N-Cyclo­heptyl­idene-N′-(2,4-dinitro­phenyl)hydrazine

Reza Kia; Hoong-Kun Fun; Hadi Kargar

doi:10.1107/S1600536809002657

. 2009 Jan 23;65(Pt 2):o382. doi: 10.1107/S1600536809002657

N-Cycloheptylidene-N′-(2,4-dinitrophenyl)hydrazine

Reza Kia ^a, Hoong-Kun Fun ^a,^*, Hadi Kargar ^b

PMCID: PMC2968402 PMID: 21581978

Abstract

The title compound, C₁₃H₁₆N₄O₄, is a new hydrazone. An intramolecular N—H⋯O hydrogen bond generates a six-membered ring, producing an S(6) ring motif. The nitro groups in the ortho and para positions are almost coplanar with the benzene ring to which they are bound, making dihedral angles of 0.60 (11) and 3.18 (11)°, respectively. Pairs of intermolecular C—H⋯O hydrogen bonds link neighbouring molecules into inversion dimers with R ₂ ²(10) motifs. The crystal structure is further stabilized by intermolecular π–π interactions, with a benzene centroid-to-centroid distance of 3.6601 (4) Å.

Related literature

For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related literature on the applications of hydrazone, see, for example: Niknam et al., (2005 ▶); Guillaumont & Nakamura (2000 ▶); Raj & Kurup (2006 ▶); Okabe et al. (1993 ▶).

Experimental

Crystal data

C₁₃H₁₆N₄O₄
M _r = 292.30
Monoclinic,
a = 6.9721 (1) Å
b = 23.7359 (5) Å
c = 8.2274 (2) Å
β = 102.351 (1)°
V = 1330.03 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100.0 (1) K
0.51 × 0.45 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.946, T _max = 0.991
26146 measured reflections
5824 independent reflections
4916 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.113
S = 1.04
5824 reflections
194 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809002657/kj2114sup1.cif

e-65-0o382-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809002657/kj2114Isup2.hkl

e-65-0o382-Isup2.hkl^{(285.1KB, 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—H1N1⋯O2	0.888 (14)	1.947 (14)	2.6225 (9)	131.7 (12)
C2—H2A⋯O3ⁱ	0.95	2.52	3.3165 (10)	142

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Symmetry code: (i) Inline graphic .

Acknowledgments

HKF and RK thank the Malaysian Government and Universiti Sains Malaysia for Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for a postdoctoral research fellowship. HK thanks PNU for financial support. HKF also thanks Universiti Sains Malaysia for Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

2,4-Dinitrophenylhydrazones play an important role as stabilizers for the detection and protection of the carbonyl group (Niknam et al., 2005). 2,4-Dinitrophenylhydrazone derivatives are widely used in as dyes (Guillaumont & Nakamura, 2000). They are also found to have versatile coordinating abilities towards different metal ions (Raj & Kurup, 2006). In addition, some phenylhydrazone derivatives have been shown to be potentially DNA-damaging and mutagenic agents (Okabe et al., 1993).

The title compound (Fig. 1) is a new hydrazone. An intramolecular N—H···O hydrogen bond generates a six-membered ring, producing an S(6) ring motif (Bernstein et al., 1995). The nitro groups in the ortho and para positions are almost coplanar with the benzene ring to which they are bound, making dihedral angles of 0.60 (11)° and 3.18 (11)°, respectively. The cycloheptanone ring is puckered with a total puckering amplitude, Q = 0.7820 (8) Å. Pairs of intermolecular C—H···O hydrogen bonds link neighbouring molecules into dimers with R₂²(10) motifs (Table 1, Fig. 2). The crystal structure is further stabilized by intermolecular π–π interactions [Cg1···Cg1(1 - x, -y, 1 - z) = 3.6601 (4) Å, with Cg the centroid of the benzene ring].

Experimental

The title compound was synthesized based on the reported procedure (Okabe et al. 1993). Single crystals suitable for X-ray diffraction analysis were grown by slow evaporation of a saturated solution of the resulted compound in DMF.