Ethyl 2-(4-chloro-3-methyl­phen­oxy)acetate

Mohammed, Y.H.I.; Naveen, S.; Lokanath, N.K.; Khanum, S.A.

doi:10.1107/S2414314616004168

organic compounds

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ISSN: 2414-3146

Volume 1| Part 3| March 2016| x160416

doi:10.1107/S2414314616004168

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Ethyl 2-(4-chloro-3-methylphenoxy)acetate

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

^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

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 25 February 2016; accepted 11 March 2016; online 18 March 2016)

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 crystal structure 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

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Chemical scheme

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 crystal structure features inversion-related dimers linked by pairs of C—H⋯O hydrogen bonds generating $[R_{2}^{2}]$ (16) loops (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

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.

Figure 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.

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) (v_max/cm⁻¹): 1750 (ester, C=O). The mass spectrum 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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₃ClO₃
M_r	228.66
Crystal system, space group	Triclinic, P $[\overline{1}]$
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 )
T_min, T_max	0.472, 0.526
No. of measured, independent and observed [I > 2σ(I)] reflections	5636, 1784, 1670
R_int	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
Δρ_max, Δρ_min (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 ).

Structural data

CCDC reference: 1463900

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616004168/tk4004sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616004168/tk4004Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616004168/tk4004Isup3.cml

checkCIF report

Experimental top

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) (v_max/cm⁻¹): 1750 (ester, C═O). The mass spectrum 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%.

Structure description top

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 crystal structure features inversion-related dimers linked by pairs of C—H···O hydrogen bonds generating R₂²(16) loops (Table 1).

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: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: Mercury (Macrae et al., 2008).

Figures top

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.

2-Chloro-6-fluorophenyl 4-chlorobenzoate top

Crystal data top

C₁₁H₁₃ClO₃	Z = 2
M_r = 228.66	F(000) = 240
Triclinic, P1	D_x = 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

Data collection top

Bruker X8 Proteum diffractometer	1784 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	1670 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.036
Detector resolution: 18.4 pixels mm^-1	θ_max = 64.4°, θ_min = 4.4°
φ and ω scans	h = −7→8
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −9→9
T_min = 0.472, T_max = 0.526	l = −12→12
5636 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.161	w = 1/[σ²(F_o²) + (0.1056P)² + 0.2726P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max = 0.001
1784 reflections	Δρ_max = 0.38 e Å⁻³
138 parameters	Δρ_min = −0.59 e Å⁻³
0 restraints

Crystal data top

C₁₁H₁₃ClO₃	γ = 110.489 (2)°
M_r = 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)°

Data collection top

Bruker X8 Proteum diffractometer	1784 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	1670 reflections with I > 2σ(I)
T_min = 0.472, T_max = 0.526	R_int = 0.036
5636 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	138 parameters
wR(F²) = 0.161	0 restraints
S = 1.13	Δρ_max = 0.38 e Å⁻³
1784 reflections	Δρ_min = −0.59 e Å⁻³

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.472, 0.526
No. of measured, independent and observed [I > 2σ(I)] reflections	5636, 1784, 1670
R_int	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
Δρ_max, Δρ_min (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.

References

Al-Ghorbani, M., Vigneshwaran, V., Ranganatha, V. L., Prabhakar, B. T. & Khanum, S. A. (2015). Bioorg. Chem. 60, 136–146. CAS PubMed Google Scholar
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Khanum, S. A., Shashikanth, S. & Deepak, A. V. (2004). Bioorg. Chem. 32, 211–222. Web of Science CrossRef PubMed CAS Google Scholar
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