Synthetic Cs(VO2)3(TeO3)2 is built up from infinite sheets of distorted octahedral VVO6 groups, sharing vertices. These octahedral layers are “capped” by Te atoms (as parts of pyramidal [TeIVO3]2– groups) on both faces of each V/O sheet, with inter‐layer, 12‐coordinate, Cs+ cations providing charge compensation. Cs(VO2)3(TeO3)2 is isostructural with M(VO2)3(SeO3)2 (M = NH4, K). Crystal data: Cs(VO2)3(TeO3)2, Mr = 732.93, hexagonal, space group P63 (No. 173), a = 7.2351(9) Å, c = 11.584(2) Å, V = 525.1(2) Å3, Z = 2, R(F) = 0.030, wR(F 2) = 0.063.

The present and three subsequent papers describe the syntheses and structural characterization of crystalline adducts, sometimes solvated, obtained from (usually methanolic) solutions of simple group 1 metal salts, MX, with the N,NЈ-aromatic bases L ϭ 2,2Ј

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 ϭ simple group 1 salt, L ϭ 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(dmp) 2 ]X(·MeOH), are described for X ϭ I, ClO 4 (nϭ1), O 3 SCF 3 (ϭ 'triflate', tfs) (n ϭ 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

Syntheses and single crystal X-ray structure characterisations are recorded for some novel series of crystalline complexes formed between salts of univalent anions of the ethane-1,2-diaminium cation, [enH 2 ]X 2 , and 1,10-phenanthroline ('phen'), variously hydrated, thus: [enH 2 ]X 2 ·mphen(·nH 2 O), for m ϭ 2, 4 and 10 (one example), n various. In all cases, the motifs constituting the arrays comprise columns of [enH 2 ] 2ϩ cations, carrying the protonic array but linked in a second dimension by hydrogen-bonding to associated anions and water molecules (where present), expanding the column in some cases to form a sheet, different degrees of hydration compensating for changing anion bulk. In a third dimension the protonic hydrogen complement also links to the nitrogenous component of phen stacks which surround the column. Thus, for the m ϭ 2 array, in a triclinic P1 cell, a, b, c broadly 10-11 (x2), 7 Å , α, β, γ 80, 70°(x2), the cation and phen columns lie parallel to c; in the unsolvated trichloroacetate compound, the cation column is associated with anions to either side, these linking into a sheet with water molecules in the more highly hydrated trifluoroacetate ('tfa') and nitrate (n ϭ 2), and chloride and bromide (n ϭ 4) arrays (the tfa adduct a superlattice doubled in c). In the m ϭ 4

Crystallizations of simple group 1 metal salts MX with N,NЈ-bidentate aromatic ligands 1,10-phenanthroline ('phen') and the hindered 2,9-dimethyl,1,10-phenanthroline ('dmp'), as well as complexes of other forms and stoichiometries described in accompanying papers, have yielded a broad array of simple mononuclear adducts of 1:2(:n) MX : L (:S) stoichiometry from methanol solutions. One of these, NaBr : phen : MeOH (1:2:2) contains a sixcoordinate metal atom, being ionic [(MeOH) 2 Na(phen) 2 ]Br, but the majority contain five-coordinate metal atoms, being either ionic (one example only, [(MeOH)Li(phen) 2 ]Cl·MeOH) or neutral 1829 [XML 2 ] species, the latter for the combinations MX : phen (M ϭ Li, X ϭ I, ClO 4 , tfs (ϵ 'triflate', F 3 CSO 3 ) (a new form), NO 3 ; M ϭ Na, X ϭ Br, I, ClO 4 , NO 3 ) and MX : dmp (M ϭ Na, X ϭ NCS, Br, I, PF 6 , ClO 4 ; M ϭ K, X ϭ I), the (coordinating) polyatomic anions being unidentate, and the coordination geometries distorted trigonal bipyramidal.