Reactions between the potentially pentadentate (N2O3), trianionic double Schiff-base ligand 2,6-bis[[(2-hydroxyethyl)imino]methyl]-4-methylphenol (H3L) and Cu(CH3CO2)(2) or Cu(ClO4)(2), in the presence of NaN3, give novel coordination polymers with chain {[Cu-2(H2L)(N-3)(3)](2)center dot H2O}(n) (1) or sheet [Cu-2(H2L)(N-3)(3)](n) (2) and [Cu-2(HL) (N-3)](n)(ClO4)(2) (3) structures, respectively. These clusters are comprised of repeating dinuclear units (1) or their dimers (2 and 3). In these compounds, H3L acts as a tridentate (N2O) monoanionic (1), tetradentate (ON2O) monoanionic (2), or pentadentate (O3N2) dianionic (3) ligand. Compound [Cu-2(HL)(N-3)(2)(H2O)]center dot 0.5CH(3)OH (4) formed from the reaction of Cu(CH3CO2)(2) with H3L under reflux, which did not afford crystals suitable for X-ray studies. X-ray structure determinations have revealed that the basic building block in 1-3 comprises two copper centers bridged through one mu-phenolate O atom from H2L- or HL2- and one mu-azido(N1,N1) ion. Compounds 1-3 unveil three different ways in which this Cue basic unit may be organized in the crystalline phase at the supramolecular level through a variety of bridging interactions involving additional azide ligands or alkoxide groups from the side arms of the ligand H3L. Bulk magnetization measurements have sented to demonstrate that the magnetic interactions are completely dominated by the strong antiferromagnetic coupling occurring within the Cue building block, with coupling constants ranging from 330 to 560 cm(-1) (in the H= -JS(1)S(2) convention). These results together have been incorporated with data from the few related copper dimers reported exhibiting the same bridging pattern into a study aimed at extracting possible magnetostructural correlations within this Cue unit. An earlier predicted correlation between J and the angle formed by the phenoxide bridge and the Cue core has been identified for the first time.