N′-[(E)-(3-Fluoro­pyridin-2-yl)methyl­idene]benzohydrazide monohydrate

Yamuna Nair; M Sithambaresan; M R Prathapachandra Kurup

doi:10.1107/S1600536812035179

. 2012 Aug 15;68(Pt 9):o2709. doi: 10.1107/S1600536812035179

N′-[(E)-(3-Fluoropyridin-2-yl)methylidene]benzohydrazide monohydrate

Yamuna Nair ^a, M Sithambaresan ^b,^*, M R Prathapachandra Kurup ^c

PMCID: PMC3435726 PMID: 22969597

Abstract

The title compound, C₁₃H₁₀FN₃O·H₂O, exists in the E conformation with respect to the azomethane C=N double bond. The molecule is close to planar with a maximum deviation of 0.286 (2) Å. The pyridine ring is essentially coplanar with the central C(= O)N₂C unit [dihedral angle = 2.02 (3)°] and the phenyl ring exhibits a dihedral angle of 14.41 (10)° with respect to the central unit. The crystal structure features O—H⋯N, N—H⋯O and O—H⋯O hydrogen-bond interactions between the solvent water and the benzohydrazide molecules, as well as C—H⋯O hydrogen bonds and C—F⋯π [3.0833 (18) Å] interactions.

Related literature

For background to the use of benzohydrazides as catalysts, see: Heravi et al. (2007 ▶); Hou et al. (2005 ▶) and for their biological activity, see: Sreeja et al. (2004 ▶). For the synthesis of related compounds, see: Fun et al. (2008 ▶). For related structures, see Mangalam et al. (2009 ▶).

Experimental

Crystal data

C₁₃H₁₀FN₃O·H₂O
M _r = 261.26
Orthorhombic,
a = 8.2540 (4) Å
b = 11.5489 (4) Å
c = 26.1962 (11) Å
V = 2497.14 (18) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.964, T _max = 0.974
34264 measured reflections
2192 independent reflections
1817 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.096
S = 1.07
2190 reflections
185 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.13 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: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812035179/zl2494sup1.cif

e-68-o2709-sup1.cif^{(22KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035179/zl2494Isup2.hkl

e-68-o2709-Isup2.hkl^{(107.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812035179/zl2494Isup3.cml

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
N3—H3′⋯O1W	0.901 (18)	1.914 (18)	2.7917 (17)	164.3 (16)
O1W—H1A⋯O1ⁱ	0.84 (3)	2.08 (3)	2.9187 (19)	172 (2)
O1W—H1A⋯N2ⁱ	0.84 (3)	2.48 (2)	2.9494 (17)	116.1 (19)
O1W—H1B⋯N1ⁱ	0.89 (2)	1.95 (3)	2.8420 (18)	178 (2)
C9—H9⋯O1W	0.93	2.30	3.209 (2)	165

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are thankful to Dr Shibu M. Eapen, SAIF, Cochin University of Science and Technology, for the data collection.

supplementary crystallographic information

Comment

Interest in coordination chemistry of benzohydrazide has been a subject of enthusiastic research since their complexes show a wide range of catalytic properties (Heravi et al., 2007; Hou et al., 2005). Benzohydrazone derivatives are also important due to their wide spectrum of biological activities (Sreeja et al., 2004).

This molecule adopts an E conformation with respect to the C6=N2 bond and it exists in the amido form with a C7=O1 bond length of 1.2258 (17) Å which is very close to the reported C=O bond length of a similar structure (Mangalam et al., 2009). The O1 and N2 atoms are in a Z conformation with respect to C7–N3 having a torsional angle of -0.4 (2)°. The molecule is almost planar with a maximum deviation of 0.286 (2) Å for the atom C12 from its least square plane. The pyridyl ring is essentially coplanar with the central C(=O)N₂C unit (dihedral angle 2.02 (3) °), the phenyl ring exhibits a dihedral angle of 14.41 (10)° with respect to the central unit.

The water molecule forms six H-bonds with two different benzohydrazone molecules. Hydrogen bond interactions such as O–H···N, O–H···O, N–H···O and C–H···O are present in the crystal system between the H atoms attached to the O1W atom and N1, N2, N3, C9 and O1 atoms of two adjacent molecules with D···A distances of 2.842 (2), 2.9495 (17), 2.7917 (17), 3.209 (2) and 2.9188 (18) Å respectively as shown in Table 1. Both H-atoms of the water molecule form bifurcated hydrogen bonds with the azomethine nitrogen, the pyridyl nitrogen and the carbonyl oxygen atoms of one neighboring molecule (Fig. 2). The water molecule acts as a hydrogen bond acceptor towards another benzohydrazone molecule through an N–H···O hydrogen bond. 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). Benzohydrazone molecules within these chains also interact through weak C–F···π [3.0833 (18) Å] interactions (Fig. 2) that augment the stronger O–H···N, O–H···O, N–H···O hydrogen bonds.

Experimental

The title compound was prepared by adapting a reported procedure (Fun et al., 2008). A solution of 3-fluoropyridine-2-carbaldehyde (1.25 g,1 mmol) in ethanol (10 ml) was mixed with an ethanolic solution (10 ml) of benzohydrazide (1.36 g,1 mmol). The mixture was boiled under reflux for 12 h after adding few drops of glacial acetic acid and then cooled to room temperature. Colorless block shaped crystals, suitable for single-crystal analysis, were obtained in 61.8% yield after slow evaporation of the solution in air for a few days. ¹H NMR spectrum, DMSO-d₆, δ, p.p.m.: 12.12 (s, 1H, NH), 8.66 (s, 1H, CH=N), 8.53 (d, 1H, py–H(C1)), 7.54–7.95 (m, 7H, Ar–H (C2, C3, C9, C10, C11, C12, C13)). IR spectrum, ν (cm^-1): 3421, 3059, 1683,1650, 1597, 1441, 1350, 1295, 1273, 1167, 1134, 1073, 922, 801, 706, 674.