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,1,10-phenanthroline ('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)](IMeOH)-Me-., 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)(3)K(mu-OH2)(2)K(phen)(3)](ClO4)(2)(.)4phen(.)4H(2)O, the unusual stereochemistry about the metal atom presumably strongly influenced by packing effects as is the lattice array itself.