organic compounds
Ethyl 2-(4-chloro-3-methylphenoxy)acetate
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: shaukathara@yahoo.co.in
In the title compound, C11H13ClO3, the pendant ethyl chain has an extended conformation and lies in the plane of the substituted benzene ring; the r.m.s. deviation of the 15 non-H atoms comprising the molecule is 0.002 Å. The features inversion-related dimers linked by pairs of benzene–carbonyl C—H⋯O hydrogen bonds, generating R22(16) loops.
Keywords: crystal structure; phenoxy acetate; C—H⋯O hydrogen bonds.
CCDC reference: 1463900
Structure description
Phenoxyacetates are very robust moieties towards various harsh reaction conditions. The stability is documented by numerous transformations on the aryl system without affecting the side chain (Al-Ghorbani et al., 2015). This alkoxy moiety turned out to be beneficial for oxidative transformations with strong Lewis acids. Ethyl phenoxyacetate derivatives have potential antimicrobial, anticancer, antitumor, antioxidant, anti-inflammatory and plant-growth-regulation activity properties (Khanum et al., 2004). These compounds are widely used as herbicides and pesticides. Ethyl phenoxyacetate analogues also show very good antiulcerogenic activity, cyclooxygenase activity and anticonvulsant activity. In view of the above, the title compound, ethyl 2-(4-chloro-3-methylphenoxy)acetate, was synthesized and we report herein its crystal structure.
The title molecule (Fig. 1) closely resembles that of ethyl 2-(2-bromophenoxy)acetate with similar geometric parameters. The pendant ethyl chain is in an extended conformation and almost lies in the plane of the substituted benzene ring, as indicated by the dihedral angle of 1.86 (2)°. The features inversion-related dimers linked by pairs of C—H⋯O hydrogen bonds generating (16) loops (Table 1).
Synthesis and crystallization
A mixture of 4-chloro-3-methylphenol (0.200 mol), ethyl chloroacetate (0.031 mol) and anhydrous potassium carbonate (0.037 mol) in dry acetone (50 ml) was refluxed for 12 h. The reaction mixture was cooled and the solvent was 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 successively with 10% sodium hydroxide solution (3 × 30 ml) and water (3 × 30 ml), and then dried over anhydrous sodium sulfate and evaporated, giving white crystals of ethyl 2-(4-chloro-3-methylphenoxy)acetate in good yield (85%).
1H NMR (400 MHz, CDCl3): δ 1.32 (t, 3H, CH3 of ester), 2.38 (s, 3H, CH3), 4.24 (q, 2H, CH2 of ester), 5.01 (s, 2H, CH2), 6.77–7.34 (m, 3H, Ar—H). IR (KBr) (vmax/cm−1): 1750 (ester, C=O). The showed molecular ion peaks at m/z = 228 [M+] and 230 (M + 2). Analysis calculated for C11H13ClO3: C 57.78, H 5.73, Cl 15.50%; found: C 57.63, H 5.65, Cl 15.40%.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1463900
10.1107/S2414314616004168/tk4004sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616004168/tk4004Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616004168/tk4004Isup3.cml
A mixture of 4-chloro-3-methylphenol (0.200 mol), ethyl chloroacetate (0.031 mol) and anhydrous potassium carbonate (0.037 mol) in dry acetone (50 ml) was refluxed for 12 h. The reaction mixture was cooled and the solvent was 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 successively with 10% sodium hydroxide solution (3 × 30 ml) and water (3 × 30 ml), and then dried over anhydrous sodium sulfate and evaporated, giving white crystals of ethyl 2-(4-chloro-3-methylphenoxy)acetate in good yield (85%).
1H NMR (400 MHz, CDCl3): δ 1.32 (t, 3H, CH3 of ester), 2.38 (s, 3H, CH3), 4.24 (q, 2H, CH2 of ester), 5.01 (s, 2H, CH2), 6.77–7.34 (m, 3H, Ar—H). IR (KBr) (vmax/cm−1): 1750 (ester, C═O). The showed molecular ion peaks at m/z = 228 [M+] and 230 (M+2). Analysis calculated for C11H13ClO3: C 57.78, H 5.73, Cl 15.50%; found: C 57.63, H 5.65, Cl 15.40%.
Crystal data, data collection and structure
details are summarized in Table 2. H atoms were fixed geometrically (C—H = 0.93–0.97 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.2–1.5Ueq(C).Phenoxyacetates are very robust moieties towards various harsh reaction conditions. The stability is documented by numerous transformations on the aryl system without affecting the side chain (Al-Ghorbani et al., 2015). This alkoxy moiety turned out to be beneficial for oxidative transformations with strong Lewis acids. Ethyl phenoxyacetate derivatives have potential antimicrobial, anticancer, antitumor antioxidant, antiinflammatory and plant-growth-regulation activity properties (Khanum et al., 2004). These compounds are widely used as herbicides and pesticides. Ethyl phenoxyacetate analogues also show very good antiulcerogenic activity, cyclooxygenase activity and anticonvulsant activity. In view of the above, the title compound, ethyl 2-(4-chloro-3-methylphenoxy)acetate, was synthesized and we report herein its crystal structure.
The title molecule (Fig. 1) closely resembles that of ethyl 2-(2-bromophenoxy)acetate with similar geometric parameters. The pendant ethyl chain is in an extended conformation and almost lies in the plane of the substituted benzene ring, as indicated by the dihedral angle of 1.86 (2)°. The
features inversion-related dimers linked by pairs of C—H···O hydrogen bonds generating R22(16) loops (Table 1).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: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: Mercury (Macrae et al., 2008).Fig. 1. A view of the molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. |
C11H13ClO3 | Z = 2 |
Mr = 228.66 | F(000) = 240 |
Triclinic, P1 | Dx = 1.371 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54178 Å |
a = 7.0296 (3) Å | Cell parameters from 1784 reflections |
b = 8.3258 (4) Å | θ = 4.4–64.4° |
c = 10.6552 (5) Å | µ = 2.94 mm−1 |
α = 106.031 (2)° | T = 296 K |
β = 92.977 (2)° | Prism, colourless |
γ = 110.489 (2)° | 0.30 × 0.27 × 0.25 mm |
V = 553.75 (5) Å3 |
Bruker X8 Proteum diffractometer | 1784 independent reflections |
Radiation source: Bruker MicroStar microfocus rotating anode | 1670 reflections with I > 2σ(I) |
Helios multilayer optics monochromator | Rint = 0.036 |
Detector resolution: 18.4 pixels mm-1 | θmax = 64.4°, θmin = 4.4° |
φ and ω scans | h = −7→8 |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | k = −9→9 |
Tmin = 0.472, Tmax = 0.526 | l = −12→12 |
5636 measured reflections |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.161 | w = 1/[σ2(Fo2) + (0.1056P)2 + 0.2726P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max = 0.001 |
1784 reflections | Δρmax = 0.38 e Å−3 |
138 parameters | Δρmin = −0.59 e Å−3 |
0 restraints |
C11H13ClO3 | γ = 110.489 (2)° |
Mr = 228.66 | V = 553.75 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.0296 (3) Å | Cu Kα radiation |
b = 8.3258 (4) Å | µ = 2.94 mm−1 |
c = 10.6552 (5) Å | T = 296 K |
α = 106.031 (2)° | 0.30 × 0.27 × 0.25 mm |
β = 92.977 (2)° |
Bruker X8 Proteum diffractometer | 1784 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | 1670 reflections with I > 2σ(I) |
Tmin = 0.472, Tmax = 0.526 | Rint = 0.036 |
5636 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 138 parameters |
wR(F2) = 0.161 | 0 restraints |
S = 1.13 | Δρmax = 0.38 e Å−3 |
1784 reflections | Δρmin = −0.59 e Å−3 |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all 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 observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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. |
x | y | z | Uiso*/Ueq | ||
Cl7 | 1.37595 (9) | 0.87199 (8) | 0.58887 (6) | 0.0312 (2) | |
O9 | 0.7485 (2) | 0.4639 (2) | 0.84725 (15) | 0.0224 (5) | |
O12 | 0.4792 (3) | 0.2730 (3) | 0.97377 (17) | 0.0284 (6) | |
O13 | 0.2155 (2) | 0.2149 (2) | 0.81678 (15) | 0.0241 (5) | |
C1 | 0.8857 (4) | 0.5586 (3) | 0.7817 (2) | 0.0198 (7) | |
C2 | 1.0925 (4) | 0.6208 (3) | 0.8362 (2) | 0.0215 (7) | |
C3 | 1.2409 (4) | 0.7181 (3) | 0.7765 (2) | 0.0222 (7) | |
C4 | 1.1822 (4) | 0.7507 (3) | 0.6622 (2) | 0.0227 (7) | |
C5 | 0.9776 (4) | 0.6918 (3) | 0.6062 (2) | 0.0218 (7) | |
C6 | 0.8291 (4) | 0.5936 (3) | 0.6680 (2) | 0.0215 (7) | |
C8 | 0.9113 (4) | 0.7284 (4) | 0.4843 (2) | 0.0283 (8) | |
C10 | 0.5383 (3) | 0.3888 (3) | 0.7888 (2) | 0.0218 (7) | |
C11 | 0.4128 (4) | 0.2861 (3) | 0.8724 (2) | 0.0207 (7) | |
C14 | 0.0719 (4) | 0.1132 (3) | 0.8866 (2) | 0.0242 (7) | |
C15 | −0.1422 (4) | 0.0697 (4) | 0.8207 (3) | 0.0300 (8) | |
H2 | 1.13040 | 0.59710 | 0.91210 | 0.0260* | |
H3 | 1.37950 | 0.76150 | 0.81250 | 0.0270* | |
H6 | 0.69040 | 0.55110 | 0.63240 | 0.0260* | |
H8A | 0.97420 | 0.85530 | 0.49600 | 0.0420* | |
H8B | 0.76420 | 0.69110 | 0.46950 | 0.0420* | |
H8C | 0.95310 | 0.66220 | 0.40940 | 0.0420* | |
H10A | 0.52010 | 0.30820 | 0.69990 | 0.0260* | |
H10B | 0.49260 | 0.48430 | 0.78320 | 0.0260* | |
H14A | 0.09320 | 0.18430 | 0.97890 | 0.0290* | |
H14B | 0.09280 | 0.00280 | 0.88250 | 0.0290* | |
H15A | −0.16000 | 0.17970 | 0.82350 | 0.0450* | |
H15B | −0.24060 | 0.00510 | 0.86630 | 0.0450* | |
H15C | −0.16280 | −0.00370 | 0.73020 | 0.0450* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl7 | 0.0252 (4) | 0.0335 (4) | 0.0300 (4) | 0.0018 (3) | 0.0071 (3) | 0.0141 (3) |
O9 | 0.0139 (9) | 0.0291 (10) | 0.0229 (9) | 0.0039 (7) | 0.0014 (6) | 0.0119 (7) |
O12 | 0.0211 (9) | 0.0383 (11) | 0.0277 (9) | 0.0088 (8) | 0.0014 (7) | 0.0168 (8) |
O13 | 0.0145 (8) | 0.0308 (10) | 0.0240 (9) | 0.0031 (7) | 0.0019 (7) | 0.0115 (7) |
C1 | 0.0199 (12) | 0.0193 (12) | 0.0197 (12) | 0.0064 (10) | 0.0035 (9) | 0.0066 (9) |
C2 | 0.0205 (12) | 0.0233 (12) | 0.0189 (11) | 0.0073 (10) | 0.0007 (9) | 0.0058 (9) |
C3 | 0.0168 (11) | 0.0232 (13) | 0.0230 (12) | 0.0058 (10) | 0.0008 (9) | 0.0047 (9) |
C4 | 0.0216 (13) | 0.0215 (12) | 0.0217 (12) | 0.0047 (10) | 0.0051 (10) | 0.0059 (10) |
C5 | 0.0249 (12) | 0.0200 (12) | 0.0193 (12) | 0.0081 (10) | 0.0024 (9) | 0.0050 (9) |
C6 | 0.0188 (12) | 0.0217 (12) | 0.0218 (12) | 0.0065 (10) | 0.0003 (9) | 0.0054 (10) |
C8 | 0.0301 (14) | 0.0304 (14) | 0.0244 (13) | 0.0097 (11) | 0.0027 (10) | 0.0113 (10) |
C10 | 0.0150 (12) | 0.0276 (13) | 0.0201 (11) | 0.0058 (10) | −0.0004 (9) | 0.0072 (10) |
C11 | 0.0179 (12) | 0.0219 (12) | 0.0213 (12) | 0.0080 (10) | 0.0026 (9) | 0.0049 (10) |
C14 | 0.0205 (12) | 0.0252 (13) | 0.0257 (12) | 0.0056 (10) | 0.0074 (9) | 0.0097 (10) |
C15 | 0.0190 (12) | 0.0301 (14) | 0.0370 (14) | 0.0051 (11) | 0.0048 (10) | 0.0101 (11) |
Cl7—C4 | 1.752 (3) | C14—C15 | 1.503 (4) |
O9—C1 | 1.372 (3) | C2—H2 | 0.9300 |
O9—C10 | 1.416 (3) | C3—H3 | 0.9300 |
O12—C11 | 1.202 (3) | C6—H6 | 0.9300 |
O13—C11 | 1.331 (3) | C8—H8A | 0.9600 |
O13—C14 | 1.455 (3) | C8—H8B | 0.9600 |
C1—C2 | 1.392 (4) | C8—H8C | 0.9600 |
C1—C6 | 1.392 (3) | C10—H10A | 0.9700 |
C2—C3 | 1.382 (4) | C10—H10B | 0.9700 |
C3—C4 | 1.391 (3) | C14—H14A | 0.9700 |
C4—C5 | 1.386 (4) | C14—H14B | 0.9700 |
C5—C6 | 1.401 (4) | C15—H15A | 0.9600 |
C5—C8 | 1.501 (3) | C15—H15B | 0.9600 |
C10—C11 | 1.509 (3) | C15—H15C | 0.9600 |
C1—O9—C10 | 116.67 (18) | C5—C6—H6 | 119.00 |
C11—O13—C14 | 115.92 (18) | C5—C8—H8A | 109.00 |
O9—C1—C2 | 115.63 (19) | C5—C8—H8B | 109.00 |
O9—C1—C6 | 124.1 (2) | C5—C8—H8C | 109.00 |
C2—C1—C6 | 120.3 (2) | H8A—C8—H8B | 109.00 |
C1—C2—C3 | 119.3 (2) | H8A—C8—H8C | 109.00 |
C2—C3—C4 | 119.8 (3) | H8B—C8—H8C | 109.00 |
Cl7—C4—C3 | 118.1 (2) | O9—C10—H10A | 110.00 |
Cl7—C4—C5 | 119.66 (17) | O9—C10—H10B | 110.00 |
C3—C4—C5 | 122.3 (2) | C11—C10—H10A | 110.00 |
C4—C5—C6 | 117.3 (2) | C11—C10—H10B | 110.00 |
C4—C5—C8 | 123.0 (2) | H10A—C10—H10B | 108.00 |
C6—C5—C8 | 119.7 (2) | O13—C14—H14A | 110.00 |
C1—C6—C5 | 121.1 (3) | O13—C14—H14B | 110.00 |
O9—C10—C11 | 108.97 (18) | C15—C14—H14A | 110.00 |
O12—C11—O13 | 125.5 (2) | C15—C14—H14B | 110.00 |
O12—C11—C10 | 125.7 (3) | H14A—C14—H14B | 108.00 |
O13—C11—C10 | 108.80 (18) | C14—C15—H15A | 109.00 |
O13—C14—C15 | 107.6 (2) | C14—C15—H15B | 109.00 |
C1—C2—H2 | 120.00 | C14—C15—H15C | 109.00 |
C3—C2—H2 | 120.00 | H15A—C15—H15B | 109.00 |
C2—C3—H3 | 120.00 | H15A—C15—H15C | 110.00 |
C4—C3—H3 | 120.00 | H15B—C15—H15C | 109.00 |
C1—C6—H6 | 119.00 | ||
C10—O9—C1—C2 | −175.9 (2) | C2—C3—C4—Cl7 | −179.15 (19) |
C10—O9—C1—C6 | 4.2 (3) | C2—C3—C4—C5 | 1.3 (4) |
C1—O9—C10—C11 | 178.42 (19) | Cl7—C4—C5—C8 | −0.6 (3) |
C14—O13—C11—O12 | −0.1 (4) | Cl7—C4—C5—C6 | 179.27 (18) |
C14—O13—C11—C10 | −179.00 (18) | C3—C4—C5—C8 | 178.9 (2) |
C11—O13—C14—C15 | 171.3 (2) | C3—C4—C5—C6 | −1.2 (4) |
C2—C1—C6—C5 | −0.1 (4) | C8—C5—C6—C1 | −179.5 (2) |
O9—C1—C2—C3 | −179.8 (2) | C4—C5—C6—C1 | 0.6 (4) |
O9—C1—C6—C5 | 179.8 (2) | O9—C10—C11—O12 | 1.5 (3) |
C6—C1—C2—C3 | 0.2 (4) | O9—C10—C11—O13 | −179.67 (18) |
C1—C2—C3—C4 | −0.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O12i | 0.93 | 2.57 | 3.194 (3) | 125 |
Symmetry code: (i) −x+2, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O12i | 0.93 | 2.57 | 3.194 (3) | 125 |
Symmetry code: (i) −x+2, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C11H13ClO3 |
Mr | 228.66 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 7.0296 (3), 8.3258 (4), 10.6552 (5) |
α, β, γ (°) | 106.031 (2), 92.977 (2), 110.489 (2) |
V (Å3) | 553.75 (5) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 2.94 |
Crystal size (mm) | 0.30 × 0.27 × 0.25 |
Data collection | |
Diffractometer | Bruker X8 Proteum |
Absorption correction | Multi-scan (SADABS; Bruker, 2013) |
Tmin, Tmax | 0.472, 0.526 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5636, 1784, 1670 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.585 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.161, 1.13 |
No. of reflections | 1784 |
No. of parameters | 138 |
Δρmax, Δρmin (e Å−3) | 0.38, −0.59 |
Computer programs: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008).
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. YHIM thanks the 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 CISEE scheme, Department of Information Technology, Biotechnology and Science and Technology, Bangalore.
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