Methyl 4-anilino-3-nitro­benzoate

Hao-Yuan Li; Yong-Zhong Wu; Bo-Nian Liu; Shi-Gui Tang; Cheng Guo

doi:10.1107/S1600536809018923

. 2009 May 23;65(Pt 6):o1381. doi: 10.1107/S1600536809018923

Methyl 4-anilino-3-nitrobenzoate

Hao-Yuan Li ^a, Yong-Zhong Wu ^b, Bo-Nian Liu ^c, Shi-Gui Tang ^a, Cheng Guo ^c,^*

PMCID: PMC2969563 PMID: 21583229

Abstract

In the molecule of the title compound, C₁₄H₁₂N₂O₄, the aromatic rings are oriented at a dihedral angle of 51.50 (4)°. An intramolecular N—H⋯O interaction results in the formation of a six-membered ring having an envelope conformation. In the crystal structure, intermolecular N—H⋯O interactions link the molecules into centrosymmetric dimers. π–π contacts between the benzene rings [centroid–centroid distance = 3.708 (1) Å] may further stabilize the structure.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For the synthesis, see: Schelz (1978 ▶).

Experimental

Crystal data

C₁₄H₁₂N₂O₄
M _r = 272.26
Monoclinic,
a = 11.641 (2) Å
b = 16.349 (3) Å
c = 7.2490 (14) Å
β = 107.50 (3)°
V = 1315.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 294 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 = 0.970, T _max = 0.990
2569 measured reflections
2367 independent reflections
1335 reflections with I > 2σ(I)
R _int = 0.026
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.178
S = 1.00
2367 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.44 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.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809018923/hk2689sup1.cif

e-65-o1381-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018923/hk2689Isup2.hkl

e-65-o1381-Isup2.hkl^{(116.3KB, hkl)}

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⋯O1	0.86	2.01	2.650 (4)	130
N1—H1A⋯O1ⁱ	0.86	2.53	3.314 (4)	152

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

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. Rings A (C1-C6) and B (C7-C12) are, of course, planar and they are oriented at a dihedral angle of A/B = 51.50 (4)°. Intramolecular N-H···O interaction (Table 1) results in the formation of a six-membered ring C (O1/N1/N2/C7/C12/H1A) having envelope conformation with atom O1 displaced by 0.125 (4) 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. The π–π contact between the benzene rings, Cg2—Cg2ⁱ [symmetry code: (i) x, 1/2 - y, z - 1/2, where Cg2 is centroid of the ring B (C7-C12)] may further stabilize the structure, with centroid-centroid distance of 3.708 (1) Å.

Experimental

For the preparation of the title compound, methyl 4-chloro-3-nitrobenzoate (5.0 g, 23 mmol) was heated in distilled aniline (10 ml) for 18 h at 393 K. After the reaction was completed, ethanol (50 ml) was added, at room temperature. The yellow precipitate was washed with cold ethanol (2 × 20 ml), and then dried (yield; 4.7 g). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.