Ethyl 4-ethyl­amino-3-nitro­benzoate

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

doi:10.1107/S1600536808043602

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o227

doi:10.1107/S1600536808043602

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Ethyl 4-ethylamino-3-nitrobenzoate

Hao-Yuan Li,^a Bo-Nian Liu,^b Shi-Gui Tang ^a and Cheng Guo ^b ^*

^aCollege of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bCollege of Science, Nanjing University of Technolgy, Xinmofan Road No.5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: guocheng@njut.edu.cn

(Received 7 December 2008; accepted 22 December 2008; online 8 January 2009)

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 ). For bond-length data, see: Allen et al. (1987 ). For ring-puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₁H₁₄N₂O₄
M_r = 238.24
Monoclinic, P 2₁
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 ) 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[F² > 2σ(F²)] = 0.077
wR(F²) = 0.173
S = 1.01
1066 reflections
154 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.86	2.00	2.645 (10)	131
N1—H1A⋯O3ⁱ	0.86	2.45	3.053 (10)	128
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+1]$ .

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

Supporting information

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

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

checkCIF report

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, Q_T, 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.

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

	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.

Ethyl 4-ethylamino-3-nitrobenzoate top

Crystal data top

C₁₁H₁₄N₂O₄	F(000) = 252
M_r = 238.24	D_x = 1.367 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 4.2360 (8) Å	θ = 10–12°
b = 16.180 (3) Å	µ = 0.11 mm⁻¹
c = 8.4890 (17) Å	T = 294 K
β = 95.80 (3)°	Block, colorless
V = 578.8 (2) Å³	0.30 × 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 tube	R_int = 0.018
Graphite monochromator	θ_max = 25.2°, θ_min = 2.4°
ω/2θ scans	h = −5→5
Absorption correction: ψ scan (North et al., 1968)	k = 0→19
T_min = 0.969, T_max = 0.990	l = 0→10
1213 measured reflections	3 standard reflections every 120 min
1066 independent reflections	intensity decay: none

Refinement top

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)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.05P)² + 1.25P] where P = (F_o² + 2F_c²)/3
1066 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.24 e Å⁻³
4 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₁H₁₄N₂O₄	V = 578.8 (2) Å³
M_r = 238.24	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 4.2360 (8) Å	µ = 0.11 mm⁻¹
b = 16.180 (3) Å	T = 294 K
c = 8.4890 (17) Å	0.30 × 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)	R_int = 0.018
T_min = 0.969, T_max = 0.990	3 standard reflections every 120 min
1213 measured reflections	intensity decay: none
1066 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.077	4 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 1.01	Δρ_max = 0.24 e Å⁻³
1066 reflections	Δρ_min = −0.30 e Å⁻³
154 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.7012 (15)	1.1050 (4)	0.7940 (7)	0.0772 (18)
O2	0.9134 (16)	1.1622 (4)	0.5988 (8)	0.083 (2)
O3	0.9764 (13)	0.7330 (4)	0.7615 (6)	0.0589 (15)
O4	0.7965 (13)	0.8254 (3)	0.9244 (6)	0.0564 (14)
N1	1.2210 (17)	1.0712 (5)	0.4054 (8)	0.065 (2)
H1A	1.1591	1.1204	0.4256	0.078*
N2	0.8667 (17)	1.0957 (5)	0.6810 (9)	0.0659 (19)
C1	1.212 (2)	1.0329 (6)	0.1174 (10)	0.071 (2)
H1B	1.3443	1.0259	0.0328	0.106*
H1C	1.0571	1.0750	0.0891	0.106*
H1D	1.1069	0.9818	0.1355	0.106*
C2	1.414 (2)	1.0581 (6)	0.2654 (10)	0.071 (3)
H2A	1.5246	1.1089	0.2453	0.085*
H2B	1.5719	1.0157	0.2925	0.085*
C3	1.1440 (15)	1.0085 (4)	0.4988 (7)	0.0383 (15)
C4	0.9754 (15)	1.0194 (5)	0.6315 (8)	0.0416 (16)
C5	0.9015 (15)	0.9543 (4)	0.7232 (8)	0.0401 (17)
H5A	0.7858	0.9646	0.8086	0.048*
C6	0.9927 (16)	0.8715 (4)	0.6946 (8)	0.0404 (16)
C7	1.1639 (14)	0.8632 (4)	0.5582 (7)	0.0393 (16)
H7A	1.2333	0.8105	0.5348	0.047*
C8	1.2314 (16)	0.9232 (4)	0.4633 (8)	0.0377 (16)
H8A	1.3342	0.9118	0.3740	0.045*
C9	0.9235 (16)	0.8047 (4)	0.7942 (8)	0.0376 (15)
C10	0.7087 (18)	0.7563 (5)	1.0314 (8)	0.0483 (19)
H10A	0.8916	0.7222	1.0650	0.058*
H10B	0.5432	0.7217	0.9787	0.058*
C11	0.590 (2)	0.8020 (6)	1.1726 (9)	0.060 (2)
H11A	0.5211	0.7625	1.2463	0.090*
H11B	0.4157	0.8372	1.1357	0.090*
H11C	0.7590	0.8348	1.2240	0.090*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.095 (4)	0.068 (4)	0.073 (4)	0.010 (4)	0.028 (4)	0.005 (4)
O2	0.094 (5)	0.079 (5)	0.078 (5)	−0.004 (4)	0.019 (4)	0.003 (4)
O3	0.068 (3)	0.052 (4)	0.059 (3)	0.004 (3)	0.015 (3)	0.002 (3)
O4	0.070 (3)	0.049 (3)	0.051 (3)	0.005 (3)	0.009 (3)	−0.002 (3)
N1	0.072 (4)	0.063 (5)	0.059 (4)	−0.011 (4)	0.005 (4)	−0.008 (4)
N2	0.068 (4)	0.068 (5)	0.061 (4)	0.001 (4)	0.002 (4)	−0.003 (4)
C1	0.083 (6)	0.070 (6)	0.061 (5)	0.008 (5)	0.012 (4)	0.004 (5)
C2	0.071 (5)	0.075 (7)	0.067 (6)	0.008 (5)	0.012 (4)	−0.005 (5)
C3	0.043 (3)	0.037 (4)	0.033 (3)	−0.006 (3)	−0.003 (3)	0.003 (3)
C4	0.040 (3)	0.045 (4)	0.039 (4)	−0.002 (3)	0.003 (3)	0.004 (3)
C5	0.039 (3)	0.043 (4)	0.038 (4)	0.001 (3)	0.002 (3)	−0.001 (3)
C6	0.044 (4)	0.034 (4)	0.043 (4)	0.002 (3)	0.006 (3)	−0.002 (3)
C7	0.044 (4)	0.037 (4)	0.037 (4)	0.004 (3)	0.005 (3)	−0.002 (3)
C8	0.050 (4)	0.029 (4)	0.035 (4)	−0.005 (3)	0.009 (3)	0.005 (3)
C9	0.047 (4)	0.029 (4)	0.037 (4)	0.002 (3)	0.004 (3)	−0.001 (3)
C10	0.055 (4)	0.052 (5)	0.038 (4)	0.002 (4)	0.005 (3)	0.006 (4)
C11	0.062 (5)	0.064 (5)	0.053 (5)	0.003 (4)	0.007 (4)	−0.002 (4)

Geometric parameters (Å, º) top

O1—N2	1.253 (9)	C3—C8	1.467 (9)
O2—N2	1.308 (10)	C4—C5	1.365 (10)
O3—C9	1.219 (9)	C5—C6	1.422 (9)
O4—C9	1.320 (8)	C5—H5A	0.9300
O4—C10	1.510 (8)	C6—C9	1.420 (9)
N1—C2	1.523 (11)	C6—C7	1.434 (9)
N1—C3	1.349 (10)	C7—C8	1.311 (9)
N1—H1A	0.8600	C7—H7A	0.9300
N2—C4	1.397 (10)	C8—H8A	0.9300
C1—C2	1.502 (12)	C10—C11	1.535 (10)
C1—H1B	0.9600	C10—H10A	0.9700
C1—H1C	0.9600	C10—H10B	0.9700
C1—H1D	0.9600	C11—H11A	0.9600
C2—H2A	0.9700	C11—H11B	0.9600
C2—H2B	0.9700	C11—H11C	0.9600
C3—C4	1.405 (9)

C2—N1—H1A	118.9	C4—C5—H5A	118.4
C3—N1—C2	122.3 (8)	C6—C5—H5A	118.4
C3—N1—H1A	118.9	C9—C6—C5	122.6 (6)
O1—N2—O2	115.9 (8)	C9—C6—C7	124.2 (6)
O1—N2—C4	124.3 (8)	C5—C6—C7	113.2 (6)
O2—N2—C4	119.6 (7)	C8—C7—C6	126.0 (7)
C9—O4—C10	117.5 (6)	C8—C7—H7A	117.0
C2—C1—H1B	109.5	C6—C7—H7A	117.0
C2—C1—H1C	109.5	C7—C8—C3	119.6 (6)
H1B—C1—H1C	109.5	C7—C8—H8A	120.2
C2—C1—H1D	109.5	C3—C8—H8A	120.2
H1B—C1—H1D	109.5	O3—C9—O4	122.1 (7)
H1C—C1—H1D	109.5	O3—C9—C6	122.3 (6)
C1—C2—N1	112.7 (7)	O4—C9—C6	115.6 (6)
C1—C2—H2A	109.0	O4—C10—C11	103.4 (6)
N1—C2—H2A	109.0	O4—C10—H10A	111.1
C1—C2—H2B	109.0	C11—C10—H10A	111.1
N1—C2—H2B	109.0	O4—C10—H10B	111.1
H2A—C2—H2B	107.8	C11—C10—H10B	111.1
N1—C3—C4	123.3 (7)	H10A—C10—H10B	109.0
N1—C3—C8	120.4 (6)	C10—C11—H11A	109.5
C4—C3—C8	116.3 (6)	C10—C11—H11B	109.5
C5—C4—N2	114.2 (6)	H11A—C11—H11B	109.5
C5—C4—C3	121.6 (7)	C10—C11—H11C	109.5
N2—C4—C3	124.2 (7)	H11A—C11—H11C	109.5
C4—C5—C6	123.2 (6)	H11B—C11—H11C	109.5

C3—N1—C2—C1	84.9 (10)	C4—C5—C6—C7	−1.2 (9)
C2—N1—C3—C4	177.9 (6)	C9—C6—C7—C8	179.8 (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—C3	3.4 (10)
O2—N2—C4—C5	−177.5 (7)	N1—C3—C8—C7	177.8 (7)
O1—N2—C4—C3	175.8 (7)	C4—C3—C8—C7	−3.1 (9)
O2—N2—C4—C3	1.9 (10)	C10—O4—C9—O3	−1.7 (10)
N1—C3—C4—C5	179.9 (7)	C10—O4—C9—C6	178.0 (6)
C8—C3—C4—C5	0.9 (8)	C5—C6—C9—O3	173.2 (7)
N1—C3—C4—N2	0.6 (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—O4	172.4 (6)
C3—C4—C5—C6	1.3 (9)	C9—O4—C10—C11	176.7 (6)
C4—C5—C6—C9	177.8 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86	2.00	2.645 (10)	131
N1—H1A···O3ⁱ	0.86	2.45	3.053 (10)	128

Symmetry code: (i) −x+2, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂O₄
M_r	238.24
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	294
a, b, c (Å)	4.2360 (8), 16.180 (3), 8.4890 (17)
β (°)	95.80 (3)
V (Å³)	578.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.969, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	1213, 1066, 841
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.077, 0.173, 1.01
No. of reflections	1066
No. of parameters	154
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.30

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86	2.00	2.645 (10)	131.00
N1—H1A···O3ⁱ	0.86	2.45	3.053 (10)	128.00

Symmetry code: (i) −x+2, y+1/2, −z+1.

Acknowledgements

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

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