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Acta Cryst. (2009). E65, o227    [ doi:10.1107/S1600536808043602 ]

Ethyl 4-ethylamino-3-nitrobenzoate

H.-Y. Li, B.-N. Liu, S.-G. Tang and C. Guo

Abstract top

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.

Comment top

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 [φ = 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.

Related literature top

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

Experimental top

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 top

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.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: 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); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bond is shown as dashed line.
[Figure 2] Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
Ethyl 4-ethylamino-3-nitrobenzoate top
Crystal data top
C11H14N2O4F(000) = 252
Mr = 238.24Dx = 1.367 Mg m−3
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 mm−1
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 top
Enraf–Nonius CAD-4
diffractometer		841 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 top
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 = 1.01 w = 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 Å−3
4 restraintsΔρmin = −0.30 e Å−3
Crystal data top
C11H14N2O4V = 578.8 (2) Å3
Mr = 238.24Z = 2
Monoclinic, P21Mo Kα radiation
a = 4.2360 (8) ŵ = 0.11 mm−1
b = 16.180 (3) ÅT = 294 K
c = 8.4890 (17) Å0.30 × 0.20 × 0.10 mm
β = 95.80 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		841 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.018
Tmin = 0.969, Tmax = 0.990θmax = 25.2°
1213 measured reflections3 standard reflections every 120 min
1066 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.077H-atom parameters constrained
wR(F2) = 0.173Δρmax = 0.24 e Å−3
S = 1.01Δρmin = −0.30 e Å−3
1066 reflectionsAbsolute structure: ?
154 parametersFlack parameter: ?
4 restraintsRogers parameter: ?
Special details top

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) top
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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.
Acknowledgements top

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

references
References top

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North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

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