A new zwitterionic bidentate ligand was synthesized incorporating a 4,4′-bipyridine core with a carboxylate group as a single building block, specifically designed for the rational construction of supramolecular structures (metal−organic frameworks) that are capable of encapsulating and aligning water aggregates leading to the formation of extended polymeric networks. In particular, both the terminal N′ end and a carboxylate oxygen of the monosubstituted 4,4′-bipyridine was found to readily coordinate in a straightforward manner with different transition metal halides in water, affording heterocyclic complexes featuring various structural motifs. However, critical to the stability and shape of the incorporated water structures is the presence of strong hydrogen bonding resulting from the directional influence exerted by an unbound oxygen center of the metal-bonded carboxylate groups. A search of the Cambridge Structural Database reveals that only a small number of complexes that feature a free carboxylate...