(E)-N′-(3,4-Di­meth­oxy­benzyl­idene)nicotinohydrazide monohydrate

J Josephine Novina; G Vasuki; M Suresh; M Syed Ali Padusha

doi:10.1107/S1600536814013798

. 2014 Jun 18;70(Pt 7):o793–o794. doi: 10.1107/S1600536814013798

(E)-N′-(3,4-Dimethoxybenzylidene)nicotinohydrazide monohydrate

J Josephine Novina ^a, G Vasuki ^b,^*, M Suresh ^c, M Syed Ali Padusha ^c

PMCID: PMC4120580 PMID: 25161576

Abstract

In the title hydrated compound, C₁₅H₁₅N₃O₃·H₂O, the nicotinohydrazide molecule adopts a trans conformation with respect to the C=N double bond. The dihedral angle between the benzene and pyridine rings is 5.10 (14)°. In the crystal, the solvent water molecule acts as an acceptor, forming an N—H⋯O hydrogen bond supported by two C—H⋯O contacts. It also acts as a donor, forming bifurcated O—H⋯(O,O) and O—H⋯N hydrogen bonds that combine with the former contacts to form zigzag chains of molecules along the c-axis direction. An additional O—H⋯O donor contact completes a set of six hydrogen bonds to and from the water molecule and connects it to a third nicotinohydrazide molecule. This latter contact combines with weaker C—H⋯O hydrogen bonds supported by a C—H⋯π contact to stack molecules along b in a three-dimensional network.

Related literature

For the biological activity of hydrazone compounds, see: Singh & Raghav (2011 ▶); Patil et al. (2011 ▶). For background to the use of nicotinohydrazides as catalysts and of their transition metal complexes in the treatment of tuberculosis, see: Torje et al. (2012 ▶). For closely related structures, see: Novina et al. (2013 ▶); Wang et al. (2010 ▶). graphic file with name e-70-0o793-scheme1.jpg

Experimental

Crystal data

C₁₅H₁₅N₃O₃·H₂O
M _r = 303.32
Monoclinic,
a = 4.9128 (6) Å
b = 25.137 (4) Å
c = 12.2950 (16) Å
β = 96.513 (4)°
V = 1508.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.50 × 0.35 × 0.30 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.952, T _max = 0.971
11633 measured reflections
3704 independent reflections
2250 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.141
S = 1.02
3704 reflections
209 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814013798/sj5412sup1.cif

e-70-0o793-sup1.cif^{(24.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013798/sj5412Isup2.hkl

e-70-0o793-Isup2.hkl^{(181.6KB, hkl)}

Click here for additional data file.^{(6KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814013798/sj5412Isup3.cml

CCDC reference: 1008073

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg2 is the centroid of the C2–C7 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N2⋯O1W ⁱ	0.86	2.06	2.8942 (19)	165
O1W—H2O1⋯O3	0.85 (2)	2.15 (2)	2.955 (2)	157 (3)
O1W—H2O1⋯N1	0.85 (2)	2.49 (2)	3.1087 (19)	130 (2)
C11—H11⋯O1W ⁱ	0.93	2.30	3.199 (3)	162
C8—H8⋯O1W ⁱ	0.93	2.67	3.425 (2)	139
O1W—H1O1⋯O3ⁱⁱ	0.86 (2)	2.09 (2)	2.901 (2)	159 (3)
C1—H1C⋯Cg2ⁱⁱ	0.96	2.88	3.729 (3)	148

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

Acknowledgments

The authors thank the Sophisticated Analytical Instrument Facility, STIC, Cochin University of Science & Technology, Cochin, for the data collection.

supplementary crystallographic information

S1. Comment

Hydrazones constitute an important class of biologically active drug molecules that have attracted the attention of medicinal chemists due to their wide range of pharmacological properties (Singh & Raghav, 2011). Hydrazone derivatives containing an azomethine (–CONHN═CH–) group have been shown to exhibit antiproliferative activities and act as cytotoxic agents with the ability to prevent cell progression in cancerous cells through different mechanisms (Patil et al., 2011). Moreover, hydrazone derivatives may act as multidentate ligands and their transition metal complexes have been used in the treatment of tuberculosis, in colorimetric or fluorimetric analytic determinations, as well as in applications involving catalytic processes (Torje et al., 2012). As part of our studies of substituent effects on the structure and other aspects of hydrazone derivatives, such as (E)—N'-(4-Methoxybenzylidene)pyridine-3-carbohydrazide dihydrate (Novina et al., 2013), in the present work we report the synthesis and crystal structure of the title compound.

The molecule of the title hydrazide derivative (Fig. 1), C₁₅H₁₅N₃O₃·H₂O, exists in a trans conformation with respect to the C8═N1 double bond [1.277 (2) Å] with the torsion angle N2—N1—-C8—C5 = -177.58 (14)°. It also adopts the amido form with the C9═O3 bond length of 1.2322 (19) Å which is very close to the reported C═O bond length of a similar structure (Wang et al., 2010). The benzene and pyridine rings (C2—C7 and N3/C10—C14, respectively) are each planar with a dihedral angle of 5.10 (14)° between their mean-planes. This is comparable to the corresponding angle found in a related structure (Novina et al., 2013). One of the methoxy group is almost coplanar with the C2—C7 benzene ring whereas the other one deviates somewhat from the benzene ring plane [torsion angles: C1—O1—C2—C7 = -3.9 (3), C15—O2—C3—C4 = 16.5 (3)°].

The water molecule forms six H–bonds with three different nicotinohydrazone molecules. N—H···O, O—H···O, O—H···N and C—H···O hydrogen bonds are present in the crystal system (Table 1). One of the H atoms of the water molecule forms bifurcated hydrogen bonds to the azomethine nitrogen and the carbonyl oxygen atoms of one neighboring molecule (Fig. 2). The water molecule acts as a hydrogen bond acceptor towards another nicotinohydrazone molecule through N–H···O and C—H···O hydrogen bonds. Through these interactions the molecules are interconnected through the water molecule to form infinite chains parallel to the b axis of the unit cell (Fig. 2). Furthermore, a C1—H1C···π interaction involving the phenyl (C2—C7) ring together with O–H···O and C–H···O contacts to generate a three dimensional network of molecules stacked along the a axis direction (Fig. 3).

S2. Experimental

3,4-dimethoxybenzaldehyde (4.1 ml, 0.025 mol) was added to an ethanolic solution of nicotinicacid hydrazide (3.4 g, 0.025 mol). After the addition was complete the reaction mixture was stirred well in an ice cold condition for 3 hrs. The colourless solid that formed was filtered and washed several times with petroleum ether (40–60%). The crude solid obtained was dried and recrystallized from absolute alcohol. The recrystallized product was dried over vacuum.