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 ▶). 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,

• a = 4.2360 (8) Å

• b = 16.180 (3) Å

• c = 8.4890 (17) Å

• β = 95.80 (3)°

• V = 578.8 (2) ų

• 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[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

• Δρ_max = 0.24 e Å⁻³

• Δρ_min = −0.30 e Å⁻³

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.

Supplementary Material

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

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) .

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, 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.

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 U_iso(H) = xU_eq(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

C11H14N2O4	F(000) = 252
Mr = 238.24	Dx = 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

Enraf–Nonius CAD-4 diffractometer	841 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
graphite	θmax = 25.2°, θmin = 2.4°
ω/2θ scans	h = −5→5
Absorption correction: ψ scan (North et al., 1968)	k = 0→19
Tmin = 0.969, Tmax = 0.990	l = 0→10
1213 measured reflections	3 standard reflections every 120 min
1066 independent reflections	intensity decay: none

Refinement

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(Fo2) + (0.05P)2 + 1.25P] where P = (Fo2 + 2Fc2)/3
1066 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.24 e Å−3
4 restraints	Δρmin = −0.30 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) −x+2, y+1/2, −z+1.