Crystal structure of ethyl 2-(4-chloro­anilino)acetate

Bouali, J.; Hafid, A.; Khouili, M.; Saadi, M.; Ketatni, E.M.

doi:10.1107/S1600536814018297

organic compounds

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ISSN: 2056-9890

Volume 70| Part 9| September 2014| Page o1017

doi:10.1107/S1600536814018297

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Crystal structure of ethyl 2-(4-chloroanilino)acetate

Jamila Bouali,^a Abderrafia Hafid,^a Mostafa Khouili,^a ^* Mohamed Saadi ^b and El Mostafa Ketatni ^c

^aLaboratoire de Chimie Organique et Analytique, Université Sultan Moulay Slimane, Faculté des Sciences et Techniques, BP 523, 23000 Béni-Mellal, Morocco, ^bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco, and ^cLaboratoire de Spectrochimie Applique et Environnement, Université Sultan Moulay Slimane, Faculté des Sciences et Techniques, BP 523, 23000 Béni-Mellal, Morocco
^*Correspondence e-mail: m.khouili@usms.ma

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 9 August 2014; accepted 10 August 2014; online 16 August 2014)

The title compound, C₁₀H₁₂ClNO₂, is close to planar (r.m.s. deviation for the 14 non-H atoms = 0.053 Å). In the crystal, inversion dimers linked by pairs of N—H⋯O_c (c = carboxyl) hydrogen bonds generate R₂²(10) loops.

Keywords: crystal structure; ethyl 2-(4-chloroanilino)acetate; syndone derivatives; biological activity; hydrogen bonding.

CCDC reference: 1018685

1. Related literature

For the biological activity of sydnone derivatives, see: Satheesha Rai et al. (2008 ); Patel & Patel (2012 ). For an overview of sydnone derivatives, see: Asundaria et al. (2010 ); Ding et al. (2013 ); Fadda & Elattar (2012 ). For a related structure, see: Zhang et al. (2010 ).

2. Experimental

2.1. Crystal data

C₁₀H₁₂ClNO₂
M_r = 213.66
Triclinic, $[P \overline 1]$
a = 5.373 (5) Å
b = 7.575 (7) Å
c = 14.127 (12) Å
α = 75.83 (4)°
β = 87.73 (3)°
γ = 72.99 (3)°
V = 532.7 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 296 K
0.40 × 0.36 × 0.29 mm

2.2. Data collection

Bruker X8 APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009) T_min = 0.693, T_max = 0.747
3672 measured reflections
2361 independent reflections
1718 reflections with I > 2σ(I)
R_int = 0.018

2.3. Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.136
S = 1.03
2361 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.82	2.37	3.172 (3)	165
Symmetry code: (i) -x+2, -y, -z+1.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1018685

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814018297/hb7269sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814018297/hb7269Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814018297/hb7269Isup3.cml

checkCIF report

Comment top

The title compound was synthesized as a precursor for the preparation of biological sydnone derivatives (Satheesha Rai et al., 2008; Patel & Patel, 2012, Asundaria et al., 2010; Ding et al., 2013; Fadda & Elattar, 2012). In the title molecule (Fig. 1), there are two planar subunits viz. the chlorophenyl amine (C1-C6N1Cl1) and ethyl acetate (C7C8O2O1C9C10) groups. The chlorophenyl amino ring is inclined at angles of 2.01 (9)° to the ethyl acetate groups. The substituted amino substituent is in an extended conformation with an N—C—C—O torsion angle of 179.8 (2)°. In the crystal structure, pairs of molecules are connected by intermolecular N—H···O hydrogen bonds to form centrosymmetric dimers (Fig. 2). Bond lengths and angles (Table 2) are compatible with those found in a related compound (Zhang et al., 2010).

Related literature top

For the biological activity of sydnone derivatives, see: Satheesha Rai et al. (2008); Patel & Patel (2012). For an overview of sydnone derivatives, see: Asundaria et al. (2010); Ding et al. (2013); Fadda & Elattar (2012). For a related structure, see: Zhang et al. (2010).

Experimental top

A solution of corresponding 4-chloroaniline (2.22 g, 0.0174 mol), anhydrous sodium acetate (2.14 g, 0.0261 mol, 1.5 equiv), and ethyl chloroacetate (2.13 g, 0.0174 mol) was heated under reflux for 18 h. Then cold water (70 ml) was added with stirring and cooling in ice bath. The reaction mixture was neutralized with NaHCO₃ and then extracted with dichloromethane (3× 25 ml). The dichloromethane extracts were dried over anhydrous Na₂SO₄ and concentrated. The crude product was purified by column chromatography on silica gel using hexane/ethyl acetate (9/1) as eluent. Yellow blocks were isolated when the solvent was allowed to evaporate

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Part of the crystal structure of the title compound, showing hydrogen-bonded (dashed lines) dimers.

Ethyl 2-(4-chloroanilino)acetate top

Crystal data top

C₁₀H₁₂ClNO₂	Z = 2
M_r = 213.66	F(000) = 224
Triclinic, P1	D_x = 1.332 Mg m⁻³
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.373 (5) Å	Cell parameters from 2361 reflections
b = 7.575 (7) Å	θ = 2.9–27.5°
c = 14.127 (12) Å	µ = 0.33 mm⁻¹
α = 75.83 (4)°	T = 296 K
β = 87.73 (3)°	Block, yellow
γ = 72.99 (3)°	0.40 × 0.36 × 0.29 mm
V = 532.7 (9) Å³

Data collection top

Bruker X8 APEX CCD diffractometer	2361 independent reflections
Radiation source: fine-focus sealed tube	1718 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→6
T_min = 0.693, T_max = 0.747	k = −9→7
3672 measured reflections	l = −18→10

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0633P)² + 0.1405P] where P = (F_o² + 2F_c²)/3
2361 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₀H₁₂ClNO₂	γ = 72.99 (3)°
M_r = 213.66	V = 532.7 (9) Å³
Triclinic, P1	Z = 2
a = 5.373 (5) Å	Mo Kα radiation
b = 7.575 (7) Å	µ = 0.33 mm⁻¹
c = 14.127 (12) Å	T = 296 K
α = 75.83 (4)°	0.40 × 0.36 × 0.29 mm
β = 87.73 (3)°

Data collection top

Bruker X8 APEX CCD diffractometer	2361 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1718 reflections with I > 2σ(I)
T_min = 0.693, T_max = 0.747	R_int = 0.018
3672 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.03	Δρ_max = 0.23 e Å⁻³
2361 reflections	Δρ_min = −0.25 e Å⁻³
127 parameters

Special details top

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

Refinement. Refinement of F² against all reflections. The weighted R-factor wR and 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 threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) 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
C1	0.2530 (4)	0.5821 (3)	0.17905 (14)	0.0493 (5)
C2	0.1089 (4)	0.5877 (3)	0.26135 (14)	0.0493 (5)
H2	−0.0633	0.6634	0.2564	0.059*
C3	0.2208 (3)	0.4803 (3)	0.35168 (14)	0.0460 (4)
H3	0.1234	0.4845	0.4074	0.055*
C4	0.4789 (3)	0.3659 (2)	0.35964 (13)	0.0408 (4)
C5	0.6209 (3)	0.3653 (3)	0.27463 (14)	0.0466 (4)
H5	0.7939	0.2912	0.2788	0.056*
C6	0.5104 (4)	0.4718 (3)	0.18512 (14)	0.0511 (5)
H6	0.6073	0.4700	0.1292	0.061*
C7	0.4644 (3)	0.2344 (3)	0.53739 (13)	0.0434 (4)
H7A	0.3204	0.1854	0.5300	0.052*
H7B	0.3945	0.3563	0.5536	0.052*
C8	0.6487 (3)	0.0983 (2)	0.61773 (13)	0.0421 (4)
C9	0.6934 (4)	−0.0457 (3)	0.78700 (13)	0.0494 (5)
H9A	0.8456	−0.0068	0.7962	0.059*
H9B	0.7510	−0.1735	0.7770	0.059*
C10	0.5267 (5)	−0.0410 (4)	0.87449 (15)	0.0683 (6)
H10A	0.6254	−0.1259	0.9314	0.102*
H10B	0.3772	−0.0802	0.8646	0.102*
H10C	0.4708	0.0861	0.8836	0.102*
N1	0.5998 (3)	0.2584 (3)	0.44760 (12)	0.0593 (5)
H1	0.7422	0.1814	0.4453	0.071*
O1	0.5353 (2)	0.08512 (18)	0.70336 (9)	0.0470 (3)
O2	0.8685 (3)	0.0108 (2)	0.60581 (10)	0.0620 (4)
Cl1	0.11032 (12)	0.71314 (11)	0.06510 (4)	0.0837 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0484 (10)	0.0478 (10)	0.0434 (10)	−0.0104 (8)	−0.0067 (8)	0.0011 (8)
C2	0.0367 (9)	0.0459 (10)	0.0546 (11)	−0.0012 (8)	−0.0042 (8)	−0.0048 (8)
C3	0.0408 (9)	0.0471 (10)	0.0415 (10)	−0.0031 (8)	0.0042 (7)	−0.0071 (8)
C4	0.0377 (9)	0.0375 (9)	0.0417 (9)	−0.0052 (7)	−0.0013 (7)	−0.0062 (7)
C5	0.0359 (9)	0.0472 (10)	0.0480 (10)	−0.0025 (8)	0.0044 (7)	−0.0079 (8)
C6	0.0487 (10)	0.0553 (11)	0.0429 (10)	−0.0120 (9)	0.0060 (8)	−0.0048 (8)
C7	0.0422 (9)	0.0403 (9)	0.0413 (9)	−0.0030 (7)	0.0006 (7)	−0.0093 (7)
C8	0.0443 (10)	0.0376 (9)	0.0398 (9)	−0.0044 (8)	0.0018 (7)	−0.0101 (7)
C9	0.0471 (10)	0.0517 (11)	0.0402 (10)	−0.0044 (8)	−0.0025 (8)	−0.0058 (8)
C10	0.0728 (15)	0.0781 (15)	0.0406 (11)	−0.0065 (12)	0.0067 (10)	−0.0096 (10)
N1	0.0437 (9)	0.0669 (11)	0.0412 (9)	0.0132 (8)	0.0029 (7)	−0.0013 (8)
O1	0.0440 (7)	0.0480 (7)	0.0375 (7)	0.0006 (5)	0.0023 (5)	−0.0068 (5)
O2	0.0479 (8)	0.0668 (9)	0.0468 (8)	0.0120 (7)	0.0062 (6)	−0.0042 (7)
Cl1	0.0720 (4)	0.1006 (5)	0.0500 (4)	−0.0037 (3)	−0.0123 (3)	0.0101 (3)

Geometric parameters (Å, º) top

C1—C2	1.373 (3)	C7—C8	1.500 (3)
C1—C6	1.384 (3)	C7—H7A	0.9700
C1—Cl1	1.742 (2)	C7—H7B	0.9700
C2—C3	1.385 (3)	C8—O2	1.202 (2)
C2—H2	0.9300	C8—O1	1.328 (2)
C3—C4	1.396 (3)	C9—O1	1.453 (2)
C3—H3	0.9300	C9—C10	1.499 (3)
C4—N1	1.374 (2)	C9—H9A	0.9700
C4—C5	1.397 (3)	C9—H9B	0.9700
C5—C6	1.372 (3)	C10—H10A	0.9600
C5—H5	0.9300	C10—H10B	0.9600
C6—H6	0.9300	C10—H10C	0.9600
C7—N1	1.436 (3)	N1—H1	0.8201

C2—C1—C6	120.88 (18)	C8—C7—H7B	109.8
C2—C1—Cl1	119.85 (16)	H7A—C7—H7B	108.2
C6—C1—Cl1	119.27 (16)	O2—C8—O1	124.56 (17)
C1—C2—C3	119.83 (18)	O2—C8—C7	124.41 (17)
C1—C2—H2	120.1	O1—C8—C7	111.03 (16)
C3—C2—H2	120.1	O1—C9—C10	107.18 (17)
C2—C3—C4	120.43 (17)	O1—C9—H9A	110.3
C2—C3—H3	119.8	C10—C9—H9A	110.3
C4—C3—H3	119.8	O1—C9—H9B	110.3
N1—C4—C3	122.69 (17)	C10—C9—H9B	110.3
N1—C4—C5	119.02 (17)	H9A—C9—H9B	108.5
C3—C4—C5	118.27 (16)	C9—C10—H10A	109.5
C6—C5—C4	121.34 (17)	C9—C10—H10B	109.5
C6—C5—H5	119.3	H10A—C10—H10B	109.5
C4—C5—H5	119.3	C9—C10—H10C	109.5
C5—C6—C1	119.24 (18)	H10A—C10—H10C	109.5
C5—C6—H6	120.4	H10B—C10—H10C	109.5
C1—C6—H6	120.4	C4—N1—C7	123.16 (16)
N1—C7—C8	109.52 (16)	C4—N1—H1	116.6
N1—C7—H7A	109.8	C7—N1—H1	117.7
C8—C7—H7A	109.8	C8—O1—C9	116.23 (15)
N1—C7—H7B	109.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.82	2.37	3.172 (3)	165

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.82	2.37	3.172 (3)	165

Symmetry code: (i) −x+2, −y, −z+1.

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements and the University Sultan Moulay Slimane, Beni-Mellal, for financial support.

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