3-Methyl-2-(4-methyl­phen­oxy)benzoic acid

Lu, K.; Long, S.

doi:10.1107/S2414314623006004

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 7| July 2023| x230600

https://doi.org/10.1107/S2414314623006004

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3-Methyl-2-(4-methylphenoxy)benzoic acid

Kangkang Lu ^a and Sihui Long ^a ^*

^aSchool of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan, Hubei 430205, People's Republic of China
^*Correspondence e-mail: sihuilong@wit.edu.cn

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 12 May 2023; accepted 7 July 2023; online 14 July 2023)

In the title compound, C₁₅H₁₄O₃, the dihedral angle between the aromatic rings is 86.7 (9)°. In the crystal, carboxylic acid inversion dimers linked by pairwise O—H⋯O hydrogen bonds are formed.

Keywords: crystal structure; carboxylic acid inversion dimer.

CCDC reference: 2280192

Structure description

2-Phenoxybenzoic acids are isosteres of anthranilic acids that are potential anti-inflammatory drugs and conformationally flexible molecules. Many anthranilic acids are polymorphic (Lopez-Mejias et al., 2012 ; Sacchi, et al., 2021 ). We wondered if 2-phenoxybenzoic acids would behave similarly to anthranilic acids in their polymorphism and as part of our work in this area, we now describe the synthesis and structure of the title compound, C₁₅H₁₄O₃.

There is one molecule in the asymmetric unit (Fig. 1). The molecule has a nearly perpendicular conformation as evidenced by the dihedral angle between the benzoic acid ring and the phenol ring [86.7 (9)°]. In the crystal, the molecules form carboxylic acid inversion dimers through pairwise O—H⋯O hydrogen bonds (Table 1, Fig. 2). Two weak C—H⋯π interactions are also observed.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3ⁱ	0.86 (2)	1.80 (2)	2.6497 (14)	169 (3)
C4—H4⋯Cg1ⁱⁱ	0.93	2.92	3.6557 (18)	137
C5—H5⋯Cg2ⁱⁱⁱ	0.93	2.97	3.8372 (15)	156
Symmetry codes: (i) ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Figure 2
Packing of the molecules in the title compound.

Synthesis and crystallization

The title compound was synthesized through an Ullmann reaction between 2-chloro-3-methyl-benzoic acid and 4-methylphenol (Fig. 3) in an effort to investigate the effect of substitution position and pattern on the solid-state behavior of 2-phenoxybenzoic acids. A pure sample was dissolved in ethyl acetate at 60°C. Then, the solution was cooled to room temperature and was allowed to evaporate slowly in a fume hood. Colorless block-shaped crystals (Fig. 4) were harvested after a week.

Figure 3
Reaction scheme.

Figure 4
A representative crystal of the title compound.

Refinement

Crystal and refinement data are listed in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₄O₃
M_r	242.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.95081 (17), 6.54110 (15), 21.9729 (4)
β (°)	91.2391 (18)
V (Å³)	1286.17 (5)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.71
Crystal size (mm)	0.11 × 0.09 × 0.07

Data collection
Diffractometer	Rigaku Oxford Diffraction, Synergy Custom system, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.856, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7830, 2527, 2197
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.124, 1.08
No. of reflections	2527
No. of parameters	169
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.17
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2280192

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314623006004/hb4431sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623006004/hb4431Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314623006004/hb4431Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2021); cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Olex2 1.5 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).

3-Methyl-2-(4-methylphenoxy)benzoic acid top

Crystal data top

C₁₅H₁₄O₃	F(000) = 512
M_r = 242.26	D_x = 1.251 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 8.95081 (17) Å	Cell parameters from 5741 reflections
b = 6.54110 (15) Å	θ = 4.0–76.9°
c = 21.9729 (4) Å	µ = 0.71 mm⁻¹
β = 91.2391 (18)°	T = 293 K
V = 1286.17 (5) Å³	Block, colourless
Z = 4	0.11 × 0.09 × 0.07 mm

Data collection top

Rigaku Oxford Diffraction, Synergy Custom system, HyPix diffractometer	2527 independent reflections
Radiation source: Rotating-anode X-ray tube, Rigaku (Cu) X-ray Source	2197 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.023
Detector resolution: 10.0000 pixels mm^-1	θ_max = 77.6°, θ_min = 4.0°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysalisPro; Rigaku OD, 2021)	k = −8→8
T_min = 0.856, T_max = 1.000	l = −27→20
7830 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0665P)² + 0.1182P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2527 reflections	Δρ_max = 0.17 e Å⁻³
169 parameters	Δρ_min = −0.17 e Å⁻³
1 restraint

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The C-bound H atoms were placed geometrically (C—H = 0.93–0.96 Å) and refined as riding atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.24620 (10)	0.17742 (14)	0.64109 (4)	0.0593 (3)
O2	0.15526 (12)	0.4152 (2)	0.54426 (5)	0.0769 (3)
H2	0.110 (3)	0.422 (5)	0.5094 (8)	0.190 (13)*
O3	−0.05029 (11)	0.58182 (18)	0.56942 (4)	0.0725 (3)
C1	0.21476 (13)	0.3529 (2)	0.67392 (6)	0.0536 (3)
C2	0.12444 (13)	0.5035 (2)	0.64797 (6)	0.0541 (3)
C3	0.08109 (16)	0.6693 (2)	0.68345 (7)	0.0656 (4)
H3	0.018988	0.769656	0.666817	0.079*
C4	0.13026 (18)	0.6842 (3)	0.74310 (7)	0.0745 (4)
H4	0.102602	0.795630	0.766625	0.089*
C5	0.22069 (17)	0.5335 (3)	0.76790 (6)	0.0728 (4)
H5	0.253775	0.546005	0.808144	0.087*
C6	0.26370 (15)	0.3642 (2)	0.73468 (6)	0.0639 (4)
C7	0.3572 (2)	0.1978 (3)	0.76307 (8)	0.0875 (5)
H7A	0.324401	0.067562	0.747699	0.131*
H7B	0.347063	0.200889	0.806463	0.131*
H7C	0.460117	0.218413	0.753209	0.131*
C8	0.38771 (14)	0.15863 (19)	0.61722 (6)	0.0531 (3)
C9	0.48515 (15)	0.3192 (2)	0.61186 (7)	0.0643 (4)
H9	0.458835	0.448913	0.625247	0.077*
C10	0.62304 (16)	0.2860 (2)	0.58630 (7)	0.0672 (4)
H10	0.688959	0.395109	0.582847	0.081*
C11	0.66564 (15)	0.0951 (2)	0.56573 (6)	0.0624 (3)
C12	0.56571 (17)	−0.0629 (2)	0.57189 (7)	0.0676 (4)
H12	0.591697	−0.192455	0.558302	0.081*
C13	0.42802 (17)	−0.0346 (2)	0.59764 (6)	0.0634 (4)
H13	0.362890	−0.144278	0.601829	0.076*
C14	0.81667 (19)	0.0625 (3)	0.53797 (9)	0.0852 (5)
H14A	0.844404	0.182635	0.515791	0.128*
H14B	0.811909	−0.052342	0.510806	0.128*
H14C	0.889706	0.036619	0.569672	0.128*
C15	0.07176 (14)	0.4993 (2)	0.58337 (6)	0.0554 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0555 (5)	0.0529 (5)	0.0694 (6)	−0.0043 (4)	−0.0001 (4)	−0.0034 (4)
O2	0.0720 (6)	0.1022 (9)	0.0567 (6)	0.0235 (6)	0.0036 (5)	−0.0043 (5)
O3	0.0633 (6)	0.0874 (8)	0.0666 (6)	0.0174 (5)	−0.0013 (4)	0.0021 (5)
C1	0.0477 (6)	0.0558 (7)	0.0573 (7)	−0.0064 (5)	0.0040 (5)	−0.0015 (5)
C2	0.0488 (6)	0.0583 (7)	0.0556 (6)	−0.0038 (5)	0.0058 (5)	−0.0010 (5)
C3	0.0608 (8)	0.0676 (9)	0.0689 (8)	0.0038 (6)	0.0092 (6)	−0.0065 (7)
C4	0.0707 (9)	0.0826 (11)	0.0707 (9)	−0.0025 (7)	0.0111 (7)	−0.0222 (8)
C5	0.0674 (8)	0.0947 (12)	0.0562 (7)	−0.0093 (8)	0.0003 (6)	−0.0114 (7)
C6	0.0559 (7)	0.0769 (9)	0.0587 (7)	−0.0078 (6)	−0.0021 (6)	0.0025 (6)
C7	0.0902 (11)	0.0955 (13)	0.0758 (10)	0.0046 (9)	−0.0197 (9)	0.0106 (9)
C8	0.0541 (6)	0.0514 (7)	0.0536 (6)	0.0022 (5)	−0.0039 (5)	0.0015 (5)
C9	0.0614 (7)	0.0487 (7)	0.0832 (9)	0.0010 (6)	0.0074 (6)	−0.0071 (6)
C10	0.0609 (8)	0.0582 (8)	0.0826 (9)	−0.0010 (6)	0.0072 (7)	−0.0027 (7)
C11	0.0651 (8)	0.0622 (8)	0.0599 (7)	0.0098 (6)	0.0012 (6)	−0.0003 (6)
C12	0.0807 (9)	0.0523 (8)	0.0698 (8)	0.0117 (7)	0.0016 (7)	−0.0061 (6)
C13	0.0735 (8)	0.0481 (7)	0.0683 (8)	−0.0023 (6)	−0.0031 (6)	−0.0007 (6)
C14	0.0781 (10)	0.0813 (11)	0.0969 (12)	0.0168 (9)	0.0168 (9)	−0.0063 (9)
C15	0.0523 (6)	0.0560 (7)	0.0581 (7)	0.0014 (5)	0.0052 (5)	0.0013 (5)

Geometric parameters (Å, º) top

O1—C1	1.3875 (15)	C7—H7B	0.9600
O1—C8	1.3868 (15)	C7—H7C	0.9600
O2—H2	0.860 (10)	C8—C9	1.3719 (19)
O2—C15	1.2759 (16)	C8—C13	1.3857 (18)
O3—C15	1.2508 (16)	C9—H9	0.9300
C1—C2	1.3890 (19)	C9—C10	1.3841 (19)
C1—C6	1.3980 (18)	C10—H10	0.9300
C2—C3	1.3957 (19)	C10—C11	1.385 (2)
C2—C15	1.4862 (18)	C11—C12	1.375 (2)
C3—H3	0.9300	C11—C14	1.510 (2)
C3—C4	1.377 (2)	C12—H12	0.9300
C4—H4	0.9300	C12—C13	1.380 (2)
C4—C5	1.380 (2)	C13—H13	0.9300
C5—H5	0.9300	C14—H14A	0.9600
C5—C6	1.386 (2)	C14—H14B	0.9600
C6—C7	1.501 (2)	C14—H14C	0.9600
C7—H7A	0.9600

C8—O1—C1	117.85 (9)	C9—C8—C13	120.10 (12)
C15—O2—H2	108 (2)	C13—C8—O1	116.38 (11)
O1—C1—C2	119.74 (11)	C8—C9—H9	120.4
O1—C1—C6	118.51 (12)	C8—C9—C10	119.27 (13)
C2—C1—C6	121.47 (12)	C10—C9—H9	120.4
C1—C2—C3	119.22 (12)	C9—C10—H10	119.1
C1—C2—C15	123.29 (12)	C9—C10—C11	121.88 (14)
C3—C2—C15	117.49 (12)	C11—C10—H10	119.1
C2—C3—H3	120.0	C10—C11—C14	120.94 (15)
C4—C3—C2	120.00 (14)	C12—C11—C10	117.47 (13)
C4—C3—H3	120.0	C12—C11—C14	121.59 (14)
C3—C4—H4	120.1	C11—C12—H12	119.0
C3—C4—C5	119.85 (14)	C11—C12—C13	121.92 (13)
C5—C4—H4	120.1	C13—C12—H12	119.0
C4—C5—H5	119.0	C8—C13—H13	120.3
C4—C5—C6	122.02 (13)	C12—C13—C8	119.36 (13)
C6—C5—H5	119.0	C12—C13—H13	120.3
C1—C6—C7	121.27 (14)	C11—C14—H14A	109.5
C5—C6—C1	117.42 (14)	C11—C14—H14B	109.5
C5—C6—C7	121.30 (14)	C11—C14—H14C	109.5
C6—C7—H7A	109.5	H14A—C14—H14B	109.5
C6—C7—H7B	109.5	H14A—C14—H14C	109.5
C6—C7—H7C	109.5	H14B—C14—H14C	109.5
H7A—C7—H7B	109.5	O2—C15—C2	118.22 (11)
H7A—C7—H7C	109.5	O3—C15—O2	122.84 (12)
H7B—C7—H7C	109.5	O3—C15—C2	118.92 (11)
C9—C8—O1	123.51 (11)

O1—C1—C2—C3	173.51 (11)	C3—C4—C5—C6	−0.5 (2)
O1—C1—C2—C15	−7.17 (18)	C4—C5—C6—C1	1.5 (2)
O1—C1—C6—C5	−174.93 (12)	C4—C5—C6—C7	−177.62 (15)
O1—C1—C6—C7	4.16 (19)	C6—C1—C2—C3	−0.29 (19)
O1—C8—C9—C10	−178.73 (12)	C6—C1—C2—C15	179.03 (12)
O1—C8—C13—C12	178.25 (12)	C8—O1—C1—C2	105.42 (13)
C1—O1—C8—C9	−15.62 (18)	C8—O1—C1—C6	−80.60 (14)
C1—O1—C8—C13	165.09 (11)	C8—C9—C10—C11	0.2 (2)
C1—C2—C3—C4	1.3 (2)	C9—C8—C13—C12	−1.1 (2)
C1—C2—C15—O2	−30.72 (19)	C9—C10—C11—C12	−0.4 (2)
C1—C2—C15—O3	150.82 (13)	C9—C10—C11—C14	179.97 (14)
C2—C1—C6—C5	−1.06 (19)	C10—C11—C12—C13	−0.2 (2)
C2—C1—C6—C7	178.03 (13)	C11—C12—C13—C8	0.9 (2)
C2—C3—C4—C5	−0.9 (2)	C13—C8—C9—C10	0.5 (2)
C3—C2—C15—O2	148.61 (14)	C14—C11—C12—C13	179.47 (14)
C3—C2—C15—O3	−29.85 (18)	C15—C2—C3—C4	−178.07 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3ⁱ	0.86 (2)	1.80 (2)	2.6497 (14)	169 (3)
C4—H4···Cg1ⁱⁱ	0.93	2.92	3.6557 (18)	137
C5—H5···Cg2ⁱⁱⁱ	0.93	2.97	3.8372 (15)	156

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, y+1/2, −z+3/2; (iii) −x+1, y+1/2, −z+3/2.

References

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