2-(2-Iso­propyl­phen­oxy)acetic acid

Mohammed, Y.H.I.; Naveen, S.; Mamatha, S.V.; Jyothi, M.; Khanum, S.A.; Lokanath, N.K.

doi:10.1107/S2414314616017144

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 10| October 2016| x161714

https://doi.org/10.1107/S2414314616017144

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2-(2-Isopropylphenoxy)acetic acid

Yasser Hussein Issa Mohammed,^a S. Naveen,^b S. V. Mamatha,^a Mahima Jyothi,^a Shaukath Ara Khanum ^a and N. K. Lokanath ^c ^*

^aDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysuru 570 005, India, ^bInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru 570 006, India, and ^cDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru 570 006, India
^*Correspondence e-mail: lokanath@physics.uni-mysore.ac.in

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 21 October 2016; accepted 25 October 2016; online 28 October 2016)

In the title compound, C₁₁H₁₄O₃, the pendant –OCH₂COOH chain is in an extended conformation and almost lies in the plane of the benzene ring, as indicated by the dihedral angle of 2.61 (5)°. In the crystal, molecules are linked by a pair of O—H⋯O hydrogen bonds, forming classical carboxylic acid inversion dimers, with an R₂²(8) loop. The crystal structure of this compound have been reported previously [Smith et al. (1992 ). Aust. J. Chem. 45, 1101–1108], however, in that report, the unit-cell dimensions differ significantly from those of the title structure and the carboxyl H atom was disordered within a cyclic hydrogen-bonded dimer.

Keywords: crystal structure; phenoxy carboxylic acid; O—H⋯O hydrogen bonds; inversion dimer.

CCDC reference: 1511437

Structure description

Phenoxyacetic acid derivatives are interesting building blocks in a variety of natural and synthetic compounds found to possess a variety of pharmacological applications, such as anticancer, analgesic, anti-inflammatory and gastrin receptor antagonistic activities (Gurupadaswamy et al., 2013 ). Moreover, derivatives of phenoxyacetic acid are characterized by a broad spectrum of physiological activity whose type and strength depends on the substituents in both the aromatic ring and the acid fragment (Okawara et al., 1988 ). As part of our ongoing research on this class of compounds (Mohammed et al., 2016 ), the title compound was synthesized and we report herein its crystal structure. The molecule is being assessed for its biological activity.

The molecular structure of the title compound is shown in Fig. 1. The pendant –OCH₂COOH chain [O10/C11/C12/O13/O14; maximum deviation = 0.031 (1) Å for atom C11] is in an extended conformation and almost lies in the plane of the benzene ring (atoms C1–C6), as indicated by the dihedral angle of 2.61 (5)°. The bond lengths and angles are similar to those reported for the tert-butyl analogue 2-(2-tert-butylphenoxy)acetic acid (Kennard et al., 1987 ).

Figure 1
A view of the molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

In the crystal, molecules are linked by a pair of O—H⋯O hydrogen bonds, forming classical carboxylic acid inversion dimers, with an R₂²(8) loop (Table 1 and Fig. 2). There are no other significant intermolecular interactions present.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13⋯O14ⁱ	0.92 (2)	1.73 (2)	2.6392 (11)	173.5 (17)
Symmetry code: (i) -x+3, -y+2, -z+1.

Figure 2
A view along the a axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1

The crystal structure of this compound have been reported previously (Smith et al., 1992), however, in that report, the unit-cell dimensions differ significantly from those of the title compound:

a, b, c (Å) 5.9946 (8), 7.944 (1), 12.177 (1); α, β, γ (°) 103.666 (9), 94.890 (9), 111.74 (1) (Smith et al., 1992)

cf. a, b, c (Å) 5.9825 (2), 7.8623 (2), 11.9240 (3); α, β, γ (°) 104.564 (1), 93.570 (1), 112.302 (1) (present structural report).

It was also found that the carboxyl H atom was disordered within a cyclic hydrogen-bonded dimer, which is not the case in the present structural report.

Synthesis and crystallization

A mixture of 2-isopropylphenol (0.03 mol), ethyl chloroacetate (0.045 mol) and anhydrous potassium carbonate (0.03 mol) in dry acetone (50 ml) was refluxed for 12 h. The reaction mixture was cooled and the solvent removed by distillation. The residual mass was triturated with cold water to remove potassium carbonate, and extracted with ether (3 × 30 ml). The ether layer was washed with 10% sodium hydroxide solution (3 × 30 ml) followed by water (3 × 30 ml) and then dried over anhydrous sodium sulfate and evaporated to give isopropyl phenoxy ethyl acetate. This compound (0.015 mol) was then dissolved in ethanol (15 ml) and a sodium hydroxide (0.025 mol) solution in water (5 ml) was added. The mixture was refluxed for 9 h and the reaction mixture was cooled and acidified with 5 M hydrochloric acid. The precipitate was filtered off, washed with water and recrystallized from ethanol to yield colourless block-like crystals (yield 88%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The carboxyl H atom (H13) was located in a difference Fourier map and freely refined.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₄O₃
M_r	194.22
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	5.9825 (2), 7.8623 (2), 11.9240 (3)
α, β, γ (°)	104.564 (1), 93.570 (1), 112.302 (1)
V (Å³)	494.38 (2)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	0.77
Crystal size (mm)	0.29 × 0.26 × 0.22

Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.807, 0.848
No. of measured, independent and observed [I > 2σ(I)] reflections	5019, 1617, 1549
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.585

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.090, 1.05
No. of reflections	1617
No. of parameters	134
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.17
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 (Sheldrick, 2008 ), Mercury (Macrae et al., 2008 ), SHELXL2014 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1511437

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616017144/su4086sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017144/su4086Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616017144/su4086Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

2-(2-Isopropylphenoxy)acetic acid top

Crystal data top

C₁₁H₁₄O₃	Z = 2
M_r = 194.22	F(000) = 208
Triclinic, P1	D_x = 1.305 Mg m⁻³
a = 5.9825 (2) Å	Cu Kα radiation, λ = 1.54178 Å
b = 7.8623 (2) Å	Cell parameters from 1549 reflections
c = 11.9240 (3) Å	θ = 6.4–64.4°
α = 104.564 (1)°	µ = 0.77 mm⁻¹
β = 93.570 (1)°	T = 296 K
γ = 112.302 (1)°	Block, colourless
V = 494.38 (2) Å³	0.29 × 0.26 × 0.22 mm

Data collection top

Bruker X8 Proteum diffractometer	1617 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	1549 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.027
Detector resolution: 18.4 pixels mm^-1	θ_max = 64.4°, θ_min = 6.4°
φ and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −8→9
T_min = 0.807, T_max = 0.848	l = −13→13
5019 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0476P)² + 0.1244P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1617 reflections	Δρ_max = 0.14 e Å⁻³
134 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (4)

Special details top

Experimental. ¹H NMR(400 MHz, CdCl₃ δ ppm) 1.25(s, 6H, 2CH₃), 4.69 (s, 2H, OCH₂), 6.73-7.26 (m, 4H, Ar-H), 9.18 (s, IH, OH)

LC-MS m/z 195 (M+1).

Anal. Calcd. for C₁₁H₁₄O₆: C, 68.02; H, 7.27; O, 24.71 Found: C, 68.31; H, 7.06; O, 24.53%.

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.

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

	x	y	z	U_iso*/U_eq
C1	0.4051 (2)	0.64683 (15)	0.21029 (9)	0.0187 (3)
C2	0.5345 (2)	0.59261 (15)	0.28716 (9)	0.0197 (3)
C3	0.4231 (2)	0.42232 (16)	0.31556 (10)	0.0230 (3)
H3	0.5119	0.3885	0.3662	0.028*
C4	0.1784 (2)	0.30264 (16)	0.26815 (10)	0.0237 (3)
H4	0.1038	0.1879	0.2863	0.028*
C5	0.0462 (2)	0.35395 (16)	0.19412 (10)	0.0237 (3)
H5	−0.1182	0.2750	0.1632	0.028*
C6	0.1600 (2)	0.52438 (16)	0.16600 (10)	0.0217 (3)
H6	0.0692	0.5575	0.1159	0.026*
C7	0.53617 (19)	0.82750 (15)	0.17505 (9)	0.0200 (3)
H7	0.6538	0.9250	0.2440	0.024*
C8	0.3630 (2)	0.91107 (16)	0.13603 (10)	0.0240 (3)
H8A	0.2581	0.8248	0.0631	0.036*
H8B	0.4572	1.0336	0.1253	0.036*
H8C	0.2647	0.9273	0.1951	0.036*
C9	0.6813 (2)	0.78602 (17)	0.07837 (11)	0.0261 (3)
H9A	0.7877	0.7322	0.1039	0.039*
H9B	0.7777	0.9037	0.0624	0.039*
H9C	0.5696	0.6961	0.0081	0.039*
O10	0.77591 (14)	0.71977 (11)	0.33094 (7)	0.0234 (2)
C11	0.9046 (2)	0.67696 (16)	0.41536 (9)	0.0212 (3)
H11A	0.9080	0.5522	0.3818	0.025*
H11B	0.8225	0.6720	0.4829	0.025*
C12	1.1617 (2)	0.82965 (15)	0.45327 (9)	0.0201 (3)
O13	1.29112 (15)	0.78801 (12)	0.52707 (7)	0.0264 (3)
H13	1.450 (4)	0.878 (3)	0.5439 (16)	0.054 (5)*
O14	1.24080 (14)	0.97255 (11)	0.42015 (7)	0.0237 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0217 (6)	0.0186 (5)	0.0165 (5)	0.0096 (4)	0.0040 (4)	0.0044 (4)
C2	0.0203 (6)	0.0192 (6)	0.0187 (5)	0.0078 (4)	0.0026 (4)	0.0048 (4)
C3	0.0275 (6)	0.0223 (6)	0.0224 (6)	0.0117 (5)	0.0037 (4)	0.0098 (4)
C4	0.0281 (6)	0.0179 (6)	0.0243 (6)	0.0074 (5)	0.0076 (5)	0.0073 (4)
C5	0.0206 (6)	0.0214 (6)	0.0242 (6)	0.0048 (5)	0.0037 (4)	0.0046 (4)
C6	0.0215 (6)	0.0229 (6)	0.0206 (6)	0.0096 (5)	0.0017 (4)	0.0063 (4)
C7	0.0199 (6)	0.0179 (5)	0.0203 (5)	0.0060 (4)	−0.0006 (4)	0.0064 (4)
C8	0.0256 (6)	0.0244 (6)	0.0266 (6)	0.0121 (5)	0.0049 (5)	0.0124 (5)
C9	0.0246 (6)	0.0264 (6)	0.0328 (7)	0.0116 (5)	0.0092 (5)	0.0151 (5)
O10	0.0209 (4)	0.0231 (4)	0.0252 (4)	0.0057 (3)	−0.0031 (3)	0.0121 (3)
C11	0.0250 (6)	0.0227 (6)	0.0189 (6)	0.0112 (5)	0.0012 (4)	0.0093 (4)
C12	0.0260 (6)	0.0225 (6)	0.0155 (5)	0.0135 (5)	0.0027 (4)	0.0063 (4)
O13	0.0244 (5)	0.0274 (5)	0.0279 (5)	0.0087 (4)	−0.0034 (3)	0.0141 (4)
O14	0.0249 (5)	0.0228 (5)	0.0245 (4)	0.0092 (3)	−0.0003 (3)	0.0106 (3)

Geometric parameters (Å, º) top

C1—C6	1.3902 (16)	C7—H7	0.9800
C1—C2	1.4071 (15)	C8—H8A	0.9600
C1—C7	1.5182 (15)	C8—H8B	0.9600
C2—O10	1.3802 (14)	C8—H8C	0.9600
C2—C3	1.3895 (16)	C9—H9A	0.9600
C3—C4	1.3897 (17)	C9—H9B	0.9600
C3—H3	0.9300	C9—H9C	0.9600
C4—C5	1.3791 (16)	O10—C11	1.4106 (13)
C4—H4	0.9300	C11—C12	1.4999 (16)
C5—C6	1.3905 (16)	C11—H11A	0.9700
C5—H5	0.9300	C11—H11B	0.9700
C6—H6	0.9300	C12—O14	1.2187 (13)
C7—C8	1.5272 (15)	C12—O13	1.3168 (13)
C7—C9	1.5297 (16)	O13—H13	0.92 (2)

C6—C1—C2	117.03 (10)	C7—C8—H8A	109.5
C6—C1—C7	122.82 (9)	C7—C8—H8B	109.5
C2—C1—C7	120.10 (9)	H8A—C8—H8B	109.5
O10—C2—C3	123.42 (10)	C7—C8—H8C	109.5
O10—C2—C1	115.23 (9)	H8A—C8—H8C	109.5
C3—C2—C1	121.34 (10)	H8B—C8—H8C	109.5
C2—C3—C4	119.81 (10)	C7—C9—H9A	109.5
C2—C3—H3	120.1	C7—C9—H9B	109.5
C4—C3—H3	120.1	H9A—C9—H9B	109.5
C5—C4—C3	120.03 (10)	C7—C9—H9C	109.5
C5—C4—H4	120.0	H9A—C9—H9C	109.5
C3—C4—H4	120.0	H9B—C9—H9C	109.5
C4—C5—C6	119.63 (10)	C2—O10—C11	116.49 (8)
C4—C5—H5	120.2	O10—C11—C12	109.23 (9)
C6—C5—H5	120.2	O10—C11—H11A	109.8
C1—C6—C5	122.15 (10)	C12—C11—H11A	109.8
C1—C6—H6	118.9	O10—C11—H11B	109.8
C5—C6—H6	118.9	C12—C11—H11B	109.8
C1—C7—C8	113.13 (9)	H11A—C11—H11B	108.3
C1—C7—C9	109.82 (9)	O14—C12—O13	124.46 (10)
C8—C7—C9	110.53 (9)	O14—C12—C11	124.79 (10)
C1—C7—H7	107.7	O13—C12—C11	110.74 (9)
C8—C7—H7	107.7	C12—O13—H13	109.0 (11)
C9—C7—H7	107.7

C6—C1—C2—O10	−178.81 (9)	C4—C5—C6—C1	−0.08 (17)
C7—C1—C2—O10	3.74 (15)	C6—C1—C7—C8	26.38 (14)
C6—C1—C2—C3	1.20 (16)	C2—C1—C7—C8	−156.33 (10)
C7—C1—C2—C3	−176.24 (10)	C6—C1—C7—C9	−97.63 (12)
O10—C2—C3—C4	179.62 (10)	C2—C1—C7—C9	79.66 (12)
C1—C2—C3—C4	−0.40 (17)	C3—C2—O10—C11	−4.86 (15)
C2—C3—C4—C5	−0.69 (17)	C1—C2—O10—C11	175.15 (9)
C3—C4—C5—C6	0.93 (17)	C2—O10—C11—C12	−179.75 (8)
C2—C1—C6—C5	−0.97 (16)	O10—C11—C12—O14	3.41 (15)
C7—C1—C6—C5	176.40 (10)	O10—C11—C12—O13	−176.35 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···O14ⁱ	0.92 (2)	1.73 (2)	2.6392 (11)	173.5 (17)

Symmetry code: (i) −x+3, −y+2, −z+1.

Acknowledgements

The authors are grateful to the Institution of Excellence, Vijnana Bhavana, University of Mysore, India, for providing the single-crystal X-ray diffractometer facility. Yasser Hussain Issa Mohammed thanks University of Hajah, Yemen, for financial support. SAK gratefully acknowledges the financial support provided by the Vision Group of Science and Technology, Government of Karnataka, under the scheme CISEE, Department of Information Technology, Biotechnology and Science and Technology, Bangalore.

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