N-(2,4-Dinitro­phen­yl)-N′-(1-p-tolyl­ethyl­idene)hydrazine

Reza Kia; Hoong-Kun Fun; Bijan Etemadi; Hadi Kargar

doi:10.1107/S1600536809009957

. 2009 Mar 25;65(Pt 4):o833–o834. doi: 10.1107/S1600536809009957

N-(2,4-Dinitrophenyl)-N′-(1-p-tolylethylidene)hydrazine

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

PMCID: PMC2969085 PMID: 21582553

Abstract

In the title molecule, C₁₅H₁₄N₄O₄, the dihedral angle between the two benzene rings is 2.21 (7)°. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. The mean planes of the ortho- and para-nitro groups make dihedral angles of 2.17 (17) and 2.05 (16)°, respectively, with the benzene ring to which they are attached. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds generate R ₂ ²(7), R ₂ ²(13) and R ₂ ¹(10) ring motifs, linking symmetry-related molecules into extended chains along the b axis. In addition, there are intermolecular C⋯C [3.332 (2)–3.343 (2) Å] contacts which are shorter than the sum of the van der Waals radii. The crystal structure is further stabilized by intermolecular C—H⋯π and π–π stacking interactions [centroid–centroid distance = 3.8090 (9) Å].

Related literature

For bond-length data, see: (Allen et al. 1987 ▶). For hydrogen-bond ring motifs, see: Bernstein et al. (1995 ▶). For related structures, see: Fun et al. (2009 ▶); Kia et al. (2009 ▶). For background information on 2,4-dinitrophenylhydrazones, see: Cordis et al. (1998 ▶); Guillaumont & Nakamura (2000 ▶); Lamberton et al. (1974 ▶); Niknam et al. (2005 ▶); Raj & Kurup (2006 ▶); Zegota (1999 ▶); Zlotorzynska & Lai (1999 ▶); For the synthetic procedure, see: Okabe et al. (1993 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₅H₁₄N₄O₄
M _r = 314.30
Monoclinic,
a = 7.6948 (1) Å
b = 14.9092 (3) Å
c = 12.5224 (2) Å
β = 91.778 (1)°
V = 1435.92 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.25 × 0.23 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.974, T _max = 0.984
16826 measured reflections
4211 independent reflections
3206 reflections with I > 2˘I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.143
S = 1.08
4211 reflections
214 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.26 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, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809009957/lh2788sup1.cif

e-65-0o833-sup1.cif^{(19KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009957/lh2788Isup2.hkl

e-65-0o833-Isup2.hkl^{(206.4KB, 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⋯O4	0.85 (2)	1.96 (2)	2.5966 (18)	131.3 (18)
C4—H4A⋯O4ⁱ	0.93	2.51	3.232 (2)	135
C5—H5A⋯O3ⁱ	0.93	2.55	3.4409 (19)	161
C9—H9A⋯O3ⁱ	0.93	2.41	3.295 (2)	158
C14—H14C⋯Cg1ⁱⁱ	0.96	2.68	3.5635 (17)	154

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of the C8–C13 benzene ring.

Acknowledgments

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

supplementary crystallographic information

Comment

2,4-Dinitrophenylhydrazones play a more important role as stabilizers for the detection, characterization and protection of carbonyl groups than do phenylhydrazones (Niknam et al., 2005). 2,4-Dinitrophenylhydrazone derivatives are widely used in various forms of analytical chemistry (Lamberton et al., 1974; Zegota, 1999; Cordis et al., 1998; Zlotorzynska & Lai, 1999) and are also used 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 above information attracted our interest in the title compound and the the crystal structure is reported herein.

The bond lengths (Allen et al., 1987) and angles in the title compound (Fig. 1) have normal values and are comparable to the related structures (Fun et al. 2009; Kia et al. 2009). An intramolecular N—H···O hydrogen bond generates a S(6) ring motif (Bernstein et al., 1995). Weak intermolecular C—H···O hydrogen bonds generate R₂²(7), R₂²(13) and R₂¹(10) ring motifs. These interactions link symmetry related molecules into extended chains along the b axis (Fig. 2). The molecule is approximately planar, with the maximum deviation from the mean plane of the molecule being 0.381 (2) Å for atom C14. The dihedral angle between the two benzene rings is 4.63 (1)°. Some interesting features of the crystal structure are the short intermolecular contacts of O2···O2ⁱ [3.0319(170 Å; (i) -x, -y, 2 - z] and O2···N3ⁱ [3.0513 (18) Å] and in addition the C2···C3ⁱⁱⁱ [3.332 (2) Å; (iii) 1 - x, -y, 2 - z ], C2···C12^iv [3.340 (2) Å; (iv) 1 - x, -y , 1 - z], C7···C13ⁱⁱ [3.343 (2) Å] contacts which are shorter than the sum of the van der Waals radii. The crystal structure is further stabilized by intermolecular C—H···π and π-π interactions [Cg1···Cg2 = 3.8090 (9) Å; Cg1 and Cg2 are the centroids of the C8–C13 and C1–C6 benzene rings].

Experimental

The title compound was synthesized based on the reported procedure (Okabe et al. 1993) except that 4-methyl-acetophenone (1 mmol) was used instead. Single crystals suitable for X-ray diffraction analysis were grown by slow evaporation of a saturated solution of the resulted compound in acetone.