Syntheses and Characterization of Thiolate-Bridged Manganese(II) Complexes with NNS-Tridentate Thiolic Ligands

Manganese(II) complexes with 2-[(2-aminoethyl)amino]ethanethiol (HLa), 2-[(3-aminopropyl)amino]ethanethiol (HLb), 2-[(2-pyridylmethyl)amino]ethanethiol (HLc), and 2-[[2-(2-pyridyl)ethyl]amino]ethanethiol (HLd)–[Mn(La)Cl]n (1), [Mn{Mn(Lb)2}2]Cl2·2CH3OH (2), [Mn(Lc)Cl]n (3), and [Mn(Ld)Cl(CH3OH)]n (4) have been synthesized and characterized by elemental analyses, infrared and electronic spectroscopies, and magnetic susceptibilities (80—300 K). The crystal structures of all these complexes were determined by the single-crystal X-ray diffraction method. Complexes 1 and 3 have a thiolate-bridged polymeric chain structure in which each manganese atom is five-coodinated in a trigonal bipyramid. Complex 2 is a thiolate-bridged trinuclear manganese(II) complex displaying a linear arrangement of the three manganese atoms with the two Mn–Mn interactions being equidistant [3.420(1) Å]. Complex 4 is a thiolate-bridged polymeric infinite chain showing a distortion in the octahedral geometry around each manganese atom. The magnetic properties are discussed in relation to the crystal structures.