The linear multidentate-type ligand 2,6-di(acetoacetyl) pyridine (H2L) selectively gave di- and octa-nuclear complexes, [M-2(HL)(2)(NO3)(2)(H2O)(2)] (M-2(HL)(2)) and [M-8(L)(6)(mu(3)-O)(2)] (M8L6), with metal ions (M-II = Mn, Co, Zn) by adjusting pH. M-2(HL)(2) formed an enolate-bridged dinuclear structure, in which metal ions were in hepta-coordinated pentagonal-bipyramid geometry. The structure of M8L6 consisted of two tetranuclear components including mononuclear [MnL3](4-) and trinuclear [Mn(mu(3)-O)](4+) units, and the tetrads were interdigitated by enolate-bridges. In methanolic solution, M-2(HL)(2) was irreversibly transformed to M8L6 with liberation extra L2- by the addition of base.