But-2-enal 2,4-dinitro­phenyl­hydrazone

Zhi-Gang Yin; Heng-Yu Qian; Yu-Zhen Chen; Jie Hu

doi:10.1107/S1600536808033254

. 2008 Oct 22;64(Pt 11):o2149. doi: 10.1107/S1600536808033254

But-2-enal 2,4-dinitrophenylhydrazone

Zhi-Gang Yin ^a,^*, Heng-Yu Qian ^a, Yu-Zhen Chen ^a, Jie Hu ^a

PMCID: PMC2959657 PMID: 21581009

Abstract

In the title compound, C₁₀H₁₀N₄O₄, the but-2-enal chain is almost planar, the largest deviation from the mean plane being 0.013 (1) Å, and this plane makes a dihedral angle of 9.95 (24)° with the benzene ring,. Of the two nitro groups, one is twisted with respect to the benzene ring, making a dihedral angle of 5.7 (1)°, whereas the other is nearly in the plane of the benzene ring, with a twist angle of only 0.7 (1)°. This difference is related to the occurence of an intramolecular N—H⋯O hydrogen bond with the O atom of the less twisted nitro group. The NH group is also involved in a weak interaction with the same O atom of a symmetry-related molecule, thus forming a pseudo inversion dimer.

Related literature

For general background, see: Okabe et al. (1993 ▶). For related structures, see: Bolte & Dill (1998 ▶); Ohba (1996 ▶).

Experimental

Crystal data

C₁₀H₁₀N₄O₄
M _r = 250.22
Monoclinic,
a = 4.6699 (8) Å
b = 13.188 (2) Å
c = 18.880 (3) Å
β = 92.565 (3)°
V = 1161.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 (2) K
0.27 × 0.23 × 0.23 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.972, T _max = 0.976
9152 measured reflections
2458 independent reflections
1326 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.111
S = 0.95
2458 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033254/dn2390sup1.cif

e-64-o2149-sup1.cif^{(16.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033254/dn2390Isup2.hkl

e-64-o2149-Isup2.hkl^{(120.8KB, 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—H2⋯O1	0.86	2.02	2.6314 (18)	127
N2—H2⋯O1ⁱ	0.86	2.52	3.331 (2)	159

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

The authors express their deep appreciation to the Outstanding Youth Fund for Henan Natural Scientific Research (grant No. 0512001100) and the Fund for Scientific and Technical Emphasis (grant No. 072102270006)

supplementary crystallographic information

Comment

2,4-Dinitrophenylhydrazine has applications in organic synthesis and some of its derivatives have been shown to be potentially DNA-damaging and mutagenic agents (Okabe et al., 1993). Some phenylhydrazone derivatives have been synthesized in our laboratory. As part of our work, we report the synthesis and crystal structure of the title compound(I).

In the title compound, the but-2-enal chain is planar with the largest deviation from the mean plane being 0.013 (1)Å at C1. This plane makes a dihedral angle of 9.95 (24)° with the benzene ring, so the whole molecule is roughly planar (Fig. 1). Of the the two nitro groups, one is twisted with respect to the benzene ring making a dihedral angle of 5.7 (1)° whereas the other is nearly in the plane of the benzene ring with a twist angle of only 0.7 (1)°. This difference is related to the occurence of an intramolecular hydrogen N-H···bond with the O atom of the less twisted nitro group (Table 1). The NH is also in weak intermolecular interaction with the same O atom of a symmetry related molecule building a pseudo dimer (Table 1, Fig. 2).

Bond lengths and bond angles are consistent with those of other dinitrophenylhydrazone derivatives(Ohba,1996; Bolte & Dill, 1998)

Experimental

2,4-Dinitrophenylhydrazine (1 mmol, 0.198 g) was dissolved in anhydrous methanol, H₂SO₄ (98% 0.5 ml) was added to this, the mixture was stirred for several minitutes at 351 K, but-2-enal (1 mmol 0.070 g) in methanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized in methanol, red single crystals of (I) was obtained after two weeks.