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

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,N′-aromatic bases L = 2,2′-bipyridine (‘bpy’), 1,10-phenanthroline (‘phen’) and 2,9-dimethyl,1,10-phenanthroline (‘dmp’) of 1:n (n = 1,2,3 and some non-integral) stoichiometries and anhydrous conditions. X are predominantly weakly basic oxyanions ClO4, NO3, O3SCF3 (= ‘triflate’, ‘tfs’) and (pseudo-) halides for M = Li, Na, K, Rb (not, as yet, Cs). The present paper describes adducts of 1:1 (or near 1:1) MX : L stoichiometry. The majority of arrays described are single-stranded one-dimensional linear polymers, LM units being bridged by oxyanions: single-stranded LiNO3 : dmp (1:1)(∞|∞), (the Na analogue is isomorphous, but with a different anion bonding mode), and double-stranded NaClO4 : bpy (1:1)(∞|∞) and Mtfs : dmp (1:1)(∞|∞) (M = Na, K, Rb); an interesting single-stranded ‘hydrolysis’ product, with supernumerary interleaving phen moieties ‘solvating’ as well as methanol, is defined as NaI : phen : H2O : MeOH (1:1(+1):2:1), [(phen)Na(μ-OH2)2](∞|∞)I·phen·MeOH. The complex LiCl : dmp (2:2) is a dimer, [(dmp)Li(μ-Cl)2Li(dmp)], while the LiBr : dmp system is defined in terms of two ionic adductsLiBr : dmp : MeOH (1:1:2.5) ≡ [(dmp)Li(HOMe)2]Br· 0.5MeOH and LiBr : dmp : MeOH : H2O (1:1(+1):1:1), ‘solvated’ with dmp, MeOH and H2O, as [(dmp)Li(HOMe)(OH2)]Br·dmp; also of this family is LiNCS : dmp : MeOH (1:1:1) ≡ [(dmp)Li(NCS)(HOMe)]. The adduct KPF6 : dmp (1:1)(∞|∞) is a novel double-stranded one-dimensional polymer in which (dmp)K units are bridged by PF6 counterions. Ktfs : dmp : MeOH (2:2:1)2 is a complex tetramer in which all species are coordinated, but its rubidium counterpart is an infinite polymer. Of more complex stoichiometry are the adducts KI : dmp : MeOH (6:8:3) ≡ [K6I4(dmp)8]I2·3MeOH containing a ‘polyiodide’ cation, and Ktfs : dmp (4:3), a double-stranded, one-dimensional polymer.