The present study represents the first systematic examination of the effects on the layered structure of simple silver aryl-monosulfonates as the breadth of the pendant aryl group is increased beyond that where a simple "phosphonate-like" motif is sustainable. Five new silver arenesulfonates are reported. On the basis of comparison with Ag benzenesulfonate, a threshold of similar to6.4 Angstrom is proposed and confirmed as the critical breadth of an aryl group for a simple layered motif to be observed in silver sulfonates. Ag 1,1'-biphenyl-4-sulfonate (1) and Ag 2-naphthalenesulfonate (2) are below this threshold and so form simple layered networks, termed type 1 solids. When the pendant group is broadened to a 1-naphthyl group, the layer incorporates coordinated water to maintain a layered structure giving Ag 1-naphthalenesulfonate hemihydrate (3a). This more diffuse structure is termed a type 2 solid. For anhydrous Ag 1-naphthalenesulfonate (3) and Ag 1-pyrenesulfonate (4), the additional breadth is compensated for by the formation of Ag-pi interactions and the formation of type 3 solids. Interactions between the pendant groups are observed to play a significant role in the packing of the solid. All frameworks are characterized by single crystal and powder X-ray diffraction, IR, DSC-TGA, and elemental analysis. The significance of this adaptable framework is discussed along with implications for design of stacked arene arrays.