Acta Cryst. (2008). E64, o2400 [ doi:10.1107/S1600536808038336 ]
In the title compound, C15H13Cl2NO2, the dihedral angle between the aromatic rings is 63.80 (12)°. The conformation may be stabilized by a weak N-H
O hydrogen bond. In the crystal structure, a short C-Cl![[pi]](/logos/entities/pi_rmgif.gif)
interaction occurs, with a Cl separation of 3.5706 (13) Å.
A mixture of 2-(2,6-dichlorophenylamino)benzoic acid (2.81 g, 10 mmol) and absolute methanol (50 ml) in the presence of a few drops of sulfuric acid was refluxed for 5 h. The excess of the solvent was removed by distillation. The solid residue was filltered off, washed with water and recystallized from ethanol (30%) to give the title compound. Suitable single crystals of the title compound were obtained by slow evaporation of an ethanol solution at room temperature. (Yield, 88%; m.p. 331–332 K)
H atoms were positioned geometrically, with O—H = 0.82 Å and C—H = 0.93, 0.97 and 0.96 Å for aryl, methylene and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.5Ueq(methyl C) and 1.2Ueq(aryl and methylene C and O)
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2003).
![[Figure 1]](./pv2122fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme; thermal ellipsoids have been plotted at 50% probability level. |
![[Figure 2]](./pv2122fig2thm.gif)
| Fig. 2. The formation of the title compound. |
| C15H13Cl2NO2 | F(000) = 640 |
| Mr = 310.16 | Dx = 1.446 Mg m−3 |
| Monoclinic, P21/n | Melting point: 331 K |
| Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
| a = 4.9319 (4) Å | Cell parameters from 9949 reflections |
| b = 20.0288 (14) Å | θ = 2.4–28.3° |
| c = 14.5542 (10) Å | µ = 0.46 mm−1 |
| β = 97.711 (1)° | T = 173 K |
| V = 1424.66 (18) Å3 | Block, pale yellow |
| Z = 4 | 0.38 × 0.24 × 0.20 mm |
| Bruker SMART APEXII CCD diffractometer | 3423 independent reflections |
| Radiation source: fine-focus sealed tube | 2777 reflections with I > 2σ(I) |
| graphite | Rint = 0.020 |
| ω and φ scans | θmax = 28.3°, θmin = 2.5° |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −6→6 |
| Tmin = 0.850, Tmax = 1.000 | k = −26→26 |
| 8526 measured reflections | l = −19→15 |
| 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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.171 | H-atom parameters constrained |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.1042P)2 + 0.5254P] where P = (Fo2 + 2Fc2)/3 |
| 3423 reflections | (Δ/σ)max < 0.001 |
| 181 parameters | Δρmax = 0.62 e Å−3 |
| 0 restraints | Δρmin = −0.52 e Å−3 |
| C15H13Cl2NO2 | V = 1424.66 (18) Å3 |
| Mr = 310.16 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 4.9319 (4) Å | µ = 0.46 mm−1 |
| b = 20.0288 (14) Å | T = 173 K |
| c = 14.5542 (10) Å | 0.38 × 0.24 × 0.20 mm |
| β = 97.711 (1)° |
| Bruker SMART APEXII CCD diffractometer | 3423 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 2777 reflections with I > 2σ(I) |
| Tmin = 0.850, Tmax = 1.000 | Rint = 0.020 |
| 8526 measured reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
| wR(F2) = 0.171 | Δρmax = 0.62 e Å−3 |
| S = 1.04 | Δρmin = −0.52 e Å−3 |
| 3423 reflections | Absolute structure: ? |
| 181 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | 0.8063 (4) | 0.18670 (11) | 0.42183 (15) | 0.0459 (5) | |
| C2 | 0.9559 (6) | 0.23352 (14) | 0.47685 (18) | 0.0592 (7) | |
| H2A | 0.9401 | 0.2361 | 0.5411 | 0.071* | |
| C3 | 1.1298 (6) | 0.27691 (13) | 0.4384 (2) | 0.0646 (7) | |
| H3A | 1.2365 | 0.3084 | 0.4764 | 0.077* | |
| C4 | 1.1462 (6) | 0.27396 (11) | 0.3451 (2) | 0.0572 (6) | |
| H4A | 1.2586 | 0.3046 | 0.3178 | 0.069* | |
| C5 | 0.9985 (5) | 0.22618 (10) | 0.29100 (16) | 0.0454 (5) | |
| C6 | 0.8295 (4) | 0.17922 (9) | 0.32730 (13) | 0.0386 (4) | |
| C7 | 0.6955 (4) | 0.06202 (9) | 0.29122 (13) | 0.0360 (4) | |
| C8 | 0.8988 (5) | 0.03457 (12) | 0.35515 (15) | 0.0468 (5) | |
| H8A | 1.0348 | 0.0624 | 0.3879 | 0.056* | |
| C9 | 0.9027 (6) | −0.03407 (14) | 0.37114 (18) | 0.0614 (7) | |
| H9A | 1.0410 | −0.0529 | 0.4153 | 0.074* | |
| C10 | 0.7088 (7) | −0.07451 (13) | 0.3237 (2) | 0.0676 (8) | |
| H10A | 0.7142 | −0.1213 | 0.3347 | 0.081* | |
| C11 | 0.5040 (5) | −0.04753 (12) | 0.25957 (19) | 0.0549 (6) | |
| H11A | 0.3696 | −0.0759 | 0.2271 | 0.066* | |
| C12 | 0.4948 (4) | 0.02126 (10) | 0.24258 (14) | 0.0388 (4) | |
| C13 | 0.2660 (4) | 0.04998 (12) | 0.17557 (15) | 0.0434 (5) | |
| H13A | 0.1975 | 0.0907 | 0.2033 | 0.052* | |
| H13B | 0.1140 | 0.0173 | 0.1670 | 0.052* | |
| C14 | 0.3438 (4) | 0.06753 (10) | 0.08154 (14) | 0.0374 (4) | |
| C15 | 0.1597 (4) | 0.09199 (12) | −0.07671 (14) | 0.0433 (5) | |
| H15A | −0.0226 | 0.0958 | −0.1125 | 0.065* | |
| H15B | 0.2626 | 0.0566 | −0.1032 | 0.065* | |
| H15C | 0.2570 | 0.1345 | −0.0789 | 0.065* | |
| Cl1 | 0.57692 (13) | 0.13766 (4) | 0.47192 (4) | 0.0602 (2) | |
| Cl2 | 1.01835 (17) | 0.22543 (3) | 0.17271 (4) | 0.0654 (2) | |
| N1 | 0.6851 (4) | 0.13126 (8) | 0.27114 (12) | 0.0425 (4) | |
| H1A | 0.5820 | 0.1447 | 0.2205 | 0.051* | |
| O1 | 0.5844 (3) | 0.07442 (10) | 0.06748 (12) | 0.0591 (5) | |
| O2 | 0.1341 (3) | 0.07623 (9) | 0.01586 (12) | 0.0550 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0417 (11) | 0.0525 (12) | 0.0422 (11) | 0.0138 (9) | 0.0005 (8) | −0.0030 (9) |
| C2 | 0.0595 (15) | 0.0663 (15) | 0.0479 (12) | 0.0187 (12) | −0.0069 (10) | −0.0198 (11) |
| C3 | 0.0656 (16) | 0.0500 (13) | 0.0718 (17) | 0.0071 (11) | −0.0138 (13) | −0.0208 (12) |
| C4 | 0.0564 (14) | 0.0363 (10) | 0.0754 (17) | −0.0006 (9) | −0.0040 (12) | −0.0007 (10) |
| C5 | 0.0512 (12) | 0.0358 (9) | 0.0473 (11) | 0.0055 (8) | −0.0006 (9) | 0.0021 (8) |
| C6 | 0.0373 (10) | 0.0373 (9) | 0.0385 (10) | 0.0064 (7) | −0.0048 (7) | −0.0008 (7) |
| C7 | 0.0370 (9) | 0.0388 (9) | 0.0331 (9) | 0.0030 (7) | 0.0075 (7) | 0.0035 (7) |
| C8 | 0.0460 (11) | 0.0554 (12) | 0.0386 (10) | 0.0100 (9) | 0.0045 (8) | 0.0072 (9) |
| C9 | 0.0735 (17) | 0.0627 (15) | 0.0506 (13) | 0.0289 (13) | 0.0176 (12) | 0.0193 (11) |
| C10 | 0.097 (2) | 0.0419 (12) | 0.0690 (17) | 0.0124 (13) | 0.0313 (16) | 0.0124 (11) |
| C11 | 0.0661 (15) | 0.0420 (11) | 0.0606 (14) | −0.0056 (10) | 0.0230 (12) | 0.0000 (10) |
| C12 | 0.0384 (10) | 0.0412 (10) | 0.0385 (10) | −0.0019 (7) | 0.0111 (8) | 0.0003 (7) |
| C13 | 0.0311 (9) | 0.0565 (12) | 0.0430 (11) | −0.0068 (8) | 0.0073 (8) | −0.0036 (9) |
| C14 | 0.0286 (9) | 0.0407 (9) | 0.0436 (10) | −0.0040 (7) | 0.0075 (7) | −0.0060 (8) |
| C15 | 0.0329 (10) | 0.0601 (12) | 0.0359 (10) | −0.0045 (8) | 0.0005 (7) | 0.0023 (8) |
| Cl1 | 0.0537 (4) | 0.0771 (4) | 0.0521 (4) | 0.0141 (3) | 0.0159 (3) | 0.0074 (3) |
| Cl2 | 0.0911 (5) | 0.0551 (4) | 0.0509 (4) | −0.0072 (3) | 0.0123 (3) | 0.0118 (2) |
| N1 | 0.0489 (10) | 0.0383 (8) | 0.0363 (8) | −0.0016 (7) | −0.0084 (7) | 0.0037 (6) |
| O1 | 0.0273 (7) | 0.1015 (14) | 0.0486 (9) | −0.0057 (7) | 0.0057 (6) | 0.0102 (9) |
| O2 | 0.0413 (8) | 0.0703 (11) | 0.0532 (10) | −0.0023 (7) | 0.0060 (7) | −0.0026 (8) |
| C1—C2 | 1.381 (3) | C9—C10 | 1.367 (5) |
| C1—C6 | 1.404 (3) | C9—H9A | 0.9500 |
| C1—Cl1 | 1.731 (3) | C10—C11 | 1.390 (4) |
| C2—C3 | 1.390 (4) | C10—H10A | 0.9500 |
| C2—H2A | 0.9500 | C11—C12 | 1.399 (3) |
| C3—C4 | 1.371 (4) | C11—H11A | 0.9500 |
| C3—H3A | 0.9500 | C12—C13 | 1.503 (3) |
| C4—C5 | 1.383 (3) | C13—C14 | 1.511 (3) |
| C4—H4A | 0.9500 | C13—H13A | 0.9900 |
| C5—C6 | 1.406 (3) | C13—H13B | 0.9900 |
| C5—Cl2 | 1.738 (2) | C14—O1 | 1.239 (2) |
| C6—N1 | 1.393 (3) | C14—O2 | 1.322 (3) |
| C7—C8 | 1.387 (3) | C15—O2 | 1.406 (3) |
| C7—C12 | 1.400 (3) | C15—H15A | 0.9800 |
| C7—N1 | 1.417 (2) | C15—H15B | 0.9800 |
| C8—C9 | 1.394 (4) | C15—H15C | 0.9800 |
| C8—H8A | 0.9500 | N1—H1A | 0.8800 |
| C2—C1—C6 | 122.2 (2) | C9—C10—H10A | 119.8 |
| C2—C1—Cl1 | 118.01 (19) | C11—C10—H10A | 119.8 |
| C6—C1—Cl1 | 119.72 (17) | C10—C11—C12 | 120.3 (2) |
| C1—C2—C3 | 120.1 (2) | C10—C11—H11A | 119.8 |
| C1—C2—H2A | 120.0 | C12—C11—H11A | 119.8 |
| C3—C2—H2A | 120.0 | C11—C12—C7 | 118.7 (2) |
| C4—C3—C2 | 119.5 (2) | C11—C12—C13 | 119.7 (2) |
| C4—C3—H3A | 120.2 | C7—C12—C13 | 121.54 (18) |
| C2—C3—H3A | 120.2 | C12—C13—C14 | 114.64 (16) |
| C3—C4—C5 | 119.8 (3) | C12—C13—H13A | 108.6 |
| C3—C4—H4A | 120.1 | C14—C13—H13A | 108.6 |
| C5—C4—H4A | 120.1 | C12—C13—H13B | 108.6 |
| C4—C5—C6 | 122.8 (2) | C14—C13—H13B | 108.6 |
| C4—C5—Cl2 | 118.4 (2) | H13A—C13—H13B | 107.6 |
| C6—C5—Cl2 | 118.79 (16) | O1—C14—O2 | 122.7 (2) |
| N1—C6—C1 | 123.1 (2) | O1—C14—C13 | 122.73 (18) |
| N1—C6—C5 | 121.52 (19) | O2—C14—C13 | 114.61 (16) |
| C1—C6—C5 | 115.29 (19) | O2—C15—H15A | 109.5 |
| C8—C7—C12 | 120.44 (19) | O2—C15—H15B | 109.5 |
| C8—C7—N1 | 121.95 (19) | H15A—C15—H15B | 109.5 |
| C12—C7—N1 | 117.59 (17) | O2—C15—H15C | 109.5 |
| C7—C8—C9 | 119.7 (2) | H15A—C15—H15C | 109.5 |
| C7—C8—H8A | 120.1 | H15B—C15—H15C | 109.5 |
| C9—C8—H8A | 120.1 | C6—N1—C7 | 123.53 (16) |
| C10—C9—C8 | 120.5 (2) | C6—N1—H1A | 118.2 |
| C10—C9—H9A | 119.8 | C7—N1—H1A | 118.2 |
| C8—C9—H9A | 119.8 | C14—O2—C15 | 124.07 (17) |
| C9—C10—C11 | 120.3 (2) |
The authors gratefully acknowledge funds from the Higher Education Commission, Islamabad, Pakistan.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
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Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Hashem, A. I., Youssef, A. S. A., Kandeel, K. A. & Abou-Elmagd, W. S. I. (2007). Eur. J. Med. Chem. 42, 934–939.
Husain, A., Khan, M. S. Y., Hasan, S. M. & Alam, M. M. (2005). Eur. J. Med. Chem. 40, 1394–1404.
Nardelli, M. (1995). J. Appl. Cryst. 28, 659.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
Esters are important intermediates in heterocyclic chemistry and have been used for the synthesis of various biologically active five-membered heterocyles such as butenolides, pyrrolones (Husain et al., 2005), oxadiazoles and triazoles (Hashem et al., 2007). In view of the versatility of these compounds, we have synthesized the title compound and report herein its crystal structure.
In the title compound (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The planar ester group (O1/O2/C13/C14/C15) is oriented with respect to the plane of the benzene ring (C7–C12) at an angle 41.33 (2)°. There is a short intramolecular N—H···O hydrogen bond (Table 1) and a π-ring interaction of the type C—Cl···Cg with Cl1···Cg1 (centroid of C1–C6 ring) perpendicular distance 3.5706 (13) Å.