Mononuclear and dinuclear manganese compounds stabilized by supramolecular interactions

New manganese compounds [Mn(HphpzMe)2(H2phpzMe)(HCO2)] (1), [Mn2(phpzMe)2(HphpzMe)2(OCH3)]·2CH3OH (2), Na{[Mn(HphpzPh)(phpzPh)(MeOH)2]2}(HCO2) (3), [Mn(HphpzPh)2(EtOH)2]ClO4·2EtOH (4) and [Mn(HphpzPh)2N3] (5) were synthesized and characterized with various techniques. 1, 4 and 5 are mononuclear manganese(III) compounds, 2 is a mixed-valence dinuclear manganese(III/IV) compound, and 3 is a trinuclear compound containing two manganese(III) ions and a sodium(I) ion. A remarkable feature is the spontaneous formation of the formate ion as a result of the methanol or methoxide oxidation in compounds 1 and 3. Using ethanol precludes the formation of the formate and compound 4 is obtained. The molecular structure of all compounds is stabilized by supramolecular interactions, including strong hydrogen bonding and π-π interactions.