New Potassium Bismuth Thiophosphates Including the Modulated K1.5Bi2.5(PS4)3

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• 作者：Matthew A. Gave ; David P. Weliky ; Mercouri G. Kanatzidis
• 刊名：Inorganic Chemistry
• 出版年：2007
• 出版时间：December 24, 2007
• 年：2007
• 卷：46
• 期：26
• 页码：11063 - 11074
• 全文大小：406K
• 年卷期：v.46,no.26(December 24, 2007)
• ISSN：1520-510X

文摘

The compounds K₃Bi₃(PS₄)₄ (I), K_1.5Bi_2.5(PS₄)₃ (II), and K₉Bi(PS₄)₄ (III) were synthesized, and their properties aredescribed. Red needles of I crystallize in the tetragonal spacegroup P4/ncc with a = 21.0116(8) Å and c =13.3454(10) Å and have a three-dimensional Bi/P/S framework structure with large channels occupied by K⁺ ions.Deep-red plates of II crystallize in the monoclinic super spacegroup P2/c(¹/₂)00 with a = 21.8034(12) Å, b =8.8064(7) Å, c = 10.0333(6) Å, and = 90.004(5). This compound has an incommensurately modulatedsuperstructure with the modulation vector q = 0.25a* + 0.5b* + 0.16c*. Bright-red irregularly shaped blocks of IIIcrystallize in the orthorhombic space group P2₁2₁2 with a = 18.306(4) Å, b = 8.926(2) Å, and c = 9.710(2) Å andhave a discrete molecular salt structure with mononuclear [Bi(PS₄)₄]^9- complexes. The structures reveal that asthe relative amount of K₃PS₄ increases, there is a marked decrease in dimensionality of the framework. It was alsopossible to form a glass with the same stoichiometry as that of compound I. When annealed at 320 C, the glasscrystallized into compound II. The ³¹P solid-state NMR spectra are reported, and they are consistent with thecrystallographic results.