Bis{2-amino-2-oxo-N-[(1E)-1-(pyridin-2-yl-κN)ethyl­idene]acetohydrazidato-κ2 N′,O 1}nickel(II)

Cheikh Hamidou Kane; Ibrahima Elhadj Thiam; Farba Bouyagui Tamboura; Mohamed Gaye; Pascal Retailleau

doi:10.1107/S1600536812014109

. 2012 Apr 6;68(Pt 5):m553. doi: 10.1107/S1600536812014109

Bis{2-amino-2-oxo-N-[(1E)-1-(pyridin-2-yl-κN)ethylidene]acetohydrazidato-κ² N′,O ¹}nickel(II)

Cheikh Hamidou Kane ^a, Ibrahima Elhadj Thiam ^a, Farba Bouyagui Tamboura ^a, Mohamed Gaye ^a,^*, Pascal Retailleau ^b

PMCID: PMC3344308 PMID: 22590074

Abstract

In the title compound, [Ni(C₉H₉N₄O₂)₂], the Ni^II ion is situated on a twofold rotation axis and is coordinated by two O and four N atoms from two tridentate {2-amino-2-oxo-N-[(1E)-1-(pyridin-2-yl-κN)ethylidene]acetohydrazidate ligands in a distorted octahedral geometry. In the crystal, N—H⋯O and N—H⋯N hydrogen bonds link the molecules into columns in [001]. The porous crystal packing is further stabilized via π–π interactions between the pyridine rings of neighbouring molecules [centroid–centroid distance = 3.746 (3) Å] with voids of 270 Å³.

Related literature

For the structures of related nickel complexes, see: Dieng et al. (2004 ▶); Tamboura et al. (2009 ▶); Mikuriya et al. (1996 ▶).

Experimental

Crystal data

[Ni(C₉H₉N₄O₂)₂]
M _r = 469.11
Monoclinic,
a = 16.703 (3) Å
b = 17.878 (4) Å
c = 8.929 (2) Å
β = 114.915 (5)°
V = 2418.2 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 293 K
0.21 × 0.14 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.778, T _max = 0.897
6288 measured reflections
1781 independent reflections
1285 reflections with I > 2σ(I)
R _int = 0.046
θ_max = 23.5°

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.137
S = 1.04
1777 reflections
142 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT (Nonius, 1999 ▶); cell refinement: DENZO and COLLECT; data reduction: SCALEPACK (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and CRYSTALBUILDER (Welter, 2006 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812014109/cv5274sup1.cif

e-68-0m553-sup1.cif^{(22.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014109/cv5274Isup2.hkl

e-68-0m553-Isup2.hkl^{(87.6KB, 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
N4—H4A⋯O2ⁱ	0.86	2.22	2.976 (5)	147
N4—H4B⋯N3ⁱⁱ	0.86	2.25	3.074 (5)	160

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

supplementary crystallographic information

Comment

In the title compound (Fig. 1), the Ni^II ion is situated on a twofold rotational and adopts a distorted octahedral geometry. The coordination of the hydrazones to Ni center results in the formation of two five-membered chelating rings. In the two rings, the Ni–N_pyridyl bond lengths of 2.094 (3) Å are larger than those for Ni–N_iminol bonds [1.980 (3) Å]. The Ni–O1 involving the hydrazonic oxygen have the metal-ligand distance of 2.074 (3) Å. The Ni—N and Ni—O bond distances are similar to those observed in other mononuclear Ni^II complexes with similar tridentate ligands (Dieng et al., 2004; Tamboura et al., 2009). The following bond C6–N2 is not altered in the complex and remains with double bond character. The bond C8–N3 which was simple in character becomes a double bond after deprotonation of the N–H function. The N_imino–Ni–O1 and N_pyridyl–Ni–N_imino angles are 78.25 (13)° and 92.04 (13)° respectively. The deviation from 90° of the bond angles involving the chelation observed is presumably due to the formation of five-membered ring (Mikuriya et al., 1996).

In the crystal structure, the intermolecular hydrogen-bonding network involving the acetamide groups and also the N3 atom (Table 1), propagates parallel to the crystallographic c axis (Fig.2). This contributes to display a double inverted X molecular pattern in the ab plane stabilized by π – π stacking interactions between adjacent pyridine rings with the centroid-centroid distance of 3.746 (3) Å.

Experimental

2-Amino-2-oxo-N^'-(1-(pyridin-2-yl)ethylidene)acetohydrazide (0.206 g, 1 mmol) was dissolved in 10 ml of ethanol and the LiOH (0.042 g, 2 mmol) was added with thorough shaking. To the resulting solution, Ni(CH₃COO)₂.4H₂O (0.2489 g, 1 mmol) was added. Immediate change of the colour was observed. The mixture was stirred at room temperature during 2 h. The solution was filtered off and concentrated to tenth. Crystals that separated from the brown solution were filtered off and recrystallized in ethanol. On standing for three weeks, suitable X-rays crystals were obtained. Yield: 73.5%. Anal. Calc. for [C₁₈H₁₈N₈O₄Ni] (%): C, 46.09; H, 3.87; N, 23.89. Found: C, 46.06; H, 3.85; N, 23.87. Selected IR data (cm^-1, KBr pellet): 3214, 1728, 1645, 1585, 1459, 768.