1-Cyclo­pentyl­idene-2-(2,4-dinitro­phenyl)­hydrazine

Ning-Ning Ji; Zhi-Qiang Shi

doi:10.1107/S1600536808033345

. 2008 Oct 18;64(Pt 11):o2141. doi: 10.1107/S1600536808033345

1-Cyclopentylidene-2-(2,4-dinitrophenyl)hydrazine

Ning-Ning Ji ^a,^*, Zhi-Qiang Shi ^b

PMCID: PMC2959650 PMID: 21581001

Abstract

The title compound, C₁₁H₁₂N₄O₄, was synthesized by the reaction of (2,4-dinitrophenyl)hydrazine with cyclopentanone. The cyclopentyl fragment is disordered over two sites with occupancies of 0.63 (1) and 0.37 (1). An intramolecular N—H⋯O hydrogen bond helps to establish the conformation. Pairs of molecules are held together by π–π interactions between adjacent benzene rings [centroid-to-centroid distance 3.589 (2) Å].

Related literature

For background literature on Schiff bases, see: Liang (2007 ▶). For information on the properties of dinitrophenylhydrazones, see: Baughman et al. (2004 ▶); Zare et al. (2005 ▶); El-Seify & El-Dossoki (2006 ▶); Kim & Yoon (1998 ▶). For bond-length data, see: Allen et al. (1987 ▶); Allen (2002 ▶).

Experimental

Crystal data

C₁₁H₁₂N₄O₄
M _r = 264.25
Monoclinic,
a = 6.962 (3) Å
b = 21.840 (10) Å
c = 8.162 (4) Å
β = 98.528 (9)°
V = 1227.3 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 295 (2) K
0.15 × 0.10 × 0.06 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.984, T _max = 0.993
6423 measured reflections
2168 independent reflections
1353 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.129
S = 1.02
2168 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033345/fb2114sup1.cif

e-64-o2141-sup1.cif^{(16.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033345/fb2114Isup2.hkl

e-64-o2141-Isup2.hkl^{(106.6KB, 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
N3—H3⋯O2	0.86	1.99	2.605 (2)	128

Open in a new tab

Acknowledgments

This project was supported by the Postgraduate Foundation of Taishan University (grant No. Y06-2-08).

supplementary crystallographic information

Comment

Schiff bases and their complexes are widely used in the fields of biology, catalysis etc. (Liang, 2007). Especially, the dinitrophenylhydrazones exhibit good nonlinear optical (NLO) and crystalline properties (Baughman et al., 2004). The benzophenone-2,4-dinitrophenylhydrazone derivatives are important because of their significant molecular nonlinearities and remarkable ability to crystallize in non-centrosymmetric crystal systems (Zare et al., 2005; El-Seify & El-Dossoki, 2006; Kim & Yoon, 1998). In order to search for new dinitrophenylhydrazones, the title compound was synthesized and its crystal structure is reported here (Fig. 1). The obtained unrestrained bond lengths and angles are in good agreement with the expected values (Allen et al., 1987) in the non-disordered region. In the crystal structure (Fig. 2), the molecules are stabilized by N—H···O hydrogen bonds (Table 1), C—H···N interactions (C6—H6···N4: 0.93, 2.39, 2.722 (3) Å and 101.1°) and by π–π electron interactions between the benzene rings. The distances between the centroids of the stacked benzene rings are 3.589 (2) Å though the molecules are situated in rather equidistant planes.

Experimental

The title compound was synthesized by the reaction of (2,4-dinitro-phenyl)-hydrazine (1 mmol, 198.1 mg) with cyclopentanone (1 mmol, 84.1 mg) in ethanol (30 ml) under reflux conditions (348 K) for 3 h. The solvent was removed and the solid product was recrystallized from tetrahydrofuran. Brown crystals that were suitable for X-ray diffraction study were grown in the course of three days. Yield, 227.2 mg, 86%; m. p. 318–320 K.

Analysis calculated for C₁₁H₁₂N₄O₄: C 50.00, H 4.58, N 21.20%; found: C 49.97, H 4.52, N 21.15%.