4-Nitro­phenyl 2-methyl­benzoate

Uzma Bibi; Humaira M Siddiqi; Michael Bolte; Zareen Akhter

doi:10.1107/S1600536809046005

. 2009 Nov 7;65(Pt 12):o3038. doi: 10.1107/S1600536809046005

4-Nitrophenyl 2-methylbenzoate

Uzma Bibi ^a, Humaira M Siddiqi ^a,^*, Michael Bolte ^b, Zareen Akhter ^a

PMCID: PMC2971988 PMID: 21578773

Abstract

The title compound, C₁₄H₁₁NO₄, crystallizes with two molecules in the asymmetric unit. The major conformational difference between these two molecules is the dihedral angle between the aromatic rings, namely 36.99 (5) and 55.04 (5)°. The nitro groups are coplanar with the phenyl rings to which they are attached, the O—N—C—C torsion angles being −1.9 (3) and 1.0 (3)° in the two molecules.

Related literature

For background to the applications of aromatic esters containing nitro groups in their aromatic rings, see: Jefford & Zaslona (1985 ▶); Jefford et al. (1986 ▶); Schauble et al. (1971 ▶). For related structures, see: Adams & Morsi (1976 ▶); Shibakami & Sekiya (1995 ▶). graphic file with name e-65-o3038-scheme1.jpg

Experimental

Crystal data

C₁₄H₁₁NO₄
M _r = 257.24
Orthorhombic,
a = 11.4748 (7) Å
b = 14.3608 (8) Å
c = 14.5944 (9) Å
V = 2405.0 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 173 K
0.48 × 0.43 × 0.42 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: none
8396 measured reflections
2536 independent reflections
2233 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.081
S = 1.00
2536 reflections
346 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809046005/pv2221sup1.cif

e-65-o3038-sup1.cif^{(23.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809046005/pv2221Isup2.hkl

e-65-o3038-Isup2.hkl^{(124.6KB, hkl)}

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

Acknowledgments

The authors are grateful to the University Research Fund (URF 2008–09) for financial support. The Department of Chemistry, Quaid-I-Azam Universit, and the Institut für Anorganische Chemie J.-W.-Goethe-Universität Frankfurt, are thanked for providing laboratory and analytical facilities.

supplementary crystallographic information

Comment

Aromatic esters containing nitro groups in their aromatic rings are potential precursors for the preparation of compounds with a number of biological activities such as analgesic and anti-inflammatory (Jefford & Zaslona, 1985). In addition, these compounds served as potential intermediates in the synthesis of many natural products (Jefford et al., 1986; Schauble et al., 1971). The nitro group can be reduced to amino group which can be utilized for the synthesis of azoxy compounds. We have synthsized the title compound (I) which is a nitro substituted ester. In this article, the crystal structure of (I) is reported.

The title compound crystallizes with two molecules (Fig. 1) in an asymmetric unit. The major conformational difference between the two molecules is the dihedral angle between the aromatic rings, namely 36.99 (5)° and 55.04 (5)°. The nitro groups in both molecules are coplanar with the phenyl rings to which they are attached with dihedral angles O3—N1—C5—C6 and O3A—N1A—C5A—C4A being -1.9 (3) and 1.0 (3)°, respectively. The bond distances and angles in (I) agree well with the corresponding distances and angles reported in closely related structures (Adams & Morsi, 1976; Shibakami & Sekiya, 1995).

Experimental

2-Toluic acid (1.5 g, 1 mol) in a 100 ml two neck round bottom flask was gradually warmed on a water bath to 323 K. Dry thionyl chloride was added in excess slowly with stirring along with 2–3 drops of DMF as catalyst. The mixture was refluxed for about 50–60 minutes at 343 K. The excess of thionyl chloride was removed by repeated evaporation at reduced pressure. In a separate flask, 4-nitrophenol (1.5 g, 0.0065 mol) was dissolved in dry dichloromethane to which triethyl amine was added at room temperature to get transparent solution. The acid chloride was added into it drop wise with constant stirring at room temperature for 30 minutes under anhydrous condition and then poured into 20 ml of cold water. Excess of triethyl amine was removed by adding cold dilute HCl solution. The reaction was monitored by TLC using ethyl acetate: n-hexane (1:2). After the completion of reaction the oily product was allowed to settle down and the supernatant liquid was decanted. The product was stirred well with distilled water and extracted with ethyl acetate (3 x 40 ml), washed with 5% NaHCO₃ solution and dried over anhydrous Na₂SO₄. After filtration the solution was concentrated to obtain the title compound which was recrystallized from n-hexane (Yield: 37 %; m.p. 336-344 K).