organic compounds
N-(2-nitrophenyl)benzamide
of 3-chloro-aDepartamento de Química, Facultad de Ciencias Naturales y Exactas, Universidad del Valle, Apartado 25360, Santiago de Cali, Colombia, and bWestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland
*Correspondence e-mail: rodimo26@yahoo.es
In the title compound, C13H9ClN2O3, the mean plane of the central amide fragment (r.m.s. deviation = 0.016 Å) subtends dihedral angles of 15.2 (2) and 8.2 (2)° with the chloro- and nitro-substituted benzene rings, respectively. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds, forming C(7) chains which propagate along [010], but no Cl⋯Cl short contacts are observed.
CCDC reference: 1416793
1. Related literature
For halogen–halogen interactions in benzanilide compounds, see: Vener et al. (2013); Nayak et al. (2011).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).
Supporting information
CCDC reference: 1416793
https://doi.org/10.1107/S2056989015014620/hb7476sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015014620/hb7476Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015014620/hb7476Isup3.cml
The title molecule was synthesized taking 0.200 g (1.270 mmol) of 3-chlorobenzoic acid and it was placed under reflux with 2 mL of thionyl chloride for two hours. After this time an equimolar amount of o-nitroaniline, dissolved in 10 mL of acetonitrile and allowed to reflux at constant stirring for 3 hours was added. The final solution was left to slow evaporation to obtain yellow crystals. [m.p. 399 (1)K].
All Hm atoms were positioned in geometrically idealized positions, C—H = 0.95 Å, and were refined using a riding-model approximation with Uiso(H) constrained to 1.2 times Ueq of the respective parent atom. H1N atom was found from the Fourier maps and its coordinates were refined freely.
The ═O1)—C1, is essentially planar (r.m.s. deviation for all non-H atoms = 0.0164 Å) and it forms dihedral angles of 15.2 (2)° with the C1-C6 and 8.2 (2)° with the C8-C13 rings respectively. In the (Fig. 2), molecules are linked by weak C-H···O intermolecular contacts. The C10-H10···O1 hydrogen bond interactions are responsible for crystal growth parallel to (2 0 -2). In this interaction, the C-H in the molecule at (x,y,z) acts as a hydrogen-bond donor to O1 atom of the carbonyl group at (-x+1,+y-1/2,-z+3/2). These interactions generate C(7) chains of molecules along [010]. Other intra N-H···O and N-H···N are observed (see Table 1, Nardelli, 1995). The shorest Cl···Cl contact distance in this structure is 3.943 (3) Å.
determination of 3-chloro-N-(2-nitrophenyl)benzamide (I), is part of a study on benzanilides carried out in our research group, and it was obtained from the reaction between 3-chlorobenzoic acid and 2-nitroaniline mediated by the presence of thionyl chloride. The study of intermolecular halogen-halogen interactions is a current problem and several authors have presented interesting results. Halogen-halogen short interactions, in other similar studies, show Cl···Cl distances of the order of 3.8 Å. Theoretical studies of density analysis, varying the Cl···Cl distance from 3.0 to 4.0 Å, using DFT solid state program, have been undertaken (Vener et al., 2013). Geometric considerations in halogen-halogen interactions, for various benzanilide systems, showed different behaviors. Interactions of fluorine with other halogens Cl, Br, I, in different benzanilide systems, include interactions type: trans, cis or L-geometry (Nayak et al., 2011). The molecular structure of (I) is shown in Fig. 1. The central amide moiety, C8—N1-C7(For halogen–halogen interactions in benzanilide compounds, see: Vener et al. (2013); Nayak et al. (2011).
Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell
CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).C13H9ClN2O3 | Dx = 1.574 Mg m−3 |
Mr = 276.67 | Melting point: 399(1) K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.6300 (9) Å | Cell parameters from 10366 reflections |
b = 14.1462 (12) Å | θ = 3.3–27.0° |
c = 6.7797 (6) Å | µ = 0.33 mm−1 |
β = 105.475 (7)° | T = 123 K |
V = 1167.39 (17) Å3 | Needle, yellow |
Z = 4 | 0.40 × 0.08 × 0.05 mm |
F(000) = 568 |
Oxford Diffraction Gemini S diffractometer | 10366 independent reflections |
Radiation source: fine-focus sealed tube | 7015 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
ω scans | θmax = 29.0°, θmin = 3.3° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | h = −17→17 |
Tmin = 0.839, Tmax = 1.000 | k = −17→17 |
10366 measured reflections | l = −9→8 |
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.179 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0657P)2] where P = (Fo2 + 2Fc2)/3 |
10367 reflections | (Δ/σ)max < 0.001 |
177 parameters | Δρmax = 0.78 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
C13H9ClN2O3 | V = 1167.39 (17) Å3 |
Mr = 276.67 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.6300 (9) Å | µ = 0.33 mm−1 |
b = 14.1462 (12) Å | T = 123 K |
c = 6.7797 (6) Å | 0.40 × 0.08 × 0.05 mm |
β = 105.475 (7)° |
Oxford Diffraction Gemini S diffractometer | 10366 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 7015 reflections with I > 2σ(I) |
Tmin = 0.839, Tmax = 1.000 | Rint = 0.000 |
10366 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.179 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.78 e Å−3 |
10367 reflections | Δρmin = −0.49 e Å−3 |
177 parameters |
Experimental. IR spectra was recorded on a FT—IR SHIMADZU IR-Affinity-1 spectrophotometer. IR (KBr), cm-1, 3348 (amide N–H); 1684 (amide, C=O); 1499 and 1342 (-NO2) Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.34.46 (release 25-11-2010 CrysAlis171 .NET) (compiled Nov 25 2010,17:55:46) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
Cl1 | −0.13525 (11) | 0.17880 (10) | 0.1877 (3) | 0.0345 (4) | |
O1 | 0.3249 (3) | 0.3758 (3) | 0.5550 (7) | 0.0413 (11) | |
O2 | 0.2403 (3) | 0.0390 (3) | 0.4902 (6) | 0.0417 (12) | |
O3 | 0.3446 (4) | −0.0604 (3) | 0.6933 (7) | 0.0467 (13) | |
N1 | 0.2996 (4) | 0.2164 (3) | 0.5084 (7) | 0.0270 (11) | |
N2 | 0.3297 (4) | 0.0170 (4) | 0.6117 (7) | 0.0306 (12) | |
C3 | −0.0406 (4) | 0.2702 (4) | 0.2478 (9) | 0.0246 (12) | |
C2 | 0.0686 (4) | 0.2489 (4) | 0.3410 (8) | 0.0266 (14) | |
H2 | 0.0914 | 0.1852 | 0.3698 | 0.032* | |
C1 | 0.1440 (5) | 0.3226 (4) | 0.3914 (8) | 0.0263 (13) | |
C6 | 0.1099 (5) | 0.4148 (4) | 0.3463 (9) | 0.0344 (16) | |
H6 | 0.1616 | 0.4650 | 0.3786 | 0.041* | |
C5 | −0.0006 (5) | 0.4342 (4) | 0.2534 (10) | 0.0384 (15) | |
H5 | −0.0242 | 0.4977 | 0.2241 | 0.046* | |
C4 | −0.0754 (5) | 0.3611 (4) | 0.2040 (10) | 0.0337 (14) | |
H4 | −0.1505 | 0.3739 | 0.1401 | 0.040* | |
C7 | 0.2650 (5) | 0.3091 (4) | 0.4934 (8) | 0.0264 (13) | |
C8 | 0.4049 (5) | 0.1813 (4) | 0.6035 (8) | 0.0250 (13) | |
C9 | 0.4207 (4) | 0.0857 (4) | 0.6545 (8) | 0.0262 (13) | |
C10 | 0.5238 (5) | 0.0478 (4) | 0.7497 (8) | 0.0313 (14) | |
H10 | 0.5320 | −0.0174 | 0.7838 | 0.038* | |
C11 | 0.6131 (5) | 0.1073 (5) | 0.7928 (9) | 0.0346 (15) | |
H11 | 0.6841 | 0.0831 | 0.8575 | 0.042* | |
C12 | 0.6003 (5) | 0.2006 (4) | 0.7434 (8) | 0.0339 (15) | |
H12 | 0.6630 | 0.2406 | 0.7739 | 0.041* | |
C13 | 0.4981 (4) | 0.2388 (4) | 0.6497 (8) | 0.0298 (14) | |
H13 | 0.4916 | 0.3041 | 0.6167 | 0.036* | |
H1N | 0.253 (6) | 0.161 (5) | 0.460 (10) | 0.07 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0180 (6) | 0.0357 (8) | 0.0445 (8) | −0.0025 (6) | −0.0009 (8) | −0.0003 (8) |
O1 | 0.023 (2) | 0.030 (3) | 0.064 (3) | −0.001 (2) | −0.001 (2) | −0.002 (2) |
O2 | 0.021 (2) | 0.035 (3) | 0.061 (3) | −0.0019 (19) | −0.004 (2) | 0.001 (2) |
O3 | 0.034 (3) | 0.028 (3) | 0.072 (3) | −0.002 (2) | 0.003 (2) | 0.012 (2) |
N1 | 0.017 (2) | 0.028 (3) | 0.032 (3) | −0.002 (2) | −0.002 (2) | 0.000 (2) |
N2 | 0.017 (3) | 0.032 (3) | 0.041 (3) | −0.002 (2) | 0.006 (2) | −0.001 (2) |
C3 | 0.018 (3) | 0.028 (3) | 0.028 (3) | −0.001 (2) | 0.005 (3) | −0.002 (3) |
C2 | 0.018 (3) | 0.030 (3) | 0.031 (3) | 0.001 (3) | 0.004 (2) | 0.003 (2) |
C1 | 0.019 (3) | 0.031 (4) | 0.028 (3) | 0.000 (3) | 0.005 (2) | 0.003 (2) |
C6 | 0.023 (3) | 0.028 (4) | 0.048 (4) | −0.001 (3) | 0.002 (3) | −0.001 (3) |
C5 | 0.024 (3) | 0.033 (4) | 0.053 (4) | 0.007 (2) | 0.000 (4) | 0.009 (4) |
C4 | 0.022 (3) | 0.039 (4) | 0.039 (3) | 0.007 (3) | 0.005 (3) | 0.005 (3) |
C7 | 0.022 (3) | 0.027 (3) | 0.027 (3) | −0.002 (3) | 0.001 (2) | 0.003 (3) |
C8 | 0.016 (3) | 0.031 (4) | 0.025 (3) | 0.001 (3) | 0.001 (2) | 0.000 (3) |
C9 | 0.015 (3) | 0.029 (3) | 0.032 (3) | −0.004 (2) | 0.003 (2) | −0.001 (3) |
C10 | 0.023 (3) | 0.029 (4) | 0.040 (4) | 0.001 (3) | 0.005 (3) | 0.003 (3) |
C11 | 0.018 (3) | 0.043 (4) | 0.041 (4) | −0.002 (3) | 0.003 (3) | −0.002 (3) |
C12 | 0.017 (3) | 0.042 (4) | 0.040 (4) | −0.004 (3) | 0.005 (3) | −0.004 (3) |
C13 | 0.022 (3) | 0.028 (3) | 0.038 (3) | 0.002 (3) | 0.005 (3) | 0.002 (3) |
Cl1—C3 | 1.735 (5) | C6—H6 | 0.9500 |
O1—C7 | 1.212 (6) | C5—C4 | 1.381 (7) |
O2—N2 | 1.247 (5) | C5—H5 | 0.9500 |
O3—N2 | 1.219 (6) | C4—H4 | 0.9500 |
N1—C7 | 1.376 (7) | C8—C9 | 1.396 (7) |
N1—C8 | 1.405 (7) | C8—C13 | 1.397 (7) |
N1—H1N | 0.98 (7) | C9—C10 | 1.397 (8) |
N2—C9 | 1.474 (7) | C10—C11 | 1.374 (8) |
C3—C4 | 1.365 (7) | C10—H10 | 0.9500 |
C3—C2 | 1.388 (7) | C11—C12 | 1.360 (8) |
C2—C1 | 1.392 (7) | C11—H11 | 0.9500 |
C2—H2 | 0.9500 | C12—C13 | 1.387 (7) |
C1—C6 | 1.382 (7) | C12—H12 | 0.9500 |
C1—C7 | 1.513 (8) | C13—H13 | 0.9500 |
C6—C5 | 1.396 (7) | ||
C7—N1—C8 | 127.8 (5) | C5—C4—H4 | 120.2 |
C7—N1—H1N | 126 (4) | O1—C7—N1 | 124.1 (5) |
C8—N1—H1N | 106 (4) | O1—C7—C1 | 121.3 (5) |
O3—N2—O2 | 121.9 (5) | N1—C7—C1 | 114.6 (5) |
O3—N2—C9 | 119.0 (5) | C9—C8—C13 | 116.8 (5) |
O2—N2—C9 | 119.1 (5) | C9—C8—N1 | 120.8 (5) |
C4—C3—C2 | 121.8 (5) | C13—C8—N1 | 122.4 (5) |
C4—C3—Cl1 | 119.3 (4) | C8—C9—C10 | 122.7 (5) |
C2—C3—Cl1 | 118.9 (4) | C8—C9—N2 | 122.5 (5) |
C3—C2—C1 | 118.7 (5) | C10—C9—N2 | 114.8 (5) |
C3—C2—H2 | 120.6 | C11—C10—C9 | 118.3 (6) |
C1—C2—H2 | 120.6 | C11—C10—H10 | 120.9 |
C6—C1—C2 | 120.0 (5) | C9—C10—H10 | 120.9 |
C6—C1—C7 | 116.0 (5) | C12—C11—C10 | 120.3 (6) |
C2—C1—C7 | 124.0 (5) | C12—C11—H11 | 119.8 |
C1—C6—C5 | 120.0 (6) | C10—C11—H11 | 119.8 |
C1—C6—H6 | 120.0 | C11—C12—C13 | 121.7 (6) |
C5—C6—H6 | 120.0 | C11—C12—H12 | 119.2 |
C4—C5—C6 | 119.9 (6) | C13—C12—H12 | 119.2 |
C4—C5—H5 | 120.0 | C12—C13—C8 | 120.1 (5) |
C6—C5—H5 | 120.0 | C12—C13—H13 | 119.9 |
C3—C4—C5 | 119.5 (5) | C8—C13—H13 | 119.9 |
C3—C4—H4 | 120.2 | ||
O2—O2—N2—O3 | 0.0 (3) | C7—N1—C8—C13 | −18.1 (9) |
O2—O2—N2—C9 | 0.0 (6) | C13—C8—C9—C10 | 0.9 (9) |
C4—C3—C2—C1 | 0.2 (9) | N1—C8—C9—C10 | −179.8 (5) |
Cl1—C3—C2—C1 | −179.1 (4) | C13—C8—C9—N2 | −179.1 (5) |
C3—C2—C1—C6 | −0.8 (8) | N1—C8—C9—N2 | 0.2 (8) |
C3—C2—C1—C7 | 179.9 (5) | O3—N2—C9—C8 | −166.2 (6) |
C2—C1—C6—C5 | 1.1 (9) | O2—N2—C9—C8 | 15.1 (8) |
C7—C1—C6—C5 | −179.6 (5) | O2—N2—C9—C8 | 15.1 (8) |
C1—C6—C5—C4 | −0.9 (10) | O3—N2—C9—C10 | 13.8 (7) |
C2—C3—C4—C5 | 0.0 (10) | O2—N2—C9—C10 | −164.8 (5) |
Cl1—C3—C4—C5 | 179.3 (5) | O2—N2—C9—C10 | −164.8 (5) |
C6—C5—C4—C3 | 0.3 (10) | C8—C9—C10—C11 | −0.6 (9) |
C8—N1—C7—O1 | 3.7 (10) | N2—C9—C10—C11 | 179.4 (5) |
C8—N1—C7—C1 | −176.5 (5) | C9—C10—C11—C12 | 0.0 (9) |
C6—C1—C7—O1 | 9.1 (8) | C10—C11—C12—C13 | 0.2 (9) |
C2—C1—C7—O1 | −171.5 (6) | C11—C12—C13—C8 | 0.1 (9) |
C6—C1—C7—N1 | −170.6 (5) | C9—C8—C13—C12 | −0.6 (8) |
C2—C1—C7—N1 | 8.7 (8) | N1—C8—C13—C12 | −179.9 (5) |
C7—N1—C8—C9 | 162.7 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2 | 0.98 (7) | 1.75 (7) | 2.612 (6) | 144 (6) |
C10—H10···O1i | 0.95 | 2.39 | 3.158 (7) | 138 |
Symmetry code: (i) −x+1, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2 | 0.98 (7) | 1.75 (7) | 2.612 (6) | 144 (6) |
C10—H10···O1i | 0.95 | 2.39 | 3.158 (7) | 138 |
Symmetry code: (i) −x+1, y−1/2, −z+3/2. |
Acknowledgements
RMF is grateful to the Universidad del Valle, Colombia, for partial financial support.
References
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The crystal structure determination of 3-chloro-N-(2-nitrophenyl)benzamide (I), is part of a study on benzanilides carried out in our research group, and it was obtained from the reaction between 3-chlorobenzoic acid and 2-nitroaniline mediated by the presence of thionyl chloride. The study of intermolecular halogen-halogen interactions is a current problem and several authors have presented interesting results. Halogen-halogen short interactions, in other similar studies, show Cl···Cl distances of the order of 3.8 Å. Theoretical studies of density analysis, varying the Cl···Cl distance from 3.0 to 4.0 Å, using DFT solid state program, have been undertaken (Vener et al., 2013). Geometric considerations in halogen-halogen interactions, for various benzanilide systems, showed different behaviors. Interactions of fluorine with other halogens Cl, Br, I, in different benzanilide systems, include interactions type: trans, cis or L-geometry (Nayak et al., 2011). The molecular structure of (I) is shown in Fig. 1. The central amide moiety, C8—N1-C7(═O1)—C1, is essentially planar (r.m.s. deviation for all non-H atoms = 0.0164 Å) and it forms dihedral angles of 15.2 (2)° with the C1-C6 and 8.2 (2)° with the C8-C13 rings respectively. In the crystal structure (Fig. 2), molecules are linked by weak C-H···O intermolecular contacts. The C10-H10···O1 hydrogen bond interactions are responsible for crystal growth parallel to (2 0 -2). In this interaction, the C-H in the molecule at (x,y,z) acts as a hydrogen-bond donor to O1 atom of the carbonyl group at (-x+1,+y-1/2,-z+3/2). These interactions generate C(7) chains of molecules along [010]. Other intra N-H···O and N-H···N are observed (see Table 1, Nardelli, 1995). The shorest Cl···Cl contact distance in this structure is 3.943 (3) Å.