Hydrogen-bonded 3-D network structures of lanthanide aquo ions and 4,4′-bipyridine with carbaborane anions

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)(2.5)Cl-3-6.5(H2O) and [Yb(H2O)(8)](4)(bpy)(9.5)Cl-12-24.5(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(C2B9H)(2)](8)-EtOH-9(H2O), and [Ln(H2O)(6)(bpy)(bpyH(0.5))](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.