Mangan(II)-Komplexe mit dem vierzähnigen Stickstoffliganden C12H22N6(L): Synthese von [MnX2L] (X = Cl, Br, I, NCS), Kristallstrukturen von [MnCl2L] und [MnBr2L] / Manganese(II) Complexes with the Tetradentate Nitrogen Ligand C12H22N6(L): Synthesis of [MnX2L] (Χ = Cl, Br, I, NCS), Crystal Structures of [MnCl2L] and [MnBr2L

Abstract

[MnCl2(C12H22N6)] (1) and [MnBr2(C12H22N6)] (2) are obtained from the reaction of MnX2 (X = Cl, Br) with C12H22N6 in methanolic solution. In chloroform MnI2, OPPh3, and C12H22N6 react to give [MnI2(C12H22N6)] (3). With small variations of the reaction conditions [MnI2(C12H22N6)] · xCHCl3 (4) may be crystallized. The reaction of [Mn(NCS)2(OPPh3)4] with C12H22N6 in CHCl3 solution gives [Mn(NCS)2(C12H22N6)] · xCHCl3 (5). The structures of 1 and 2 were determined from single crystal X-ray diffraction data. The isotypic compounds crystallize in the orthorhombic space group Pbcn with Z = 4; 1: a = 1592.4(1), b = 785.0(1), c = 1270.7(1) pm; 2: a = 1590.0(1), b = 802.6(1), c = 1316.6(1) pm. C12H22N6 acts as a tetradentate ligand. The isolated complexes exhibit a twofold symmetry. Manganese(II) is in a six-coordinate environment, which can be described better as a distorted tetrahedron with two additional Mn-N bonds rather than as a distorted octahedron. The Mn-N bond lengths are 229.9(1) and 248.7(1) pm for 1 and 228.2(3) and 248.4(3) pm for 2. The Mn-Hal bond lengths are 239.2(1) (1) and 254.2(1) pm (2)