3- and 4-Pyridinecarboxylic acidN-oxide complexes with manganese(II), cobalt(II) and nickel(II) chlorides

Summary During interaction of ethanol-triethyl orthoformate solutions of nicotinic or isonicotinic acidN-oxides (LH and LH, respectively) with MCl₂ (M = Mn, Co, Ni), only one true adduct, of the Ni(LH)₃Cl₂ · 2 H₂O type was obtained. In all other cases, partial substitution of Cl^– ions with the corresponding pyridinecarboxylateN-oxide anionic ligands (L or L) occurred. As a result, mixed ligands (LH-L or LH-L) were precipitated, as follows: Mn(LH)₂LCl, Co(LH)LCl, Mn(LH)LCl · 4H₂O, Co(LH)LCl · H₂O and Ni₂(LH)LCl₃ · 6 H₂O. The insolubility of the new complexes in all common solvents, combined with the pronounced tendency of the 3- and 4-pyridinecarboxylates and theirN-oxides to function as bidentate bridging ligands, favours bi- or polynuclear structures. Spectral data suggest that Ni(LH)₃Cl₂ · 2 H₂O is hexacoordinate, and the rest of the new complexes pentacoordinate. Bi- or polynuclear structures, involving double -M-(L)₂-M- or-M-(LH)₂-M- and single -M-(L)-M- or-M(L)-M-(LH)-M- bridges, were proposed on the basis of the overall evidence; additional features of the proposed structural types are: exclusively coordinated chloro ligands, in all cases; aqua ligands Co(LH)LCl · H₂O]; lattice water Ni(LH)₂Cl₂ · 2H₂O]; both lattice and coordinated H₂O Mn(LH)LCl · 4H₂O, and Ni₂(LH)LCl₃ · 6H₂O]; and, with the exception of Ni₂(LH)LCl₃ · 6 H₂O, terminal, unidentate, N-O oxygen-bonded LH or LH ligands.Abstracted in part from the Ph.D. Thesis (in preparation) of L. S. Gelfand, Drexel University.