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 MX : 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 (l:2(:n)), isomorphous [Li(dmp)₂]X(·MeOH), are described for X = I, ClO₄ (n = 1), O₃SCF₃ (= 'triflate'. tfs) (n = 0). Adducts MX : phen (:MeOH) (1:2(:n)) 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 × 13 × 24 Å (axes sometimes doubled), variously monoclinic, P2₁/x (β ~ 90°) or orthorhombic Pca2₁ 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)₂M(μ-phen)₂M(OSO₂CF ₃)₂].