4-Nitro­phenyl N-phenyl­carbamate

Yun-Hua Xu; Fanqi Qu

doi:10.1107/S1600536807068274

. 2008 Jan 9;64(Pt 2):o404. doi: 10.1107/S1600536807068274

4-Nitrophenyl N-phenylcarbamate

Yun-Hua Xu ^a, Fanqi Qu ^b,^*

PMCID: PMC2960206 PMID: 21201432

Abstract

The title compound, C₁₃H₁₀N₂O₄, was synthesized as an intermediate for the preparation of ureas. The two aromatic rings are twisted about the central carbamate group with a C—C—N—C torsion angle of 139.6 (2)° and a C—C—O—C torsion angle of 95.9 (2)°. The molecules are linked into one-dimensional chains by N—H⋯O hydrogen bonds along the b axis. Weak interactions between O atoms of the nitro groups (O⋯O = 3.012 Å) connect two adjacent chains.

Related literature

For related literature, see: Allen et al. (1987 ▶); Izdebski & Pawlak (1989 ▶); Olma et al. (2006 ▶); Tye et al. (2002 ▶).

Experimental

Crystal data

C₁₃H₁₀N₂O₄
M _r = 258.23
Monoclinic,
a = 6.0170 (2) Å
b = 5.0650 (1) Å
c = 18.8960 (5) Å
β = 92.538 (1)°
V = 575.31 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 90 (2) K
0.50 × 0.40 × 0.26 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.946, T _max = 0.971
2630 measured reflections
1473 independent reflections
1363 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.104
S = 1.14
1473 reflections
172 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO–SMN (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1995 ▶); software used to prepare material for publication: SHELXL97 and local procedures.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068274/fl2180sup1.cif

e-64-0o404-sup1.cif^{(15.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068274/fl2180Isup2.hkl

e-64-0o404-Isup2.hkl^{(72.6KB, 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—H1⋯O1ⁱ	0.88	2.05	2.903 (3)	164

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Symmetry code: (i) Inline graphic .

Acknowledgments

FQ and Y-HX thank Dr Sihui Long for helpful discussions during the preparation of this paper.

supplementary crystallographic information

Comment

The title compound (I), along with other 4-nitrophenyl carbamates, are important intermediates for the synthesis of ureas (Olma, et al. 2006; Izdebski & Pawlak, 1989). Although it has been used in organic sythesis for a long time, the crystal structure, as far as we know, is reported here for the first time.

The compound, two aromatic rings connected by a carbamate group, is not planar as would be expected. This is evidenced by the dihedral angles between the nitrophenyl ring and the carbamate, C13—C8—O2—C7=95.9 (2)°, and the benzyl ring and the carbamate, C2—C1—N1—C7=139.6 (2)°. Bond lengths and angles for (I) are within normal ranges (Allen et al., 1987). The molecules form one-dimensional chains formed through N—H···O hydrogen bonds along the b axis (Table 1). In addition, intermolecular O···O interactions exists between nitro groups in neighboring chains (Fig. 2).

Experimental

Aniline (1.0 g, 10.7 mmol) was added dropwise to a round-bottom flask containing 4-nitrophenyl chloroformate (2.2 g, 10.9 mmol) and pyridine (0.9 ml, 11.1 mmol) in 20 ml me thylene chloride cooled with ice water. After the solutuion was warmed to ambient temperature, the mixture was refluxed overnight with stirring. The solution was then washed with 1 N NaHCO₃, water and brine, and then dried with anhydrous Na₂SO₄. After removal of the solvent, the product was recovered as a yellow solid (2.5 g, 90%) (Tye, et al. 2002). Colorless crystals of (I) were obtained by recrystallization from ethyl acetate.