Metal organic frameworks featuring ligands with open chelating groups are versatile platforms for the preparation of a diverse set of heterogeneous catalysts through postsynthetic metalation. The crystalline nature of these materials allows them to be characterized via X-ray diffraction, which provides valuable insight into the structure of the metal sites that facilitate catalysis. A highly porous and thermally robust zirconium-based metal organic framework, Zr6O4(OH)(4)(bpydc)(6)(bpydc(2-) = 2,2'-bipyridne-5,5'-dicarboxylate), bears open bipyridine sites that readily react with a variety of solution- and gas-phase metal sources to form the corresponding metalated frameworks. Remarkably, Zr6O4(OH)(4)(bpydc)(6) undergoes a single-crystal-to-single-crystal transformation upon metalation that involves a change in space group from Fm (3) over barm to Pa (3) over bar. This structural transformation leads to an ordering of the metalated linkers within the framework, allowing structural characterization of the resulting metal complexes. Furthermore, Zr6O4(OH)(4)(bpydc)(6) yields an active heterogeneous catalyst for arene C-H borylation when metalated with [Ir(COD)(2)]BF4 (COD = 1,5-cyclooctadiene). These results highlight the unique potential of metal-organic frameworks as a class of heterogeneous catalysts that allow unparalleled structural characterization and control over their active sites.