)	C13—C8—C9—C10	−176.4 (3)
C4—C5—C6—O1	172.1 (2)	C8—C9—C10—C11	−0.5 (5)
C2—C1—C6—C5	1.7 (4)	C9—C10—C11—C12	−0.1 (5)
Cl—C1—C6—C5	−177.9 (2)	O1—C7—C12—C11	−175.8 (3)
C2—C1—C6—O1	−172.3 (3)	C8—C7—C12—C11	1.6 (4)
Cl—C1—C6—O1	8.1 (4)	C10—C11—C12—C7	−0.4 (5)
C7—O1—C6—C5	95.1 (3)	C9—C8—C13—O3	179.5 (3)
C7—O1—C6—C1	−90.9 (3)	C7—C8—C13—O3	1.7 (4)
C6—O1—C7—C12	−21.0 (4)	C9—C8—C13—O2	−0.2 (4)
C6—O1—C7—C8	161.5 (2)	C7—C8—C13—O2	−178.1 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···O3ⁱ	0.82	1.81	2.621 (3)	172
C11—H11A···Cg1ⁱⁱ	0.93	2.74	3.582 (4)	151

Symmetry codes: (i) −x, −y+2, −z; (ii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	C₁₃H₉ClO₃
M_r	248.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.9930 (14), 24.986 (5), 7.5140 (15)
β (°)	115.79 (3)
V (Å³)	1182.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
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	0.912, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	4651, 2177, 1061
R_int	0.088
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.110, 1.01
No. of reflections	2177
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.31

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

Cg1 is the centroid of C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···O3ⁱ	0.82	1.81	2.621 (3)	172
C11—H11A···Cg1ⁱⁱ	0.93	2.74	3.582 (4)	151

Symmetry codes: (i) −x, −y+2, −z; (ii) x, y, z−1.

Acknowledgements

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

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
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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
Parkin, A., et al. (2005). Acta Cryst. E61, o2280–o2282. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Yang, N. C., Kumler, P. & Yang, S. S. (1972). J. Org. Chem. 37, 4022–4026. CrossRef CAS Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o748

doi:10.1107/S1600536811006301

Open

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