Reticular Chemistry of Homoleptic Complexes of Acetylacetone and Polymorphism of Their Crystals

We studied the crystal structures of acetylacetone and of its 300 homoleptic coordination compounds using reticular chemistry methods. Topological representations of the crystal structures as coordination compounds and as packings of primary and secondary building units (SBUs) were examined, allowing us to propose new criteria for classifying and unambiguously identifying their polymorphic modifications. We also established a number of structural patterns in the crystals of acetylacetone and metal acetylacetonates. Specifically, analysis of the hierarchical assembly revealed that a characteristic feature of metal(III) complexes is the presence of a network with hex topology, and each polymorph corresponds to at least one assembly level with a specific topology, the presence of which distinguishes it from other polymorphs.