Ethyl 3-nitro-4-(n-propyl-amino)benzoate.

In the mol-ecule of the title compound, C(12)H(16)N(2)O(4), an intra-molecular 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 & n class="Chemical">Buyukbingol (2001 ▶); Oezden et al. (2005 ▶).

Experimental

Crystal data

C12H16N2O4

M = 252.27

Triclinic,

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[F 2 > 2σ(F 2)] = 0.067

wR(F 2) = 0.165

S = 1.00

2281 reflections

157 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.14 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 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

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

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901873X/hk2690Isup2.hkl

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

C12H16N2O4	Z = 2
Mr = 252.27	F(000) = 268
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.057P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
2281 reflections	Δρmax = 0.19 e Å−3
157 parameters	Δρmin = −0.14 e Å−3
Primary atom site location: structure-invariant direct methods

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) .