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Synthesis, crystal structure, and supramolecular interactions in a bis(tetrachlorocatecholate) chelated manganese(III) complex

A mononuclear manganese(III) complex [DABH2][Mn2(Cl4Cat)2(H2O)2]·4DMF (1) (DAB = 1,4-diaminobutane, Cl4CatH2 = tetrachlorocatechol) is synthesized by a one-pot reaction involving manganese(II) chloride tetrahydrate and tetrachlorocatechol in a 1:2 molar ratio in the presence of 1,4-diaminobutane in a DMF-water mixture under aerobic conditions, and is structurally characterized. X-ray crystallography reveals that the complex anion is constructed with two tetrachlorocatecholate ligands coordinated to the manganese(III) center in equatorial positions, and two axial positions are occupied by two water molecules. The crystal packing of 1 is stabilized by complex networks of hydrogen bonding interactions in which oxygen atoms of coordinated tetrachlorocatecholate ligands and lattice DMF molecules serve as hydrogen bond acceptors, while the axially coordinated water molecules together with doubly protonated 1,4-diaminobutane act as hydrogen bond donors. The solid state packing of 1 is further stabilized by Cl⋯Cl halogen bonding interactions within tetracholorocatecholate units and the C—H⋯π and π⋯π interactions involving DMF solvates and aromatic rings of the tetracholorocatecholate ligands. The complex is further characterized by IR spectroscopy and cyclic voltammetry, and the results are analyzed.