Two six-coordinated manganese(II) complexes [Mn(pydien)Cl](ClO4) center dot C2H5OH (1), [Mn(pydien)NCS](ClO4) (2) and two seven-coordinated manganese(II) complexes [Mn(pydado)Cl](ClO4) (3), [Mn(pydado)NCS](ClO4) (4) have been obtained using linear penta and hexadentate ligands pydien and pydado (pydien: 1,7-bis(2-pyridylmethyl)-1,4,7-triazaheptane and pydado: 1,10-bis(pyridylmethyl)- 1, 10-diaza-4,7-dioxadecane). The crystal structures for all compounds have been determined. 1 and 3 crystallize in the triclinic space group P (1) over bar, 2 crystallizes in the orthorhombic space group Pbca, whereas 4 crystallizes in the monoclinic space group P2(1)/c. The bound anion (chloro or isothiocyanato) in complexes 1 and 2 has no influence on the geometry of six-coordinate manganese(II) complexes, whereas the geometry and the wrapping of the hexadentate ligand (pydado) around Mn2+ cation depend on the nature of the bound anion. The complex 3 has a capped octahedron geometry with the two pyridyl groups in trans position, while the geometry of complex 4 can be described as pentagonal bipyramid with one pyridyl group and a thiocyanate anion in the axial positions. (c) 2005 Elsevier B.V. All rights reserved.