We designed a series of metal–organic solids using ligands with similar molecular structures that were expected to afford coordination complexes with similar solid-state structures. The metal component is silver(I) p-toluenesulfonate, and the ligands differ in their ability to undergo dynamic molecular motion. Although the ligands are similar in their molecular structure, the metal complexes exhibit different solid-state structures because of differences in π-stacking arrangements and the presence or lack of Ag···Ag interactions. The coordination units (ligand-Ag-ligand) in each complex respond differently to temperature changes, which results in thermal expansion behaviors ranging from negative to zero to positive within the series. Two unique complexes were obtained with the azo-containing ligand, and preparation of each complex in bulk was controlled by synthetic conditions. Two polymorphs were obtained with the olefin-containing ligand, and both complexes undergo dynamic molecular motion, although the supramolecular structures differed dramatically. Overall, we show that simple modifications to the ligand structure can significantly affect solid-state structure, crystal form, and subsequent thermal expansion behavior.