Solvent effects on the dimensionality of oxamato-bridged manganese(II) compounds

Abstract

<p>Two new oxamate-containing manganese(II) complexes, [{Mn(H₂edpba)(H₂O)₂}₂]_n (<b>1</b>) and [Mn(H₂edpba)(dmso)₂]∙dmso∙CH₃COCH₃∙H₂O (<b>2</b>) (H₄edpba = <i>N,N′</i>-ethylenediphenylenebis(oxamic acid) and dmso = dimethylsulfoxide), have been synthesized and the structures of <b>1</b> and <b>2</b> were characterized by single crystal X-ray diffraction. The structure of <b>1</b> consists of neutral honeycomb networks in which each manganese(II) is six-coordinate by one H₂edpba²⁻ ligand and two carboxylate–oxygens from two other H₂edpba²⁻ ligands building the equatorial plane. Each manganese is connected to its nearest neighbor through two carboxylate(monoprotonated oxamate) bridges in an <i>anti</i>-<i>syn</i> conformation. A dmso solution of single crystals of <b>1</b> was placed under acetone atmosphere affording <b>2</b>, whereas putting <b>2</b> in equimolar water:ethanol mixture results in <b>1</b>. The molecular structure of <b>2</b> is made up of mononuclear manganese(II) units which are interlinked by weak C–H⋯π and edge-to-face π-stacking interactions leading to supramolecular chains along the crystallographic <i>b</i> axis. Magnetic measurements reveal the occurrence of an antiferromagnetic coupling between two manganese(II) ions through <i>anti-syn</i> carboxylate bridges for <b>1</b> [<i>J</i> = −1.18 cm⁻¹, the Hamiltonian being defined as <b><i>H</i> </b>= −<i>J</i> <b><i>S</i></b>₁^.<b><i>S</i></b>₂] and very weak intrachain ferromagnetic interactions in <b>2</b> [<i>J</i> = + 0.046 cm⁻¹, <b><i>H</i></b> = −<i>J</i> ∑_i<b><i>S</i></b>_i^.<b><i>S</i></b>_i + 1].</p