Ethyl 2-[(E)-4-(dimethyl­amino)benzyl­idenehydrazino]-5-nitro­benzoate

Hoong-Kun Fun; Adithya Adhikari; P S Patil; B Kalluraya; Suchada Chantrapromma

doi:10.1107/S1600536808035939

. 2008 Nov 8;64(Pt 12):o2286–o2287. doi: 10.1107/S1600536808035939

Ethyl 2-[(E)-4-(dimethylamino)benzylidenehydrazino]-5-nitrobenzoate

Hoong-Kun Fun ^a,^*, Adithya Adhikari ^b, P S Patil ^c,^‡, B Kalluraya ^b, Suchada Chantrapromma ^d,^§

PMCID: PMC2959927 PMID: 21581265

Abstract

The title compound, C₁₈H₂₀N₄O₄, exists in the E configuration with respect to the C=N bond of the methylidine unit. The dihedral angle between the two benzene rings is 9.01 (6)°. An intramolecular N—H⋯O hydrogen bond involving the benzoate unit generates an S(6) ring motif. In the crystal, the molecules are linked by weak C—H⋯O interactions into infinite chains along the b axis. These chains are further connected into sheets parallel to the ab plane which are stacked approximately along the c axis. A C—H⋯π interaction is also observed.

Related literature

For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For background to the applications of hydrazones, see, for example: Barton et al. (1962 ▶); Bedia et al. (2006 ▶); Buu-Hoi et al. (1953 ▶); Paquette (1995 ▶); Rollas et al. (2002 ▶); Terzioglu & Gürsoy (2003 ▶).

Experimental

Crystal data

C₁₈H₂₀N₄O₄
M _r = 356.38
Monoclinic,
a = 10.8216 (4) Å
b = 15.9175 (6) Å
c = 10.4136 (4) Å
β = 107.091 (2)°
V = 1714.56 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100.0 (1) K
0.44 × 0.41 × 0.31 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.957, T _max = 0.970
16368 measured reflections
3929 independent reflections
3275 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.105
S = 1.04
3929 reflections
242 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.27 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/S1600536808035939/is2354sup1.cif

e-64-o2286-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808035939/is2354Isup2.hkl

e-64-o2286-Isup2.hkl^{(192.6KB, 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
N2—H1N2⋯O4	0.875 (18)	1.978 (17)	2.6736 (14)	135.6 (14)
C7—H7A⋯O1ⁱ	0.93	2.49	3.3599 (16)	156
C12—H12A⋯O4ⁱⁱ	0.93	2.59	3.3961 (16)	145
C16—H16C⋯O2ⁱⁱⁱ	0.96	2.59	3.5116 (19)	162
C17—H17B⋯Cg1ⁱⁱⁱ	0.96	2.64	3.4629 (14)	144

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 is the centroid of the C1–C6 ring.

Acknowledgments

This work is supported by the Department of Science and Technology (DST), Government of India, under grant No. SR/S2/LOP-17/2006. The authors also thank Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

Hydrazine is widely used as a reagent in synthetic organic chemistry but is probably most frequently associated with the transformation of carbonyl-containing compounds to the corresponding hydrazones (Paquette, 1995). These are intermediates in the Wolff-Kishner reduction as well as many other reactions of synthetic utility, such as the Barton vinyl iodide preparation (Barton et al., 1962). Hydrazones have been demonstrated to possess antimicrobial, anticonvulsant, analgesic, antiinflammatory, antiplatelet, antitubercular, anticancer and antitumoral activities (Bedia et al., 2006; Rollas et al., 2002; Terzioglu & Gürsoy, 2003). Hydrazones possessing an azometine –NHN=CH– proton constitute an important class of compounds for new drug development. Therefore, many researchers have synthesized these compounds as target structures to evaluate their biological activities. These observations have been the guides for the development of new hydrazones that possess varied biological activities. Some synthesized hydrazide-hydrazones were reported to have lower toxicity than hydrazides because of the blockage of –NH2 group (Buu-Hoi et al., 1953). These findings further support the growing importance of the synthesis of hydrazide-hydrazones compounds.

Figure 1 shows the molecular structure of the title compound. The total molecule is not planar and exist in the E configuration with respect to the C═N bond of methylidine moiety. The dihedral angle between the two benzene rings is 9.01 (6)°. The methylidine is co-planar with the C1–C6 benzene ring [the most deviation of 0.044 (1) Å of atom C3] with the torsion angle N2–N1–C7–C6 = -179.18 (10)°. The dimethylamino group is slightly twisted from the plane C1–C6 ring as indicated by the torsions angle of C17–N3–C3–C4 = -6.57 (18)° and C18–N3–C3–C4 = -177.96 (12)°. The nitro group is slightly twisted from the C8–C13 benzene ring with the interplanar angle between the mean plane through N4/O1/O2/C11 and C8–C13 planes [8.17 (7)°]. The ethyl group is nearly perpendicularly attached to the benzoate unit which can be reflected by the torsion angle C14–O3–C15–C16 = 88.66 (13)°. An intramolecular N2—H1N2···O4 hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995) (Fig. 1 and Table 1). Bond lengths and angles in the title compound are in normal ranges (Allen et al., 1987).

Figure 2 shows that the molecules are linked into infinite chains along the b axis through weak C7—H7A···O1 interaction (Table 1) and these chains are further connected through weak C—H···O interactions (Table 1) forming sheets parallel to the ab plane. These sheets are stacked approximately along the c axis (Fig. 3). The crystal is stabilized by intramolecular N—H···O hydrogen bond, weak C—H···O interactions (Table 1) and C—H···π interactions (Table 1); Cg1 is the centroid of the C1–C6 ring.

Experimental

The title compound was obtained by refluxing ethyl 2-hydrazinyl-5-nitrobenzoate (0.01 mol) and 4-(dimethylamino) benzaldehyde (0.01 mol) in ethanol (40 ml) by adding 3 drops of concentrated sulfuric acid for 8 hrs. Excess ethanol was removed from the reaction mixture under reduced pressure. The solid product obtained was filtered, washed with water and dried. Red single crystals of the title compound suitable for x-ray structure determination were grown by slow evaporation of an ethanol solution at room temperature (m.p. 439 K).