2,5-Pyridinedicarboxylic acid has been reacted with three different diorganotin(IV) oxides (R = Me, nBu, Ph) to study the molecular and supramolecular structures of the resulting diorganotin(IV) 2,5-pyridinedicarboxylates. It has been found that coordinating solvent molecules can change the supramolecular structure completely. The molecular structures found are either polymeric (zigzag) or cyclotrimeric; the supramolecular arrangements include (i) systems having only loosely bound discrete molecules (van der Waals contacts), (ii) systems having a 2D or 3D hydrogen-bonded structure, and (iii) systems having a 3D polymeric coordination structure. Channels or cavities are formed in several cases. For a particular case, evidence has been provided that molecular aggregation to capsules through hydrogen bonding interactions is possible in solution.