Synthesis and Characterization of Open-Framework Niobium Silicates: Rb2(Nb2O4)(Si2O6)·H2O and the Dehydrated Phase Rb2(Nb2O4)(Si2O6)

Abstract

A new niobium(V) silicate, Rb(2)(Nb(2)O(4))(Si(2)O(6)).H(2)O, has been synthesized by a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and solid-state NMR spectroscopy. It crystallizes in the tetragonal space group P4(3)22 (No. 95) with a = 7.3431(2) A, c = 38.911(3) A, and Z = 8. Its structure contains tetrameric units of the composition Nb(4)O(18), which share corners to form a layer of niobium oxide. The Nb-O layer is a slice of the pyrochlore structure. Neighboring Nb-O layers are linked by vierer single-ring silicates generating eight-ring and six-ring channels running parallel to <100> directions, in which the Rb(+) cations and water molecules reside. The tantalum analogue was prepared and characterized by powder X-ray diffraction. Upon heating to 500 degrees C, Rb(2)(Nb(2)O(4))(Si(2)O(6)).H(2)O loses lattice water molecules, while the framework structure is retained to give the anhydrous compound Rb(2)(Nb(2)O(4))(Si(2)O(6)), whose structure was also characterized by single-crystal X-ray diffraction. The dehydrated sample absorbs water reversibly, as indicated by powder X-ray diffraction. Rb(2)(Nb(2)O(4))(Si(2)O(6)) crystallizes in the tetragonal space group I4(1) (No. 80) with a = 10.2395(6) A, c = 38.832(3) A, and Z = 16.