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The title compounds, [Cu(C5H7O2)2(C5H6N2)], (I), and [Cu(C5H7O2)2(C4H5N3)], (II), were prepared by the reaction of bis­(pentane-2,4-dionato-κ2O,O′)copper(II) with pyridin-2-am­ine and pyrimidin-2-amine, respectively. From a chemical point of view, it is inter­esting that no Schiff base formation was observed. The compounds are isostructural, with both having a square-pyramidal coordination of the CuII atom and intra­molecular N—H...O hydrogen bonding. The additional N atom of the pyrimidin-2-amine ligand is not involved in hydrogen bonding or in metal coordination. In the crystal structure, chelate rings are involved in π–π inter­actions and mol­ecules of (I) are linked together via N—H...O hydrogen bonds.
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