Complexes of Group 1 Salts with N,N′-Aromatic Bidentate Ligands, of 1 : 3 Salt : Base Ratio

Following reports of the synthesis and single crystal X-ray structural characterization of adducts of simple group 1 metal salts with the N,N′-aromatic bidentate ligands 2,2′-bipyridine (‘bpy’), 1,10-phenanthroline (‘phen’) and 2,9-dimethyl,1,10phenanthroline (‘dmp’) (= L), of 1:1 and 1:2 MX : L stoichiometry in the preceding papers, adducts of 1:3 stoichiometry are described in the present, for M = Na, of the form [NaL3]X(·S) representative of all L = bpy, phen, dmp. [Na(bpy)3]I is of interest, the cation stereochemistry being essentially trigonal prismatic; in [Na(phen)3](F3CSO3)·2MeOH, it is a more usual twisted octahedron, while, in [Na(dmp)3]I·MeOH, in consequence, presumably, of constraints imposed by the ligand substituents, a novel array of quasi-m symmetry, with out-of-plane coordination of the metal atom, is found for the first structurally defined [M(dmp)3]n± species. A hydrated adduct, KClO4 : phen : H2O (1:5:6) is also described, being of the form [(phen)3K(μ-OH2)2K(phen)3](ClO4)2·4phen·4H2O, the unusual stereochemistry about the metal atom presumably strongly influenced by packing effects as is the lattice array itself.