Syntheses, Crystal Structures, Weak Interactions, and Magnetic Properties of Two Tetrachloromanganate(II) Salts With Substituted Benzyl Triphenylphosphonium

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Two new tetrachloromanganate(II) salts, [BzTPP]2[MnCl4] (1) and [4NO2BzTPP]2[MnCl4] (2) ([BzTPP]+ = 1-benzyl- triphenylphosphonium; [4NO2BzTPP]+ = 1-(4′-nitrobenzyl) triphenylphosphonium), have been prepared and characterized. Compound 1 crystallizes in the triclinic space group P-1, while 2 is monoclinic P21/c. Both 1 and 2 comprise one [MnCl4]2− anion and two cations, and the [MnCl4]2− anion exhibits distorted tetrahedral coordination geometry. The cations of 1 form a dimer through C-H···π hydrogen bonds and π···π stacking interactions. The C-H···Cl and C-H···O hydrogen bonds result in a complicated hydrogen-bonded network. Magnetic susceptibility measurements in the temperature range 2–300 K show that both 1 and 2 exhibit very weak antiferromagnetic coupling behavior.