Ethyl 3-nitro-4-(n-propyl­amino)benzoate

Zhang, G.-H.; Wu, Y.-Z.; Li, H.-Y.; Liu, B.-N.; Guo, C.

doi:10.1107/S160053680901873X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1380

doi:10.1107/S160053680901873X

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Ethyl 3-nitro-4-(n-propylamino)benzoate

Guo-Hua Zhang,^a Yong-Zhong Wu,^b Hao-Yuan Li,^c Bo-Nian Liu ^a and Cheng Guo ^a ^*

^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

(Received 14 May 2009; accepted 18 May 2009; online 23 May 2009)

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 envelope conformation. In the crystal structure, 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

C₁₂H₁₆N₂O₄
M_r = 252.27
Triclinic, $[P \overline 1]$
a = 4.4400 (9) Å
b = 12.606 (3) Å
c = 13.209 (3) Å
α = 61.710 (19)°
β = 83.02 (3)°
γ = 81.75 (3)°
V = 643.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 294 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.981, T_max = 0.990
2593 measured reflections
2281 independent reflections
924 reflections with I > 2σ(I)
R_int = 0.083
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.165
S = 1.00
2281 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

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 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680901873X/hk2690sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901873X/hk2690Isup2.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 (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.

Related literature top

For bond-length data, see: Allen et al. (1987). For the synthesis, see: Ates-Alagoz & Buyukbingol (2001); Oezden et al. (2005).

Experimental top

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.

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) and PLATON (Spek, 2009); 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 3-nitro-4-(n-propylamino)benzoate top

Crystal data top

C₁₂H₁₆N₂O₄	Z = 2
M_r = 252.27	F(000) = 268
Triclinic, P1	D_x = 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

Data collection top

Enraf–Nonius CAD-4 diffractometer	924 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.083
Graphite monochromator	θ_max = 25.2°, θ_min = 1.8°
ω/2θ scans	h = 0→5
Absorption correction: ψ scan (North et al., 1968)	k = −14→15
T_min = 0.981, T_max = 0.990	l = −15→15
2593 measured reflections	3 standard reflections every 120 min
2281 independent reflections	intensity decay: 1%

Refinement top

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(F_o²) + (0.057P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2281 reflections	Δρ_max = 0.19 e Å⁻³
157 parameters	Δρ_min = −0.14 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₂H₁₆N₂O₄	γ = 81.75 (3)°
M_r = 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)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	924 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.083
T_min = 0.981, T_max = 0.990	3 standard reflections every 120 min
2593 measured reflections	intensity decay: 1%
2281 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	157 parameters
wR(F²) = 0.165	H-atom parameters constrained
S = 1.00	Δρ_max = 0.19 e Å⁻³
2281 reflections	Δρ_min = −0.14 e Å⁻³

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	−0.3870 (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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.981, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	2593, 2281, 924
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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

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