Ethyl 4-anilino-3-nitro­benzoate

Yeong Keng Yoon; Elumalai Manogaran; Mohamed Ashraf Ali; Suhana Arshad; Ibrahim Abdul Razak

doi:10.1107/S1600536812019903

. 2012 May 12;68(Pt 6):o1684. doi: 10.1107/S1600536812019903

Ethyl 4-anilino-3-nitrobenzoate

Yeong Keng Yoon ^a, Elumalai Manogaran ^b, Mohamed Ashraf Ali ^a, Suhana Arshad ^c, Ibrahim Abdul Razak ^c,^*,^‡

PMCID: PMC3379280 PMID: 22719478

Abstract

In the title compound, C₁₅H₁₄N₂O₄, the dihedral angle between the benzene and phenyl rings is 73.20 (6)°. An intramolecular N—H⋯O hydrogen bond forms an S(6) ring motif. In the crystal, molecules are linked by N—H⋯O and C—H⋯O hydrogen bonds into a layer parallel to the bc plane.

Related literature

For applications of nitrophenyleneamines, see: Stephane (2006 ▶); Glebowska et al. (2009 ▶); Remusat et al. (2004 ▶). For related structures, see: Mohdaidin et al. (2008 ▶); Zhang et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-68-o1684-scheme1.jpg

Experimental

Crystal data

C₁₅H₁₄N₂O₄
M _r = 286.28
Monoclinic,
a = 10.6464 (2) Å
b = 9.9178 (2) Å
c = 14.7885 (2) Å
β = 120.244 (1)°
V = 1348.96 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.35 × 0.20 × 0.16 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.965, T _max = 0.984
17988 measured reflections
4639 independent reflections
3276 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.124
S = 1.04
4639 reflections
195 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812019903/is5128sup1.cif

e-68-o1684-sup1.cif^{(23.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019903/is5128Isup2.hkl

e-68-o1684-Isup2.hkl^{(227.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812019903/is5128Isup3.cml

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—H1N1⋯O4	0.859 (18)	2.00 (2)	2.6375 (17)	130.6 (17)
N1—H1N1⋯O2ⁱ	0.858 (17)	2.288 (16)	2.9411 (14)	133.0 (14)
C15—H15A⋯O2ⁱⁱ	0.93	2.45	3.342 (2)	160

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia for the Research University grants Nos. 1001/PFIZIK/811151 and 1001/PSK/8620012. The authors also thank Pharmacogenetic and Novel Therapeutic Research, Institute for Research in Molecular Medicine, Universiti Sains Malaysia.

supplementary crystallographic information

Comment

In chemistry, nitrophenyleneamines are important building blocks for many pharmaceutical compounds. Phenylenediamine themselves are also used as composition in making dyes (Stephane, 2006), metallomesogens (Glebowska et al., 2009) as well as ligand precursors. Condensation of substituted ο-phenylenediamine with various diketones is then used in the preparation of a variety of pharmaceuticals (Remusat et al., 2004).

In the molecular structure (Fig. 1), an intramolecular N1—H1N1···O4 hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995). The C1–C6 benzene ring [maximum deviation of 0.007 (1) Å at atoms C5 and C6] and C10–C15 phenyl ring [maximum deviation of 0.005 (2) Å at atom C12] make a dihedral angle of 73.20 (6)° with each other. Bond lengths and angles are within normal ranges and are comparable to related structures (Mohd. Maidin et al., 2008; Zhang et al., 2009).

The crystal packing is shown in Fig. 2. The intermolecular N1—H1N1···O2 and C15—H15A···O2 (Table 1) hydrogen bonds linked the molecules into a two-dimensional network parallel to the bc plane.

Experimental

Ethyl-4-fluro-3-nitro benzoate (1 g) in dichloromethane (20 ml) was added into the solution of aniline (0.51 g) and N,N-diisopropylethylamine (0.72 g) in dichloromethane (20 ml). The reaction mixture was stirred overnight at room temperature. After completion of the reaction, evidenced by TLC analysis. The reaction mixture was washed with water (10 ml × 2) and 10% Na₂CO₃ (10 ml × 2). The dichloromethane layer was collected and dried over Na₂SO₄ and evaporated in vacuo to yield the product. The product was recrystallised from ethyl acetate.