Sr{sub 3}Bi{sub 2}(SeO{sub 3}){sub 6}·H{sub 2}O: A novel anionic layer consisting of second-order Jahn–Teller (SOJT) distortive cations

• Published in: Journal of solid state chemistry Vol. 221
• Main Authors: Ahn, Hyun Sun, Lee, Eun Pyo, Chang, Hong-Young, Lee, Dong Woo, Ok, Kang Min
• Format: Journal Article
• Language: English
• Published: United States 15.01.2015
• Subjects: BISMUTH; BISMUTH IONS; BISMUTH OXIDES; CATIONS; CRYSTAL STRUCTURE; DIPOLE MOMENTS; ELECTRONIC STRUCTURE; HYDRATES; HYDROTHERMAL SYNTHESIS; INFRARED SPECTRA; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MONOCRYSTALS; SELENITES; SELENIUM IONS; SELENIUM OXIDES; STRONTIUM CARBONATES; SUBLIMATION; WATER; X-RAY DIFFRACTION
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/J.JSSC.2014.09.018

A new layered bismuth selenite hydrate material, Sr{sub 3}Bi{sub 2}(SeO{sub 3}){sub 6}·H{sub 2}O has been synthesized through a hydrothermal reaction using SrCO{sub 3}, Bi{sub 2}O{sub 3}, SeO{sub 2}, and water as reagents. The crystal structure of the reported material has been determined by single crystal X-ray diffraction analysis. The anionic layered framework of Sr{sub 3}Bi{sub 2}(SeO{sub 3}){sub 6}·H{sub 2}O consists of polyhedra of second-order Jahn–Teller (SOJT) distortive cations, Bi{sup 3+} and Se{sup 4+}. Attributable to the variable and asymmetric coordination geometry of the constituent cations, a rich structural chemistry including uni-dimensional bands and linkers is observed in the layer. The material is thermally stable up to about 390 °C and starts decomposing due to the sublimation of SeO{sub 2} above the temperature. The UV–vis diffuse reflectance spectrum suggests a band gap of 3.3 eV. Elemental analysis, infrared spectrum, local dipole moment calculations, and electronic structure calculations are also reported. - Graphical abstract: Ball-and-stick and polyhedral representation of Sr{sub 3}Bi{sub 2}(SeO{sub 3}){sub 6}·H{sub 2}O in the ab-plane. The stereoactive lone pairs are visualized around the Bi{sup 3+} and Se{sup 4+} as lobelike isosurfaces through ELF calculations with η=0.9. - Highlights: • A novel layered bismuth selenite, Sr{sub 3}Bi{sub 2}(SeO{sub 3}){sub 6}·H{sub 2}O has been hydrothermally synthesized. • The layer is only composed of second-order Jahn–Teller distortive cations in asymmetric environments. • The stereoactive lone pairs are visualized as lobelike isosurfaces through ELF calculations.