organic compounds
of ethyl 2-(4-chloroanilino)acetate
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
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⋯Oc (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
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2.3. Refinement
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Data collection: APEX2 (Bruker, 2009); cell 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
10.1107/S1600536814018297/hb7269sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814018297/hb7269Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814018297/hb7269Isup3.cml
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
on silica gel using hexane/ethyl acetate (9/1) as Yellow blocks were isolated when the solvent was allowed to evaporateAll H atoms could be located in a difference Fourier map. However, they were placed in calculated positions with C–H = 0.93–0.97 Å; N—H = 0.86 Å, and refined as riding on their parent atoms with Uiso(H) = 1.2 Ueq for aromatic, ethylene C—H, N–H and Uiso(H) = 1.5 Ueq for methyl. One outlier (0 0 1) was omitted in the last cycles of refinement.
Data collection: APEX2 (Bruker, 2009); cell
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).C10H12ClNO2 | Z = 2 |
Mr = 213.66 | F(000) = 224 |
Triclinic, P1 | Dx = 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 |
Bruker X8 APEX CCD diffractometer | 2361 independent reflections |
Radiation source: fine-focus sealed tube | 1718 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −6→6 |
Tmin = 0.693, Tmax = 0.747 | k = −9→7 |
3672 measured reflections | l = −18→10 |
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(Fo2) + (0.0633P)2 + 0.1405P] where P = (Fo2 + 2Fc2)/3 |
2361 reflections | (Δ/σ)max < 0.001 |
127 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C10H12ClNO2 | γ = 72.99 (3)° |
Mr = 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)° |
Bruker X8 APEX CCD diffractometer | 2361 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1718 reflections with I > 2σ(I) |
Tmin = 0.693, Tmax = 0.747 | Rint = 0.018 |
3672 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.23 e Å−3 |
2361 reflections | Δρmin = −0.25 e Å−3 |
127 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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 |
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. |
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.
References
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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).