The title compound, [Co(C(32)H(35)N(3)O(6))(H2O)2](ClO4)(2).H2O, contains a cationic complex with a novel facultative hexadentate sugar-derived ligand coordinated in a tetradentate fashion to give a CoN(2)O(4) coordination. The partial coordination is imposed by the rigid conformation of the sugar. The pyridine group that is not bound to the metal is free to participate in intermolecular hydrogen bonding and pi-pi stacking interactions.