N′-[(E)-(3-Fluoro­pyridin-2-yl)methyl­idene]pyridine-3-carbohydrazide dihydrate

Yamuna Nair; M Sithambaresan; S Muraleedharan Nair; M R Prathapachandra Kurup

doi:10.1107/S1600536814006072

. 2014 Mar 26;70(Pt 4):o483–o484. doi: 10.1107/S1600536814006072

N′-[(E)-(3-Fluoropyridin-2-yl)methylidene]pyridine-3-carbohydrazide dihydrate

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

PMCID: PMC3998601 PMID: 24826177

Abstract

The organic molecule in the title dihydrate, C₁₂H₉FN₄O·2H₂O, exists in the E conformation with respect to the azomethane C=N double bond. The molecule is approximately planar, with a maximum deviation of 0.117 (1) Å for the carbonyl O atom from the mean plane of the molecule. Both pyridine rings are essentially coplanar with the central C(=O)N₂C unit [dihedral angles = 1.99 (7) and 5.71 (8)°], exhibiting a significant difference in dihedral angles from its benzohydrazide analogue. The crystal packing features N—H⋯O, O—H⋯N and O—H⋯O hydrogen-bond interactions, which lead to the formation of a chain along the c-axis direction through one of the water molecules present, and these chains are stacked one over the other by means of π–π interactions [with centroid–centroid distances of 3.7099 (10) and 3.6322 (10) Å] between the aromatic rings in neighbouring antiparallel molecules, building a three-dimensional supramolecular network.

Related literature

For the biological activity of carbohydrazide derivatives, see: Sreeja et al. (2004 ▶); Havanur et al. (2010 ▶); Despaigne et al. (2010 ▶). For the synthesis of related compounds, see: Kuriakose et al. (2007 ▶). For a related structure, see Nair et al. (2012 ▶). graphic file with name e-70-0o483-scheme1.jpg

Experimental

Crystal data

C₁₂H₉FN₄O·2H₂O
M _r = 280.26
Monoclinic,
a = 7.3023 (7) Å
b = 14.4031 (17) Å
c = 12.6422 (13) Å
β = 94.842 (3)°
V = 1324.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.41 × 0.21 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.963, T _max = 0.969
9779 measured reflections
3237 independent reflections
2339 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.149
S = 1.04
3237 reflections
202 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.20 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 for Windows (Farrugia, 2012 ▶) 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/S1600536814006072/bv2232sup1.cif

e-70-0o483-sup1.cif^{(22.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814006072/bv2232Isup2.hkl

e-70-0o483-Isup2.hkl^{(158.8KB, hkl)}

Click here for additional data file.^{(5.3KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814006072/bv2232Isup3.cml

CCDC reference: 992525

Additional supporting information: 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′⋯O1S	0.88 (1)	2.04 (1)	2.8821 (19)	160 (2)
O1S—H1A⋯N4ⁱ	0.87 (1)	2.09 (1)	2.946 (2)	170 (3)
O2S—H2A⋯N1ⁱ	0.87 (1)	2.10 (1)	2.965 (2)	177 (2)
O2S—H2B⋯O1ⁱ	0.86 (1)	1.97 (1)	2.816 (2)	172 (2)

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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 single-crystal XRD measurements.

supplementary crystallographic information

1. Comment

Carbohydrazides have attracted much attention for their excellent biological properties. Moreover, carbohydrazides derived from 2-acetylpyridine are known to inhibit the proliferation of tumour cells to a greater extent compared to standard anticancer agents (Havanur et al., 2010; Sreeja et al., 2004). In addition, metal complexes with carbohydrazides exhibit antimicrobial, DNA-binding and cytotoxic activities. It has also been shown that these metal complexes can be potent inhibitors of cell growth and DNA synthesis (Despaigne et al., 2010). We report herein the crystal structure of the title compound, a new carbohydrazide.

This molecule adopts an E configuration (Fig. 1) with respect to the C6=N2 bond and it exists in the amido form with a C7=O1 bond length of 1.2211 (18) Å which is very close to the reported C=O bond length of similar structure of benzene analogue (Nair et al., 2012). The O1 and N2 atoms are in a Z configuration with respect to C7–N3 having a tortional angle of -0.6 (3)°. The molecule is almost planar with maximum deviation of 0.117 (1) Å for the atom O1 from the mean plane of the molecule (r.m.s. deviation, 0.0513). The pyridyl ring having F atom is essentially coplanar with the central C(=O)N₂C unit (dihedral angle 5.71 (8)°), the other pyridyl ring exhibits a torsion angle of 1.99 (7)°.

Whilst one of the water molecules connects two adjacent molecules through two O–H···N and N–H···O H-bonding interactions with D···A distances of 2.946 (2) and 2.882 (1) Å respectively, the other water molecule forms two O–H···N and O–H···O H-bonds with D···A distances of 2.965 (2) and 2.816 (2) Å with the same molecule (Fig. 2, Table 1). One of the water molecules acts as both a hydrogen bond acceptor as well as a donor towards another carbohydrazide molecule while the other acts only as hydrogen bond donor. By means of these interactions the molecules are chained through one of the water molecules to form infinite chains parallel to the c axis of the unit cell (Fig. 3). These parallel chains are stacked one over the other by means of two π–π interactions between the two aromatic rings of the neighbouring anti parallel molecules (Fig. 4) with centeroid-centeroid distances of 3.7099 (10) and 3.6322 (10) Å. Fig. 5 shows the stacked packing of the molecules along a axis in the unit cell.

2. Experimental

The title compound was prepared by adapting a reported procedure (Kuriakose et al., 2007). 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 pyridine-3-carbohydrazide (1.37 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 needle shaped crystals, suitable for single-crystal analysis, were obtained after slow evaporation of the solution in air for a few days.