N′-[(Z)-4-Methyl­benzyl­idene]-4-nitro­benzohydrazide monohydrate

Hoong-Kun Fun; Samuel Robinson Jebas; K V Sujith; B Kalluraya

doi:10.1107/S1600536808037008

. 2008 Nov 13;64(Pt 12):o2338. doi: 10.1107/S1600536808037008

N′-[(Z)-4-Methylbenzylidene]-4-nitrobenzohydrazide monohydrate

Hoong-Kun Fun ^a,^*, Samuel Robinson Jebas ^a,^‡, K V Sujith ^b, B Kalluraya ^b

PMCID: PMC2960119 PMID: 21581313

Abstract

In the title compound, C₁₅H₁₃N₃O₃·H₂O, the two benzene rings form a dihedral angle of 2.03 (2)°. In the crystal structure, adjacent hydrazide molecules are linked into dimers by water molecules; these dimers are then stacked along the b axis. Intermolecular O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds and a π–π stacking interaction between the nitrobenzene and tolyl rings with a centroid–centroid distance of 3.8208 (3) Å are observed. There is also a short O⋯N contact [2.6824 (7) Å].

Related literature

For related literature on hydrazones, see: Sridhar & Perumal (2003 ▶). For the biological applications of hydrazides/hydrazones, see: Bedia et al. (2006 ▶). For a related structure, see: Fun et al. (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₅H₁₃N₃O₃·H₂O
M _r = 301.30
Triclinic,
a = 6.5387 (1) Å
b = 6.9730 (1) Å
c = 15.9064 (3) Å
α = 80.524 (1)°
β = 82.628 (1)°
γ = 85.036 (1)°
V = 707.85 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100.0 (1) K
0.68 × 0.44 × 0.23 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.932, T _max = 0.976
31311 measured reflections
7380 independent reflections
6571 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.118
S = 1.05
7380 reflections
211 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.59 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/S1600536808037008/is2358sup1.cif

e-64-o2338-sup1.cif^{(19.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037008/is2358Isup2.hkl

e-64-o2338-Isup2.hkl^{(353.8KB, 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—H1N2⋯O1W	0.864 (8)	1.978 (9)	2.8191 (7)	164.4 (11)
O1W—H2W1⋯O1ⁱ	0.837 (9)	2.013 (9)	2.8327 (7)	166.1 (11)
O1W—H1W1⋯O1ⁱⁱ	0.851 (9)	2.258 (11)	2.9430 (6)	137.7 (10)
O1W—H1W1⋯N1ⁱⁱ	0.851 (9)	2.357 (9)	3.1287 (7)	151.0 (11)
C1—H1A⋯O1Wⁱⁱⁱ	0.93	2.50	3.4090 (7)	165
C4—H4A⋯O2^iv	0.93	2.58	3.4565 (8)	157
C7—H7A⋯O1W	0.93	2.55	3.2393 (7)	132

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

FHK and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post–doctoral research fellowship.

supplementary crystallographic information

Comment

Hydrazones are versatile intermediates and important building blocks. Aryl hydrazones are important building blocks for the synthesis of a variety of heterocyclic compounds such as pyrazolines and pyrazoles (Sridhar & Perumal, 2003). Hydrazones of aliphatic and aromatic methyl ketones yield pyrazole-4-carboxaldehyde on diformylation by the treatment with Vilsmeier reagent. A series of hydrazide-hydrazones were reported to possess good antituberculosis activity (Bedia et al., 2006). Prompted by these review and in continuation of our work (Fun et al., 2008), we here in report the crystal structure of the title compound, (I).

Bond lengths and angles in (I) (Fig. 1) are found to have normal values (Allen et al., 1987). The two benzene rings are essentially planar with the maximum deviation from planarity being -0.004 (1) Å for atom C6 and 0.002 (1) Å for atom C12, respectively. The dihedral angle formed by the benzene (C1—C6) and (C9—C14) rings is 2.03 (2)°.

The crystal packing is consolidated by O—H···O, O—H···N, C—H···O and N—H···O inter and intramolecular hydrogen bonding (Table 1). Furthermore, the packing is strengthened by π-π stacking interactions involving the benzene (C1—C6) (Cg1) and the symmetry related (C9—C14) ring (Cg2) [Cg1···Cg2ⁱ = 3.8208 (3) Å; symmetry code: (i) 2-x, 1-y, -z] together with O···N short contacts [2.6824 (7) Å]. In the crystal packing, adjacent molecules are linked into dimers by water molecules and the dimers were then stacked down the [010] direction (Fig. 2).

Experimental

The title compound, C₁₅H₁₅N₃O₄, was obtained by refluxing 4-nitrobenzhydrazide (0.01 mol) and 4-methylbenzaldehyde (0.01 mol) in ethanol (30 ml) by adding 3 drops of concentrated sulfuric acid for 3 h. Excess ethanol was removed from the reaction mixture under reduced pressure. The solid product obtained was filtered, washed with water and dried. Crystals suitable for X-ray analysis were obtained from ethanol by slow evaporation.