(E)-Methyl 2-[(4-nitro­phen­yl)­hydrazono]­propanoate

Hai-Yang Yu; Xin Fang; Ming-Lei Cao; Yan-Jun Zhang; Jun-Dong Wang

doi:10.1107/S1600536807067268

. 2007 Dec 21;64(Pt 1):o344. doi: 10.1107/S1600536807067268

(E)-Methyl 2-[(4-nitrophenyl)hydrazono]propanoate

Hai-Yang Yu ^a, Xin Fang ^a, Ming-Lei Cao ^a, Yan-Jun Zhang ^a, Jun-Dong Wang ^a,^*

PMCID: PMC2915385 PMID: 21200906

Abstract

The title compound, C₁₀H₁₁N₃O₄, is a condensation product of 4-nitrophenylhydrazine and methyl pyruvate. The complete molecule except for the methyl groups can be considered as a conjugated π system. All non-H atoms are approximately coplanar (r.m.s. deviation 0.117 Å). The crystal packing involves an N—H⋯O hydrogen bond and a π–π interaction between the aromatic rings, with a centroid–centroid distance of 3.617 Å.

Related literature

For related literature, see: Humphrey & Kuethe (2006 ▶); Tietze et al. (2003 ▶); Van Order & Lindwall (1942 ▶).

Experimental

Crystal data

C₁₀H₁₁N₃O₄
M _r = 237.22
Monoclinic,
a = 12.836 (3) Å
b = 6.9260 (14) Å
c = 11.915 (2) Å
β = 90.11 (3)°
V = 1059.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 173 (2) K
0.60 × 0.54 × 0.16 mm

Data collection

Rigaku R-AXIS SPIDER diffractometer
Absorption correction: none
9730 measured reflections
2416 independent reflections
1997 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.126
S = 1.09
2416 reflections
176 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2004 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEX (McArdle, 1995 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067268/bt2665sup1.cif

e-64-0o344-sup1.cif^{(14.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067268/bt2665Isup2.hkl

e-64-0o344-Isup2.hkl^{(118.7KB, 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
N2—H5⋯O3ⁱ	0.853 (18)	2.200 (18)	2.9928 (17)	154.6 (16)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Foundations of Fujian Province (No. 2006F5058) and Fuzhou University (No. XRC0527).

supplementary crystallographic information

Comment

The title compound, a phenylhydrazone derivative, is an important intermediate for the synthesis of indoles by the Fischer indole reaction (Van Order & Lindwall, 1942; Humphrey & Kuethe, 2006).

The molecular structure of the title compound is shown in Fig. 1. The complete molecule except the methyl groups can be considered as a conjugated π-system. All non-H atoms lie in a common plane (r.m.s. deviation 0.117 Å). The crystal packing shows an N—H···O hydrogen bond (Table 1) and a π-π interaction between the aromatic rings with a centroid-centroid distance of 3.617Å (symmetry operator: 1 - x, -y, 1 - z).

Experimental

A suspension of 4-nitrophenylhydrazine (7.65 g, 50 mmol) in concd. HCl (20 ml) and H₂O (20 ml) was heated to reflux untill the suspension solved. The solution was cooled to room temperature. Then the precipitate was filtrated off and dried. The solid was dissolved in methanol (100 ml) and treated with NaOAc (4.92 g, 60 mmol) and methyl pyruvate (5.10 g, 50 mmol). The mixture was stirred at room temperature for 18 h. Then the yellow precipitate was filtered off, washed with methanol and dried to afford 11.13 g of the title compound (47 mmol, 94%) (Tietze et al., 2003). mp: 209.6–211.1°C. IR: (KBr, ν, cm^-1): 3301 (N—H), 2962 (C—H), 1716 (C—O), 1611 (C—N), 1578, 1504, 1486, 1438, 1338, 1399, 1253, 1177, 1130, 1113, 847, 751.