Copper-linked hexaniobate lindqvist clusters-variations on a theme

Four new one-dimensional materials and one dimer complex based on the linkage of [Nb6O19] clusters and [CuLx] (L=ethylenediamine (en), NH3, H2O) assemble under ambient conditions. These phases include the following: Rb4[Cu(en)2(H2O)2]3[(Nb6O19H2)2Cu(en)2].24H2O (1), space group P; [Cu(en)2(H2O)2]2[(Nb6O19H2)Cu(en)2].14H2O (2), space group P; Rb2[Cu(NH3)2(H2O)4][Cu(NH3)4(H2O)2]2{[Nb6O19][Cu(NH3)]2}(2).6H2O (3), space group P; {[Nb6O19][Cu(NH3)2(H2O)]2[Cu(H2O)4]2}.3H2O (4), space group P2/n; and {[Nb6O19][Cu(NH3)2(H2O)]2[Cu(H2O)4]2} (5), space group C2/m. All structures have been solved by single-crystal methods, and compounds 1-5 were characterized by thermogravimetric analysis, Fourier transform IR, chemical analysis, and magnetic measurements. It has been demonstrated that the conformation, charge, and geometry of the [Nb6O19]-[CuLx] chains can be modulated by varying the type and amount of the [CuLx]2+ species. The charge balance is provided by mixed Rb+/[CuLx]2+ or [CuLx]2+ cations only for structures 1-3, whereas 4 and 5 are neutral chains with no counterions. There are weak antiferromagnetic Cu2+-Cu2+ interactions in all phases. Compounds 2-5 represent the first examples in which the [Nb6O19] Lindqvist ion forms extended solids rather than dimers or decorated monomers when reacted with transition-metal, cationic complexes.