We describe an unexpected, cyclic supramolecular complex that results from self-assembly of the nonsteroidal anti-inflammatory drug, diclofenac and 4,4′-azopyridine. The cycles self-assemble into 1D columns occupied by solvent, which can be removed at elevated temperatures (>100 °C) while retaining crystallinity. The complex exhibits solvent exchange ability that occurs through crystal-to-crystal transformations. Finally, the complex can be synthesized using mechanochemistry. Materials exhibiting the structural framework and robustness described here could be applied to removal of hazardous materials or undesirable solvents.