The reaction of the asymmetric 3-aminomethylpyridine (3-amp) ligand with silver(I) tetrafluoroborate (AgBF4) produces an array of structural motifs that depend on the ratio of the reactants present and crystallization temperature. With a 1:1 ratio of 3-amp to silver, either a folded macrocycle, 1a, or a linear coordination polymer, 1, is formed, depending upon whether the crystals are grown at -35 or 5 degrees C. A 3:2 ratio forms two-dimensional sheets of 2 regardless of temperature of crystallization. The 2:1 ratio of ligand to metal again sees a temperature dependence with either a one-dimensional, 3a, or two-dimensional, 3, coordination polymer formed upon crystallization at low and high temperatures, respectively. Addition of 2,2'-bipyridine to any of the previous reaction mixtures stops the formation of their respective structures, instead constructing the discrete Ag-Ag-linked 4.