Crystal structures reveal that [PY(CO2)4]4− coordinates in a pentadentate fashion to allow for a nearly ideal octahedral coordination geometry upon binding an exogenous water ligand. Additionally, depending on the nature of the chargebalancing countercation (Li+, Na +, or K +), the [(PY(CO2)4)M(H2O)]2− complexes can assemble in the solid state to form onedimensional channels filled with water molecules. Aqueous electrochemistry performed on [(PY(CO2)4)M(H2O)]2− suggested accessible trivalent oxidation states for the Fe, Co, and Ni complexes, and the trivalent Co3+ species [(PY(CO2)4)Co(OH)]2− could be isolated via chemical oxidation. The successful synthesis of the [PY(CO2)4]4− ligand and its transition metal complexes illustrates the still-untapped versatility within the tetrapodal ligand family, which may yet hold promise for the isolation of more reactive and higher-valent metal complexes.