The reaction of the asymmetric 4-(aminomethyl)pyridine (4-amp) ligand with silver(l) salts of trifluoromethanesulfonate (triflate, OTf-), trifluoroacetate (tfa(-)), or tetrafluoroborate (BF4-) have produced a variety of one- and two-dimensional structural motifs depending upon the ratio in which the components are mixed. When the proportion of ligand to metal is 1:1, linear coordination polymers are formed with silver(1) OTf- (1) and tfa- (2). Altering the ratio to 2:1, a linear polymer of corner-shared boxes (3) is formed with tfa-, a linear box-in-box "chain link" polymer (4) is formed with OTf-, and a two-dimensional sheet (5) is constructed with BF4-. Addition of 5,5'-dimethyl-2,2'-bipyridine to a solution of 4-ampAgBF(4) disrupts the polymerization of the previous structure and results in the construction of the infinite metal-metal bound strings of 6a regardless of ratio of amp to silver present. H-bonding, pi-stacking, and closed-shell Ag-Ag interactions are all involved in the overall conformations of the final structures.