Special attention has been devoted to the coordination chemisty of ligands such as oxolate and 2,2’-bipyrimidine (hereafter noted ox and bpm, respectively) in the context magnetostructural studies.(2,3) This interest is mainly based on two features : (i) the design of both mono- and polynuclear species becomes easier when chelating and bischelating ligands such as ox and bpm are used; (ii) these bridging ligands have a remarkable ability to mediate strong exchange interactions between metal ions separated by more than 5 Angstrom. Oxalatobridged homo- and heteropolynuclear complexes are examples of species wherein tunable exchange can be accomplished by varying the nature of the terminal ligands(2a,b) and the nature of the atoms of the bridge, (2d) high-spin molecules because of strict orthogonality between nearest neighbor magnetic cen dimensional magnetic chains, (2c) and more recently molecular-based ferromagnets.(2g) As far as bpm-containing metal complexes are concerned, the most interesting results are the easy preparation of dimers with a large variety of transition metal ions, (3a,b) the controlled polymerization from the mononuclear complex to the nD network (n = 1-3), (3c-f) and the rational design of 1D structures with alternating ferro- and antiferromagnetic interactions.(3g) In a recent communication, (4) we showed that the reaction of copper(II) with the mononuclear mixed-ligand complex [Cu(bpm)(ox)(H2O)(2)] .5H(2)O yielded the novel 2D compound of formula [Cu-2(bpm)(ox)(2)].5H(2)O where bpm and ox act o bridging ligands. In order to investigate the possibility of extending the preparation of this kind of layered material to that of complexes with other metal ions and establishing the basis of a new strategy aimed at designing magnetic layered compounds, we have undertaken a systematic study of complex formation with first-row transition metal ions and bpm and ox as ligands. In this contribution we present the isolation and the structural and magnetic characterization of the dinuclear complex [Mn-2(bpm)(H2O)(4)(SO4)(2)] (1) and the novel sheetlike polymeric compound [Mn-2(bpm)(ox)(2)].6H(2)O (2).