Synthesis and characterization of cobalt(II)-salicylate complexes derived from N₄-donor ligands: Stabilization of a hexameric water cluster in the lattice host of a cobalt(III)-salicylate complex

The syntheses and structural characterization of four cobalt(II)-salicylate complexes, [(TPA)Co^II(HSA)](ClO₄) (1), [(isoBPMEN)Co ^II(HSA)](BPh₄) (2), [(TPzA)Co^II(HSA)](ClO ₄) (3) and [(6Me₃TPA)Co^II(HSA)](BPh ₄) (4) [TPA = tris(2-pyridylmethyl)amine, isoBPMEN = N ¹,N¹-dimethyl-N²,N²-bis(2- pyridylmethyl)ethane-1,2-diamine, TPzA = tris((3,5-dimethyl-1H-pyrazole-1-yl) methyl)amine and 6Me₃TPA = tris(6-methyl-2-pyridylmethyl)amine] are described. While 2, 3 and 4 are unreactive towards dioxygen, 1 reacts slowly with molecular oxygen to a cobalt(III)-salicylate complex, [(TPA)Co ^III(SA)](ClO₄) (1a). Two different crystalline forms, 1a and 1a·4H₂O were isolated depending upon the condition of oxidation and crystallization. The solid-state structures of cobalt(III)-salicylate unit in both 1a and 1a·4H₂O show a six-coordinate distorted octahedral coordination geometry at the cobalt(III) center ligated by the tetradentate ligand (TPA) where the dianionic salicylate (SA) binds in a bidentate fashion through one carboxylate and one phenolate oxygen. The hydrated form 1a·4H₂O reveals a hexameric water cluster formation in the inorganic lattice host. The complex cation and the perchlorate counterion are involved in stabilizing the (H₂O) ₆ cluster in a rare 'pentamer planar+1' conformation. A one-dimensional water tape consisting of edge-shared water hexamers is observed. The water tape represents a subunit of ice structure.