organic compounds
2-(2-Isopropylphenoxy)acetic acid
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
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 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.
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 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).
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.
|
The et al., 1992), however, in that report, the unit-cell dimensions differ significantly from those of the title compound:
of this compound have been reported previously (Smitha, 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 . The carboxyl H atom (H13) was located in a difference Fourier map and freely refined.
details are summarized in Table 2Structural data
CCDC reference: 1511437
https://doi.org/10.1107/S2414314616017144/su4086sup1.cif
contains datablocks global, I. DOI: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
Data collection: APEX2 (Bruker, 2013); cell
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).C11H14O3 | Z = 2 |
Mr = 194.22 | F(000) = 208 |
Triclinic, P1 | Dx = 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 |
Bruker X8 Proteum diffractometer | 1617 independent reflections |
Radiation source: Bruker MicroStar microfocus rotating anode | 1549 reflections with I > 2σ(I) |
Helios multilayer optics monochromator | Rint = 0.027 |
Detector resolution: 18.4 pixels mm-1 | θmax = 64.4°, θmin = 6.4° |
φ and ω scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | k = −8→9 |
Tmin = 0.807, Tmax = 0.848 | l = −13→13 |
5019 measured reflections |
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(Fo2) + (0.0476P)2 + 0.1244P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1617 reflections | Δρmax = 0.14 e Å−3 |
134 parameters | Δρmin = −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) |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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.
References
Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gurupadaswamy, H. D., Girish, V., Kavitha, C. V., Raghavan, S. C. & Khanum, S. A. (2013). Eur. J. Med. Chem. 63, 536–543. CrossRef CAS PubMed Google Scholar
Kennard, C. H. L., Astbury, I. C., Smith, G., Sagatys, D. S. & Moore, F. H. (1987). Z. Kristallogr. 180, 227. CrossRef Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mohammed, Y. H. I., Naveen, S., Lokanath, N. K. & Khanum, S. A. (2016). IUCrData, 1, x160416. Google Scholar
Okawara, T., Ikeda, N., Yamasaki, T. & Furukawa, M. (1988). Chem. Pharm. Bull. 36, 3628–3631. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Smith, G., Lynch, D. E., Sagatys, D. S., Kennard, C. H. L. & Katekar, G. F. (1992). Aust. J. Chem. 45, 1101–1108. CSD CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.