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Updated: Aug 1, 2026

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
Synthesis, structure, and characterization of two new layered mixed-metal phosphates, BaTeMO4(PO4) (M = Nb5+ or Ta5+
Kang Min Ok1, Joseph Orzechowski, P Shiv Halasyamani
1Department of Chemistry and Center for Materials Chemistry, 136 Fleming Building, University of Houston, Houston, Texas 77204-5003, USA.
Abstract:
Two new isostructural mixed-metal phosphates, BaTeMO(4)(PO(4)) (M = Nb(5+) or Ta(5+)), have been synthesized as bulk phase powders and single crystals by standard solid-state techniques using BaCO(3), TeO(2), Nb(2)O(5) (or Ta(2)O(5)), and NH(4)H(2)PO(4) as reagents. The materials have novel layered crystal structures consisting of [M(5+)O(6/2)](-) corner-sharing octahedral chains that are connected to [Te(4+)O(4/2)](0) polyhedra and [P(5+)O(2/1)O(2/2)](-) tetrahedra. The Ba(2+) cations reside between the layers and maintain charge balance. The Te(4+) cations are in asymmetric coordination environments attributable to their lone pairs. The Nb(5+) distorts along the local C(4) direction of its octahedron resulting in a "short-long-short-long" Nb-O-Nb bond motif. The Nb(5+) cation displaces away from the oxide ligands that are bonded to Te(4+) or P(5+) cations, attributable to the structural rigidity of the TeO(4) and PO(4) polyhedra. Thus, the TeO(4) and PO(4) polyhedra support and reinforce the intraoctahedral distortion observed within the NbO(6) octahedra. Infrared and Raman spectroscopy, thermogravimetric analysis, and ion-exchange experiments are also presented. Crystal data: BaTeNbO(4)(PO(4)), orthorhombic, space group Pbca (No. 61), with a = 6.7351(9) A, b = 7.5540(10) A, c = 27.455(4) A, V = 1396.8(3) A(3), and Z = 8; BaTeTaO(4)(PO(4)), orthorhombic, space group Pbca (No. 61), with a = 6.734(2) A, b = 7.565(3) A, c = 27.435(9) A, V = 1372.6(8) A(3), and Z = 8.
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