Complexes of Group 1 Salts with N,N'-Aromatic Bidentate Ligands, of (Oligo-/Poly-) Nuclear or Ionic 1:2 Salt Base Ratio

In the preceding paper an array of salts of NIX : L(:S) (1:2(:n)) stoichiometry of simple mononuclear form, with coordinated X or S were described, MX = simple group 1 salt, L = 1,10-phenanthroline ('phen') or 2,9-dimethyl,1,10-phenanthroline ('dmp'), crystallized from (methanol) solution and characterized by single crystal X-ray studies. This paper describes a parallel isostoichiometric array in which the metal atoms exist in environments of nitrogen atoms only, of polymeric/ionic form. Adducts LiX : dmp : MeOH (1:2(:n)), isomorphous [Li(dvrP)(2)]X((MeOH)-Me-.), are described for X = I, ClO4 (n=1), O3SCF3 (= 'triflate', tfs) (n = 0). Adducts MX : phen (:MeOH) (1:2(m)) form a wide-ranging array of structures with discrete anions and stacked cations with a variety of metal geometries and L coordination modes, the stacks discrete in monoclinic C2/c (MX = NaPF6, n = 0), interleaving/overlapping in orthorhombic Pnc2 (MX = LiI), expanded to Pnna (MX = LiClO4), and a familial array with a basis ca. 6 x 13 x 24 angstrom (axes sometimes doubled), variously monoclinic, P2(1)/x (beta similar to 90 degrees) or orthorhombic Pca2(1) or Pbcn for MX = LiI, NaBr, NaPF6, NaSCN, KI, KSCN, KPF6, RbI, culminating in a remarkable 'defective cation' adduct of NaPF6 : phen (6:13) stoichiometry. Two isomorphous binuclear adducts, Mtfs : phen (1:2)2, M = K, Rb, are interesting examples of 'terminated stacks' of the form [(phen)(2)M(mu-phen)(2)M(OSO2CF3)(2)].