A new uranyl niobate sheet in the cesium uranyl niobate Cs9[(UΟ2)8Ο4(NbO5)(Nb2Ο8)2]

• Published in: Journal of solid state chemistry 2008-04, Vol.181 (4), p.741-750
• Main Authors: SAAD, S, OBBADE, S, YAGOUBI, S, RENARD, C, ABRAHAM, F
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Dielectric, piezoelectric, ferroelectric and antiferroelectric materials; Dielectrics, piezoelectrics, and ferroelectrics and their properties; Exact sciences and technology; Growth from solid phases (including multiphase diffusion and recrystallization); Inorganic compounds; Material chemistry; Materials science; Methods of crystal growth; physics of crystal growth; Niobates, titanates, tantalates, pzt ceramics, etc; Physics; Structure of solids and liquids; crystallography; Structure of specific crystalline solids
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2008.01.015

A new cesium uranyl niobate, Cs9[(UO2)8O4(NbO5)(Nb2O8)2] or Cs9U8Nb5O41 has been synthesized by high-temperature solid-state reaction, using a mixture of U3O8, Cs2CO3 and Nb2O5. Single crystals were obtained by incongruent melting of a starting mixture with metallic ratio=Cs/U/Nb=1/1/1. The crystal structure of the title compound was determined from single crystal X-ray diffraction data, and solved in the monoclinic system with the following crystallographic data: a=16.729(2) Å, b=14.933(2) Å, c=20.155(2) Å β=110.59(1)°, P21/c space group and Z=4. The crystal structure was refined to agreement factors R1=0.049 and wR2=0.089, calculated for 4660 unique observed reflections with I ≥ 2σ(I), collected on a BRUKER AXS diffractometer with MoKα radiation and a CCD detector. In this structure the UO7 uranyl pentagonal bipyramids are connected by sharing edges and corners to form a uranyl layer ∞2[U8O36] corresponding to a new anion-sheet topology, and creating triangular, rectangular and square vacant sites. The two last sites are occupied by Nb2O8 entities and NbO5 square pyramids, respectively, to form infinite uranyl niobate sheets ∞2[(UO2)8O4(NbO5)(Nb2O8)2]9- stacking along the [010] direction. The Nb2O8 entities result from two edge-shared NbO5 square pyramids. The Cs+ cations are localized between layers and ensured the cohesion of the structure.The cesium cation mobility between the uranyl niobate sheets was studied by electrical measurements. The conductivity obeys the Arrhenius law in all the studied temperature domains. The observed low conductivity values with high activation energy may be explained by the strong connection of the Cs+ cations to the infinite uranyl niobate layers and by the high density of these cations in the interlayer space without vacant site.Infrared spectroscopy investigated at room temperature in the frequency range 400–4000 cm−1, showed some characteristic bands of uranyl ion and niobium polyhedra