Synthesis, characterization, solution study and crystal structure of complexes of Cr(III), Co(II), Ni(II) and Cu(II) with chelidamic acid and 2,9-dimethyl-1,10-phenanthroline

The title compounds, (dmpH)[Cr(chelH) 2 ]·3H 2 O, 1 , (dmpH)[Co(chelH 2 )(chelH)]·3H 2 O, 2 , (dmpH)[Ni(chelH 2 )(chelH)]·2H 2 O, 3 and [Cu(chelH)(dmp)]·3H 2 O, 4 (dmp is 2,9-dimethyl-1,10-phenanthroline and chelH 3 is chelidamic acid or 4-hydroxypyridine-2,6-dicarboxylic acid) were obtained by one-pot reaction of 2,9-dimethyl-1,10-phenanthroline and 4-hydroxypyridine-2,6-dicarboxylic acid with corresponding salts in aqueous solution. The compounds were identified by IR, MS, elemental analysis and single crystal X-ray crystallography; also they were studied in the solution phase. The compounds 1 , 2 and 3 are similar in coordination sphere around the metal ions, with some differences between protonation sites of chelidamate ion and the charge of complex, but compound 4 is essentially different. The compounds 1 , 2 and 3 are six coordinated, but 4 is five coordinated. There are various O–H···O, O–H···N and N–H···O hydrogen bonds found in the structures. In a solution study, the protonation constants of dmp and chel, the equilibrium constants of the chel–dmp proton-transfer system and the stoichiometry and stability of complexation of this system with Cr(III), Co(II), Ni(II) and Cu(II) ions in an aqueous solution were investigated by potentiometric pH titration method. The stoichiometry of the most complexes species in solution was found to be very similar to the crystalline cited metal ion complexes.