Nucleation of crystals from solution is a universal phenomenon that significantly impacts thedevelopment of advanced functional materials. In this context, metal organic frameworks (MOFs) whichencompass a plethora of metal and multidentate organic ligand architectures offer potential applications inareas such as gas storage, gas separation and catalysis. The experimental and theoretical proceduresemployed, however, lack insights into the chemistry of molecular aggregation which is key to formulatesynthetic protocols towards obtaining solids with desired structural features. Monitoring crystallization on areal timescale, especially at supersaturation involving a relatively small number of molecules, calls foradvanced imaging and spectroscopic techniques supported by logical theoretical models. In this perspective,we have examined the crystal structures of zinc terephthalates grown from solution reported in the CambridgeStructural Database with an objective to rationalize the aggregation of molecular species occurring in thesolution transforming into a crystal with a defined stoichiometry and dimensionality of zinc terephthalatecoordination interaction. The structural chemistry described here addresses the influence of solvent, particularly water in the formation of MOF-5 and other related solids.

A neutral 1:1 zinc terephthalate complex drives the nucleation and growth of all crystals known in the structural landscape of zinc salt-terephthalic acid-solvent.