The aqueous solution and solid state properties of (4-hydroxypyridine-2,6-dicarboxylato)dioxovanadate(V) (also referred to as (4-hydroxydipicolinato)dioxovanadate(V) or (chelidamato)dioxovanadate(V) and abbreviated [VO2-(dipic-OH)](-)) were investigated. By using H-1, C-13, O-17, and V-51 NMR 1D and 2D spectroscopy, the species present in solution, together with pK(a) values, equilibrium constants, and labilities, were characterized. The complex is most stable at acidic pH down to pH I where it is protonated. The stability of this complex is higher than that of the parent dipicolinatodioxovanadate(V) complex. The dipic-OH ligand is coordinated in a tridentate manner throughout the pH range studied, and the vanadium(V) atom is five-coordinate. Solid state structures of (NMe4)[VO2(dipicOH)].H2O (monoclinic, P2(1)/n) and Na[VO2(dipic-OH)]-2H(2)O (triclinic, P (1) over bar) were determined. The discrete complex anions in (NMe4)[VO2(dipic-OH)]-H2O are connected by hydrogen bonding between the hydroxyl group, a water molecule, and a carboxylate oxygen atom. Changing the counterion from NMe4+ to sodium ion in Na[VO2(dipicOH)]-2H(2)O leads to the formation of a polymeric structure. Dynamic processes in solution were explored by using H-1 and (13) C EXSY NMR spectroscopy; exchange between complex and free ligand below pH 4 was observed. The differences between the dipicolinatodioxovanadate(V) parent complex and the [VO2(dipic-OH)]- complex in the solid state and in solution demonstrate the subtle consequences of the one substitutional difference between the two ligands. The insulin-mimetic properties of this compound are likely to be of mechanistic interest in developing an understanding of the mode of action of the few known insulin-mimetic vanadium(V) complexes.