Hydrogen-Bonded 3-D Network Structures of Lanthanide Aquo Ions and 4,4‘-Bipyridine with Carbaborane Anions

Abstract

A series of three-dimensional (3-D) hydrogen-bonded structures of lanthanide aquo ions and 4,4‘-bipyridine (bpy) or protonated bpyH+ as ligands and hydrogen-bonding tectons have been characterized by single-crystal X-ray crystallography, with both Cl- and [Co(C2B9H11)2]- counteranions. All show related structures with unidirectional rectangular channels filled by additional bpy molecules for the complexes [Yb(H2O)8](bpy)2.5Cl3·6.5(H2O) and [Yb(H2O)8]4(bpy)9.5Cl12·24.5(H2O) or by [Co(C2B9H11)2]- anions for the complexes [Ln(bpy)(H2O)8]2(bpy)10[Co(C2B9H11)2]6·1.5(EtOH)·15(H2O) where Ln = La, Ce, [Sm(H2O)5(bpy)2(EtOH)][Sm(H2O)6(bpyH)(EtOH)](bpyH)(bpy)10[Co(C2B9H11)2]8·EtOH·9(H2O), and [Ln(H2O)6(bpy)(bpyH0.5)]2[Ln(H2O)7(bpy)](bpyH)2(bpy)14[Co(C2B9H11)2]12·n(EtOH)·5(H2O) where Ln = Gd, Tb, and Ho. The smaller (CB11H12)- anion does not template a similar structure; instead the complex [(bpyH)3(bpy)(CB11H12)3] is isolated with a one-dimensional (1-D) hydrogen-bonded ladder structure.