Six reaction products of ZnII and NiII with pyridine-2,6-di-carb-oxy-lic acid (H2Lig1), 4-chloro-pyridine-2,6-di-carb-oxy-lic acid (H2Lig2) and 4-hy-droxy-pyridine-2,6-di-carb-oxy-lic acid (H2Lig3) are used to pinpoint the structural consequences of crystal field stabilization by an incomplete d shell. The pseudo-octa-hedral ZnII coordination sphere in bis-(6-carb-oxy-picolinato)zinc(II) trihydrate, [Zn(C7H4NO4)2]·3H2O or [Zn(HLig1)2]·3H2O, (1), is significantly less regular than that about NiII in the isostructural compound bis-(6-carb-oxy-picolinato)nickel(II) trihydrate, [Ni(C7H4NO4)2]·3H2O or [Ni(HLig1)2]·3H2O, (2). The ZnII complexes poly[(4-chloro-pyridine-2,6-di-carboxyl-ato)zinc(II)], [Zn(C7H2ClNO4)] n or [Zn(Lig2)] n , (3), and poly[[(4-hy-droxy-pyridine-2,6-di-carboxyl-ato)zinc(II)] monohydrate], {[Zn(C7H3NO5)]·H2O} n or {[Zn(Lig3)]·H2O} n , (4), represent two-dimensional coordination polymers with chelating and bridging pyridine-2,6-di-carboxyl-ate ligands in which the coordination polyhedra about the central cations cannot be associated with any regular shape; their coordination environments range between trigonal-bipyramidal and square-pyramidal geometries. In contrast, the corresponding adducts of the diprotonated ligands to NiII, namely tri-aqua-(4-chloro-pyridine-2,6-di-carboxyl-ato)nickel(II), [Ni(C7H2ClNO4)(H2O)3] or [NiLig2(OH2)3)], (5), and tri-aqua-(4-hy-droxy-pyridine-2,6-di-carboxyl-ato)nickel(II) 1.7-hydrate, [Ni(C7H3NO5)(H2O)3]·1.7H2O or [NiLig3(OH2)3)]·1.7H2O, (6), feature rather regular octa-hedral coordination spheres about the transition-metal cations, thus precluding the formation of analogous extended structures.
Keywords: NiII complexes; ZnII complexes; coordination polymers; crystal field stabilization; crystal structure; polydentate ligands; pyridine dicarboxylic acids.