New potassium bismuth thiophosphates including the modulated K 1.5Bi2.5(PS4)3

Matthew A. Gave, David P. Weliky, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

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Abstract

The compounds K3Bi3(PS4)4 (I), K1.5Bi2.5(PS4)3 (II), and K 9Bi(PS4)4 (III) were synthesized, and their properties are described. Red needles of I crystallize in the tetragonal spacegroup PA/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(α1/2γ)00 with a = 21.8034(12) Å, b = 8.8064(7) Å, c = 10.0333(6) Å, and β = 90.004(5)°. This compound has an incommensurately modulated superstructure with the modulation vector q = 0.25a* + 0.5b* + 0.16c*. Bright-red irregularly shaped blocks of III crystallize in the orthorhombic space group P2 1212 with a = 18.306(4) Å, b = 8.926(2) Å, and c = 9.710(2) Å and have a discrete molecular salt structure with mononuclear [Bi(PS4)4]9- complexes. The structures reveal that as the relative amount of K3PS4 increases, there is a marked decrease in dimensionality of the framework. It was also possible to form a glass with the same stoichiometry as that of compound I. When annealed at 320°C, the glass crystallized into compound II. The 31P solid-state NMR spectra are reported, and they are consistent with the crystallographic results.

Original languageEnglish
Pages (from-to)11063-11074
Number of pages12
JournalInorganic Chemistry
Volume46
Issue number26
DOIs
Publication statusPublished - Dec 24 2007

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Bismuth
bismuth
potassium
Potassium
Glass
glass
needles
Stoichiometry
Needles
stoichiometry
Salts
Nuclear magnetic resonance
Modulation
Ions
salts
solid state
modulation
nuclear magnetic resonance
ions
thiophosphoric acid

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

New potassium bismuth thiophosphates including the modulated K 1.5Bi2.5(PS4)3. / Gave, Matthew A.; Weliky, David P.; Kanatzidis, Mercouri G.

In: Inorganic Chemistry, Vol. 46, No. 26, 24.12.2007, p. 11063-11074.

Research output: Contribution to journalArticle

Gave, Matthew A. ; Weliky, David P. ; Kanatzidis, Mercouri G. / New potassium bismuth thiophosphates including the modulated K 1.5Bi2.5(PS4)3. In: Inorganic Chemistry. 2007 ; Vol. 46, No. 26. pp. 11063-11074.
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abstract = "The compounds K3Bi3(PS4)4 (I), K1.5Bi2.5(PS4)3 (II), and K 9Bi(PS4)4 (III) were synthesized, and their properties are described. Red needles of I crystallize in the tetragonal spacegroup PA/ncc with a = 21.0116(8) {\AA} and c = 13.3454(10) {\AA} 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(α1/2γ)00 with a = 21.8034(12) {\AA}, b = 8.8064(7) {\AA}, c = 10.0333(6) {\AA}, and β = 90.004(5)°. This compound has an incommensurately modulated superstructure with the modulation vector q = 0.25a* + 0.5b* + 0.16c*. Bright-red irregularly shaped blocks of III crystallize in the orthorhombic space group P2 1212 with a = 18.306(4) {\AA}, b = 8.926(2) {\AA}, and c = 9.710(2) {\AA} and have a discrete molecular salt structure with mononuclear [Bi(PS4)4]9- complexes. The structures reveal that as the relative amount of K3PS4 increases, there is a marked decrease in dimensionality of the framework. It was also possible to form a glass with the same stoichiometry as that of compound I. When annealed at 320°C, the glass crystallized into compound II. The 31P solid-state NMR spectra are reported, and they are consistent with the crystallographic results.",
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N2 - The compounds K3Bi3(PS4)4 (I), K1.5Bi2.5(PS4)3 (II), and K 9Bi(PS4)4 (III) were synthesized, and their properties are described. Red needles of I crystallize in the tetragonal spacegroup PA/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(α1/2γ)00 with a = 21.8034(12) Å, b = 8.8064(7) Å, c = 10.0333(6) Å, and β = 90.004(5)°. This compound has an incommensurately modulated superstructure with the modulation vector q = 0.25a* + 0.5b* + 0.16c*. Bright-red irregularly shaped blocks of III crystallize in the orthorhombic space group P2 1212 with a = 18.306(4) Å, b = 8.926(2) Å, and c = 9.710(2) Å and have a discrete molecular salt structure with mononuclear [Bi(PS4)4]9- complexes. The structures reveal that as the relative amount of K3PS4 increases, there is a marked decrease in dimensionality of the framework. It was also possible to form a glass with the same stoichiometry as that of compound I. When annealed at 320°C, the glass crystallized into compound II. The 31P solid-state NMR spectra are reported, and they are consistent with the crystallographic results.

AB - The compounds K3Bi3(PS4)4 (I), K1.5Bi2.5(PS4)3 (II), and K 9Bi(PS4)4 (III) were synthesized, and their properties are described. Red needles of I crystallize in the tetragonal spacegroup PA/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(α1/2γ)00 with a = 21.8034(12) Å, b = 8.8064(7) Å, c = 10.0333(6) Å, and β = 90.004(5)°. This compound has an incommensurately modulated superstructure with the modulation vector q = 0.25a* + 0.5b* + 0.16c*. Bright-red irregularly shaped blocks of III crystallize in the orthorhombic space group P2 1212 with a = 18.306(4) Å, b = 8.926(2) Å, and c = 9.710(2) Å and have a discrete molecular salt structure with mononuclear [Bi(PS4)4]9- complexes. The structures reveal that as the relative amount of K3PS4 increases, there is a marked decrease in dimensionality of the framework. It was also possible to form a glass with the same stoichiometry as that of compound I. When annealed at 320°C, the glass crystallized into compound II. The 31P solid-state NMR spectra are reported, and they are consistent with the crystallographic results.

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