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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): o227.
Published online 2009 January 8. doi:  10.1107/S1600536808043602
PMCID: PMC2968249

Ethyl 4-ethyl­amino-3-nitro­benzoate

Abstract

In the mol­ecule of the title compound, C11H14N2O4, a bifurcated intra/intermolecular N—H(...)(O,O) hydrogen bond occurs.The intramolecular component results in a non-planar six-membered ring with a flattened-boat conformation. In the crystal structure, the inter­molecular interaction links the mol­ecules into chains parallel to the b axis.

Related literature

For a related structure, see: Ates-Alagoz et al. (2001 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For ring-puckering parameters, see: Cremer & Pople (1975 [triangle]).

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Object name is e-65-0o227-scheme1.jpg

Experimental

Crystal data

  • C11H14N2O4
  • M r = 238.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o227-efi1.jpg
  • a = 4.2360 (8) Å
  • b = 16.180 (3) Å
  • c = 8.4890 (17) Å
  • β = 95.80 (3)°
  • V = 578.8 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 294 (2) K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.969, T max = 0.990
  • 1213 measured reflections
  • 1066 independent reflections
  • 841 reflections with I > 2σ(I)
  • R int = 0.018
  • 3 standard reflections frequency: 120 min intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.077
  • wR(F 2) = 0.173
  • S = 1.01
  • 1066 reflections
  • 154 parameters
  • 4 restraints
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.30 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808043602/hk2598sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043602/hk2598Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank Dr Shan Liu, Nanjing University of Technology, for useful discussions and the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

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 (C3-C8) is, of course, planar. The intramolecular N-H···O hydrogen bond (Table 1) results in a nonplanar six-membered ring B (O2/N1/N2/C3/C4/H1A), having total puckering amplitude, QT, of 0.163 (2) Å, flattened-boat conformation [[var phi] = 52.00 (3)° and θ = 19.29 (4)°] (Cremer & Pople, 1975).

In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 1) link the molecules into chains parallel to the b axis (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, ethyl 4-chloro-3-nitrobenzoate (5.3 g, 0.023 mol) was refluxed in ethyl amine (20 ml) and tetrahydrofuran (50 ml) for 2 h. Then, solvents were evaporated and water was added to give yellow precipate. It was collected by filtration and washed with cold ethanol (2 X 15 ml) to afford the yellow solid (yield; 4.4 g, 80%) (Ates-Alagoz et al., 2001). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Refinement

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.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bond is shown as dashed line.
Fig. 2.
A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C11H14N2O4F(000) = 252
Mr = 238.24Dx = 1.367 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 25 reflections
a = 4.2360 (8) Åθ = 10–12°
b = 16.180 (3) ŵ = 0.11 mm1
c = 8.4890 (17) ÅT = 294 K
β = 95.80 (3)°Block, colorless
V = 578.8 (2) Å30.30 × 0.20 × 0.10 mm
Z = 2

Data collection

Enraf–Nonius CAD-4 diffractometer841 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.018
graphiteθmax = 25.2°, θmin = 2.4°
ω/2θ scansh = −5→5
Absorption correction: ψ scan (North et al., 1968)k = 0→19
Tmin = 0.969, Tmax = 0.990l = 0→10
1213 measured reflections3 standard reflections every 120 min
1066 independent reflections intensity decay: none

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.077Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.05P)2 + 1.25P] where P = (Fo2 + 2Fc2)/3
1066 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 0.24 e Å3
4 restraintsΔρmin = −0.30 e Å3

Special details

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)

xyzUiso*/Ueq
O10.7012 (15)1.1050 (4)0.7940 (7)0.0772 (18)
O20.9134 (16)1.1622 (4)0.5988 (8)0.083 (2)
O30.9764 (13)0.7330 (4)0.7615 (6)0.0589 (15)
O40.7965 (13)0.8254 (3)0.9244 (6)0.0564 (14)
N11.2210 (17)1.0712 (5)0.4054 (8)0.065 (2)
H1A1.15911.12040.42560.078*
N20.8667 (17)1.0957 (5)0.6810 (9)0.0659 (19)
C11.212 (2)1.0329 (6)0.1174 (10)0.071 (2)
H1B1.34431.02590.03280.106*
H1C1.05711.07500.08910.106*
H1D1.10690.98180.13550.106*
C21.414 (2)1.0581 (6)0.2654 (10)0.071 (3)
H2A1.52461.10890.24530.085*
H2B1.57191.01570.29250.085*
C31.1440 (15)1.0085 (4)0.4988 (7)0.0383 (15)
C40.9754 (15)1.0194 (5)0.6315 (8)0.0416 (16)
C50.9015 (15)0.9543 (4)0.7232 (8)0.0401 (17)
H5A0.78580.96460.80860.048*
C60.9927 (16)0.8715 (4)0.6946 (8)0.0404 (16)
C71.1639 (14)0.8632 (4)0.5582 (7)0.0393 (16)
H7A1.23330.81050.53480.047*
C81.2314 (16)0.9232 (4)0.4633 (8)0.0377 (16)
H8A1.33420.91180.37400.045*
C90.9235 (16)0.8047 (4)0.7942 (8)0.0376 (15)
C100.7087 (18)0.7563 (5)1.0314 (8)0.0483 (19)
H10A0.89160.72221.06500.058*
H10B0.54320.72170.97870.058*
C110.590 (2)0.8020 (6)1.1726 (9)0.060 (2)
H11A0.52110.76251.24630.090*
H11B0.41570.83721.13570.090*
H11C0.75900.83481.22400.090*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.095 (4)0.068 (4)0.073 (4)0.010 (4)0.028 (4)0.005 (4)
O20.094 (5)0.079 (5)0.078 (5)−0.004 (4)0.019 (4)0.003 (4)
O30.068 (3)0.052 (4)0.059 (3)0.004 (3)0.015 (3)0.002 (3)
O40.070 (3)0.049 (3)0.051 (3)0.005 (3)0.009 (3)−0.002 (3)
N10.072 (4)0.063 (5)0.059 (4)−0.011 (4)0.005 (4)−0.008 (4)
N20.068 (4)0.068 (5)0.061 (4)0.001 (4)0.002 (4)−0.003 (4)
C10.083 (6)0.070 (6)0.061 (5)0.008 (5)0.012 (4)0.004 (5)
C20.071 (5)0.075 (7)0.067 (6)0.008 (5)0.012 (4)−0.005 (5)
C30.043 (3)0.037 (4)0.033 (3)−0.006 (3)−0.003 (3)0.003 (3)
C40.040 (3)0.045 (4)0.039 (4)−0.002 (3)0.003 (3)0.004 (3)
C50.039 (3)0.043 (4)0.038 (4)0.001 (3)0.002 (3)−0.001 (3)
C60.044 (4)0.034 (4)0.043 (4)0.002 (3)0.006 (3)−0.002 (3)
C70.044 (4)0.037 (4)0.037 (4)0.004 (3)0.005 (3)−0.002 (3)
C80.050 (4)0.029 (4)0.035 (4)−0.005 (3)0.009 (3)0.005 (3)
C90.047 (4)0.029 (4)0.037 (4)0.002 (3)0.004 (3)−0.001 (3)
C100.055 (4)0.052 (5)0.038 (4)0.002 (4)0.005 (3)0.006 (4)
C110.062 (5)0.064 (5)0.053 (5)0.003 (4)0.007 (4)−0.002 (4)

Geometric parameters (Å, °)

O1—N21.253 (9)C3—C81.467 (9)
O2—N21.308 (10)C4—C51.365 (10)
O3—C91.219 (9)C5—C61.422 (9)
O4—C91.320 (8)C5—H5A0.9300
O4—C101.510 (8)C6—C91.420 (9)
N1—C21.523 (11)C6—C71.434 (9)
N1—C31.349 (10)C7—C81.311 (9)
N1—H1A0.8600C7—H7A0.9300
N2—C41.397 (10)C8—H8A0.9300
C1—C21.502 (12)C10—C111.535 (10)
C1—H1B0.9600C10—H10A0.9700
C1—H1C0.9600C10—H10B0.9700
C1—H1D0.9600C11—H11A0.9600
C2—H2A0.9700C11—H11B0.9600
C2—H2B0.9700C11—H11C0.9600
C3—C41.405 (9)
C2—N1—H1A118.9C4—C5—H5A118.4
C3—N1—C2122.3 (8)C6—C5—H5A118.4
C3—N1—H1A118.9C9—C6—C5122.6 (6)
O1—N2—O2115.9 (8)C9—C6—C7124.2 (6)
O1—N2—C4124.3 (8)C5—C6—C7113.2 (6)
O2—N2—C4119.6 (7)C8—C7—C6126.0 (7)
C9—O4—C10117.5 (6)C8—C7—H7A117.0
C2—C1—H1B109.5C6—C7—H7A117.0
C2—C1—H1C109.5C7—C8—C3119.6 (6)
H1B—C1—H1C109.5C7—C8—H8A120.2
C2—C1—H1D109.5C3—C8—H8A120.2
H1B—C1—H1D109.5O3—C9—O4122.1 (7)
H1C—C1—H1D109.5O3—C9—C6122.3 (6)
C1—C2—N1112.7 (7)O4—C9—C6115.6 (6)
C1—C2—H2A109.0O4—C10—C11103.4 (6)
N1—C2—H2A109.0O4—C10—H10A111.1
C1—C2—H2B109.0C11—C10—H10A111.1
N1—C2—H2B109.0O4—C10—H10B111.1
H2A—C2—H2B107.8C11—C10—H10B111.1
N1—C3—C4123.3 (7)H10A—C10—H10B109.0
N1—C3—C8120.4 (6)C10—C11—H11A109.5
C4—C3—C8116.3 (6)C10—C11—H11B109.5
C5—C4—N2114.2 (6)H11A—C11—H11B109.5
C5—C4—C3121.6 (7)C10—C11—H11C109.5
N2—C4—C3124.2 (7)H11A—C11—H11C109.5
C4—C5—C6123.2 (6)H11B—C11—H11C109.5
C3—N1—C2—C184.9 (10)C4—C5—C6—C7−1.2 (9)
C2—N1—C3—C4177.9 (6)C9—C6—C7—C8179.8 (7)
C2—N1—C3—C8−3.1 (11)C5—C6—C7—C8−1.2 (9)
O1—N2—C4—C5−3.6 (10)C6—C7—C8—C33.4 (10)
O2—N2—C4—C5−177.5 (7)N1—C3—C8—C7177.8 (7)
O1—N2—C4—C3175.8 (7)C4—C3—C8—C7−3.1 (9)
O2—N2—C4—C31.9 (10)C10—O4—C9—O3−1.7 (10)
N1—C3—C4—C5179.9 (7)C10—O4—C9—C6178.0 (6)
C8—C3—C4—C50.9 (8)C5—C6—C9—O3173.2 (7)
N1—C3—C4—N20.6 (10)C7—C6—C9—O3−7.9 (11)
C8—C3—C4—N2−178.5 (6)C5—C6—C9—O4−6.5 (10)
N2—C4—C5—C6−179.3 (6)C7—C6—C9—O4172.4 (6)
C3—C4—C5—C61.3 (9)C9—O4—C10—C11176.7 (6)
C4—C5—C6—C9177.8 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.862.002.645 (10)131
N1—H1A···O3i0.862.453.053 (10)128

Symmetry codes: (i) −x+2, y+1/2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2598).

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.
  • Ates-Alagoz, Z. & Buyukbingol, E. (2001). Heterocycl. Commun.7, 455-460.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc 97, 1354–1358.
  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography