organic compounds
Ethyl 3-nitro-4-(n-propylamino)benzoate
aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, bDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Geguan Road No. 625 Dachang District Nanjing, Nanjing 210048, People's Republic of China, and cCollege of Biotechnology and Pharmaceutical Engineering, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
*Correspondence e-mail: guocheng@njut.edu.cn
In the molecule of the title compound, C12H16N2O4, an intramolecular N—H⋯O hydrogen bond results in the formation of a six-membered ring having an In the a bifurcated intra/intermolecular N—H⋯(O,O) hydrogen bond generates inversion dimers.
Related literature
For bond-length data, see: Allen et al. (1987). For the synthesis, see: Ates-Alagoz & Buyukbingol (2001); Oezden et al. (2005).
Experimental
Crystal data
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Refinement
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Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); 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, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S160053680901873X/hk2690sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053680901873X/hk2690Isup2.hkl
For the preparation of the title compound, ethyl 4-chloro-3-nitrobenzoate (5.3 g, 23 mmol) was refluxed in n-propyl amine (25 ml) and tetrahydrofuran (50 ml) for 2 h. Then, solvents were evaporated and water was added to give yellow precipate, which was collected by filtration and washed with cold ethanol (2 × 15 ml) to afford the yellow solid (yield; 4.8 g). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.
H atoms were positioned geometrically, with N-H = 0.86 Å (for NH) and C-H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell
CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C12H16N2O4 | Z = 2 |
Mr = 252.27 | F(000) = 268 |
Triclinic, P1 | Dx = 1.303 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.4400 (9) Å | Cell parameters from 25 reflections |
b = 12.606 (3) Å | θ = 9–11° |
c = 13.209 (3) Å | µ = 0.10 mm−1 |
α = 61.710 (19)° | T = 294 K |
β = 83.02 (3)° | Block, colorless |
γ = 81.75 (3)° | 0.20 × 0.10 × 0.10 mm |
V = 643.1 (3) Å3 |
Enraf–Nonius CAD-4 diffractometer | 924 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.083 |
Graphite monochromator | θmax = 25.2°, θmin = 1.8° |
ω/2θ scans | h = 0→5 |
Absorption correction: ψ scan (North et al., 1968) | k = −14→15 |
Tmin = 0.981, Tmax = 0.990 | l = −15→15 |
2593 measured reflections | 3 standard reflections every 120 min |
2281 independent reflections | intensity decay: 1% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.067 | H-atom parameters constrained |
wR(F2) = 0.165 | w = 1/[σ2(Fo2) + (0.057P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
2281 reflections | Δρmax = 0.19 e Å−3 |
157 parameters | Δρmin = −0.14 e Å−3 |
Primary atom site location: structure-invariant direct methods |
C12H16N2O4 | γ = 81.75 (3)° |
Mr = 252.27 | V = 643.1 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.4400 (9) Å | Mo Kα radiation |
b = 12.606 (3) Å | µ = 0.10 mm−1 |
c = 13.209 (3) Å | T = 294 K |
α = 61.710 (19)° | 0.20 × 0.10 × 0.10 mm |
β = 83.02 (3)° |
Enraf–Nonius CAD-4 diffractometer | 924 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.083 |
Tmin = 0.981, Tmax = 0.990 | 3 standard reflections every 120 min |
2593 measured reflections | intensity decay: 1% |
2281 independent reflections |
R[F2 > 2σ(F2)] = 0.067 | 157 parameters |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.19 e Å−3 |
2281 reflections | Δρmin = −0.14 e Å−3 |
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 | ||
O1 | −0.3870 (7) | −0.0274 (2) | 0.8647 (2) | 0.0865 (10) | |
O2 | −0.2837 (8) | −0.1310 (3) | 0.7632 (3) | 0.1130 (12) | |
O3 | −0.0492 (8) | 0.3592 (2) | 0.7202 (2) | 0.1056 (12) | |
O4 | 0.2630 (7) | 0.4310 (3) | 0.5801 (2) | 0.104 | |
N1 | 0.1072 (8) | 0.3526 (3) | 0.6413 (3) | 0.0706 (10) | |
N2 | 0.4396 (8) | 0.3293 (3) | 0.4457 (3) | 0.0842 (11) | |
H2A | 0.4491 | 0.3936 | 0.4521 | 0.101* | |
C1 | −0.3968 (13) | −0.2145 (4) | 1.0388 (4) | 0.127 (2) | |
H1A | −0.5267 | −0.2746 | 1.0918 | 0.190* | |
H1B | −0.3079 | −0.1811 | 1.0788 | 0.190* | |
H1C | −0.2379 | −0.2511 | 1.0058 | 0.190* | |
C2 | −0.5738 (10) | −0.1193 (4) | 0.9484 (4) | 0.1006 (16) | |
H2B | −0.7339 | −0.0825 | 0.9819 | 0.121* | |
H2C | −0.6696 | −0.1538 | 0.9100 | 0.121* | |
C3 | −0.2502 (11) | −0.0448 (4) | 0.7781 (4) | 0.0809 (13) | |
C4 | −0.0655 (9) | 0.0540 (3) | 0.6944 (3) | 0.0664 (11) | |
C5 | −0.0537 (8) | 0.1582 (3) | 0.7019 (3) | 0.0592 (10) | |
H5A | −0.1638 | 0.1678 | 0.7620 | 0.071* | |
C6 | 0.1163 (8) | 0.2486 (3) | 0.6230 (3) | 0.0584 (10) | |
C7 | 0.2859 (8) | 0.2413 (3) | 0.5268 (3) | 0.0588 (10) | |
C8 | 0.2554 (10) | 0.1315 (4) | 0.5233 (3) | 0.0820 (13) | |
H8A | 0.3503 | 0.1217 | 0.4612 | 0.098* | |
C9 | 0.1030 (11) | 0.0445 (4) | 0.6018 (4) | 0.0834 (14) | |
H9A | 0.1064 | −0.0264 | 0.5961 | 0.100* | |
C10 | 0.5976 (13) | 0.3193 (4) | 0.3427 (4) | 0.129 (2) | |
H10A | 0.8040 | 0.2821 | 0.3610 | 0.155* | |
H10B | 0.4927 | 0.2659 | 0.3281 | 0.155* | |
C11 | 0.6104 (14) | 0.4292 (5) | 0.2425 (4) | 0.138 (2) | |
H11A | 0.7199 | 0.4821 | 0.2561 | 0.165* | |
H11B | 0.4046 | 0.4674 | 0.2246 | 0.165* | |
C12 | 0.7633 (11) | 0.4158 (4) | 0.1409 (3) | 0.1116 (17) | |
H12A | 0.7768 | 0.4944 | 0.0758 | 0.167* | |
H12B | 0.6465 | 0.3692 | 0.1229 | 0.167* | |
H12C | 0.9645 | 0.3752 | 0.1591 | 0.167* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.082 (2) | 0.0819 (19) | 0.0924 (19) | −0.0227 (18) | −0.0007 (18) | −0.0351 (17) |
O2 | 0.149 (3) | 0.0806 (19) | 0.122 (2) | −0.028 (2) | −0.029 (2) | −0.0475 (19) |
O3 | 0.128 (3) | 0.103 (2) | 0.104 (2) | −0.035 (2) | 0.038 (2) | −0.0672 (19) |
O4 | 0.123 | 0.115 | 0.097 | −0.056 | 0.021 | −0.063 |
N1 | 0.068 (2) | 0.076 (2) | 0.0711 (19) | −0.031 (2) | 0.0100 (19) | −0.0344 (17) |
N2 | 0.073 (3) | 0.088 (2) | 0.074 (2) | 0.010 (2) | 0.006 (2) | −0.0304 (18) |
C1 | 0.133 (5) | 0.088 (3) | 0.104 (3) | 0.007 (4) | 0.004 (4) | −0.007 (3) |
C2 | 0.070 (4) | 0.089 (3) | 0.126 (4) | −0.012 (3) | −0.017 (3) | −0.033 (3) |
C3 | 0.079 (4) | 0.063 (3) | 0.094 (3) | 0.001 (3) | −0.041 (3) | −0.025 (3) |
C4 | 0.058 (3) | 0.066 (2) | 0.084 (3) | 0.016 (2) | −0.030 (2) | −0.041 (2) |
C5 | 0.050 (3) | 0.065 (2) | 0.067 (2) | 0.002 (2) | −0.010 (2) | −0.034 (2) |
C6 | 0.053 (3) | 0.071 (2) | 0.059 (2) | 0.005 (2) | −0.013 (2) | −0.037 (2) |
C7 | 0.043 (2) | 0.064 (2) | 0.054 (2) | 0.021 (2) | −0.0114 (19) | −0.0212 (19) |
C8 | 0.092 (4) | 0.090 (3) | 0.068 (3) | 0.036 (3) | −0.019 (3) | −0.049 (2) |
C9 | 0.104 (4) | 0.069 (3) | 0.089 (3) | 0.014 (3) | −0.023 (3) | −0.048 (2) |
C10 | 0.132 (4) | 0.115 (4) | 0.088 (3) | 0.026 (3) | 0.038 (3) | −0.026 (3) |
C11 | 0.155 (5) | 0.133 (4) | 0.091 (3) | 0.031 (4) | 0.014 (4) | −0.041 (3) |
C12 | 0.106 (4) | 0.132 (4) | 0.066 (2) | 0.012 (3) | 0.005 (3) | −0.030 (3) |
O1—C3 | 1.326 (5) | C4—C9 | 1.400 (5) |
O1—C2 | 1.446 (4) | C5—C6 | 1.373 (4) |
O2—C3 | 1.223 (4) | C5—H5A | 0.9300 |
O3—N1 | 1.211 (3) | C6—C7 | 1.432 (4) |
O4—N1 | 1.188 (3) | C7—C8 | 1.432 (5) |
N1—C6 | 1.436 (4) | C8—C9 | 1.304 (5) |
N2—C7 | 1.326 (4) | C8—H8A | 0.9300 |
N2—C10 | 1.505 (5) | C9—H9A | 0.9300 |
N2—H2A | 0.8600 | C10—C11 | 1.393 (5) |
C1—C2 | 1.443 (5) | C10—H10A | 0.9700 |
C1—H1A | 0.9600 | C10—H10B | 0.9700 |
C1—H1B | 0.9600 | C11—C12 | 1.500 (5) |
C1—H1C | 0.9600 | C11—H11A | 0.9700 |
C2—H2B | 0.9700 | C11—H11B | 0.9700 |
C2—H2C | 0.9700 | C12—H12A | 0.9600 |
C3—C4 | 1.488 (5) | C12—H12B | 0.9600 |
C4—C5 | 1.372 (4) | C12—H12C | 0.9600 |
C3—O1—C2 | 117.2 (3) | C5—C6—N1 | 115.8 (3) |
O4—N1—O3 | 120.0 (3) | C7—C6—N1 | 121.9 (3) |
O4—N1—C6 | 119.2 (3) | N2—C7—C6 | 123.9 (4) |
O3—N1—C6 | 120.8 (3) | N2—C7—C8 | 123.4 (3) |
C7—N2—C10 | 121.4 (4) | C6—C7—C8 | 112.6 (3) |
C7—N2—H2A | 119.3 | C9—C8—C7 | 124.2 (4) |
C10—N2—H2A | 119.3 | C9—C8—H8A | 117.9 |
C2—C1—H1A | 109.5 | C7—C8—H8A | 117.9 |
C2—C1—H1B | 109.5 | C8—C9—C4 | 122.3 (4) |
H1A—C1—H1B | 109.5 | C8—C9—H9A | 118.8 |
C2—C1—H1C | 109.5 | C4—C9—H9A | 118.8 |
H1A—C1—H1C | 109.5 | C11—C10—N2 | 114.4 (4) |
H1B—C1—H1C | 109.5 | C11—C10—H10A | 108.7 |
C1—C2—O1 | 111.7 (4) | N2—C10—H10A | 108.7 |
C1—C2—H2B | 109.3 | C11—C10—H10B | 108.7 |
O1—C2—H2B | 109.3 | N2—C10—H10B | 108.7 |
C1—C2—H2C | 109.3 | H10A—C10—H10B | 107.6 |
O1—C2—H2C | 109.3 | C10—C11—C12 | 113.1 (4) |
H2B—C2—H2C | 107.9 | C10—C11—H11A | 109.0 |
O2—C3—O1 | 123.7 (4) | C12—C11—H11A | 109.0 |
O2—C3—C4 | 121.8 (5) | C10—C11—H11B | 109.0 |
O1—C3—C4 | 114.4 (4) | C12—C11—H11B | 109.0 |
C5—C4—C9 | 116.8 (4) | H11A—C11—H11B | 107.8 |
C5—C4—C3 | 122.8 (4) | C11—C12—H12A | 109.5 |
C9—C4—C3 | 120.4 (4) | C11—C12—H12B | 109.5 |
C4—C5—C6 | 121.8 (3) | H12A—C12—H12B | 109.5 |
C4—C5—H5A | 119.1 | C11—C12—H12C | 109.5 |
C6—C5—H5A | 119.1 | H12A—C12—H12C | 109.5 |
C5—C6—C7 | 122.2 (3) | H12B—C12—H12C | 109.5 |
C3—O1—C2—C1 | 87.3 (5) | C5—C6—C7—N2 | 176.3 (4) |
C2—O1—C3—O2 | 3.0 (6) | N1—C6—C7—N2 | −2.0 (6) |
C2—O1—C3—C4 | 179.2 (3) | C5—C6—C7—C8 | 0.2 (5) |
O2—C3—C4—C5 | 172.1 (4) | N1—C6—C7—C8 | −178.1 (3) |
O1—C3—C4—C5 | −4.1 (6) | N2—C7—C8—C9 | −179.4 (4) |
O2—C3—C4—C9 | −6.9 (7) | C6—C7—C8—C9 | −3.2 (6) |
O1—C3—C4—C9 | 176.9 (4) | C7—C8—C9—C4 | 4.6 (7) |
C9—C4—C5—C6 | −0.4 (6) | C5—C4—C9—C8 | −2.6 (6) |
C3—C4—C5—C6 | −179.4 (4) | C3—C4—C9—C8 | 176.5 (4) |
C4—C5—C6—C7 | 1.5 (6) | C7—N2—C10—C11 | 148.5 (5) |
C4—C5—C6—N1 | 179.9 (3) | N2—C10—C11—C12 | −178.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O4 | 0.86 | 2.02 | 2.635 (5) | 128 |
N2—H2A···O4i | 0.86 | 2.55 | 3.324 (6) | 150 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H16N2O4 |
Mr | 252.27 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 4.4400 (9), 12.606 (3), 13.209 (3) |
α, β, γ (°) | 61.710 (19), 83.02 (3), 81.75 (3) |
V (Å3) | 643.1 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.20 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.981, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2593, 2281, 924 |
Rint | 0.083 |
(sin θ/λ)max (Å−1) | 0.598 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.165, 1.00 |
No. of reflections | 2281 |
No. of parameters | 157 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.14 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O4 | 0.86 | 2.02 | 2.635 (5) | 128 |
N2—H2A···O4i | 0.86 | 2.55 | 3.324 (6) | 150 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Acknowledgements
The authors thank the Center of Testing and Analysis, Nanjing University, for support.
References
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. CrossRef Web of Science Google Scholar
Ates-Alagoz, Z. & Buyukbingol, E. (2001). Heterocycl. Commun. 7, 455–460. CAS Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Some derivatives of benzoic acid are important chemical materials. We report herein the crystal structure of the title compound.
In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C4-C9) is, of course, planar. Intramolecular N-H···O hydrogen bond (Table 1) results in the formation of a six-membered ring B (O4/N1/N2/C6/C7/H2A) having envelope conformation with atom O4 displaced by -0.116 (3) Å from the plane of the other ring atoms.
In the crystal structure, intra- and intermolecular N-H···O interactions (Table 1) link the molecules into centrosymmetric dimers (Fig. 2), in which they may be effective in the stabilization of the structure.