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(C 2 B 9 H 11 ) 2 ] - counteranions. All show related structures with unidirectional rectangular channels filled by additional bpy molecules for the complexes [Yb(H 2 O) 8 ](bpy) 2.5 Cl 3 ·6.5(H20) and [Yb(H20)8]4(bpy) 9.5 Cl 12 ·24.5(H20) or by [Co(C 2 B 9 H 11 ) 2 ] - anions for the complexes [Ln(bpy)(H20)8]2(bpy) 10 [Co(C 2 B 9 H 11 ) 2 ] 6 ·1.5(EtOH)·15(H20) where Ln = La, Ce, [Sm(H 2 O) 5 (bpy)2(EtOH)]-[Sm(H20)6(bpyH)(EtOH)](bpyH)(bpy) 10 [Co(C 2 B 9 H 11 ) 2 ] 8 ·EtOH·9(H20), and [Ln(H20)6(bpy)(bpyH 0.5 )] 2 [Ln(H20)7(bpy)](bpyH)2-(bpy)i4[Co(C 2 B 9 H 11 ) 2 ] 12 ·n(EtOH)·5(H20) where Ln = Gd, Tb, and Ho. The smaller (CB 11 H 12 )- anion does not template a similar structure; instead the complex [(bpyH)3(bpy)(CB 11 H 12 ) 3 ] is isolated with a one-dimensional (1-D) hydrogen-bonded ladder structure.