New Layered Compounds through Polysulfide Flux Synthesis;A2Sn4S9(A=K, Rb, Cs) Present a New Form of the [Sn4S9]2-Network

Gregory A. Marking; M. Evain; V. Petricek; Mercouri G. Kanatzidis

doi:10.1006/jssc.1998.7889

New Layered Compounds through Polysulfide Flux Synthesis;A₂Sn₄S₉(A=K, Rb, Cs) Present a New Form of the [Sn₄S₉]^2-Network

Gregory A. Marking^*, M. Evain, V. Petricek, Mercouri G. Kanatzidis

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

28 Scopus citations

Abstract

Crystals of Cs₂Sn₄S₉, Rb₂Sn₄S₉, and K₂Sn₄S₉were synthesized by reacting Sn with Cs₂S_x, Rb₂S_x, or K₂S_xfluxes at 500°°C. They can also be prepared as microcrystalline products through direct combination reactions at temperatures ranging from 720 to 750°C. The new ternary sulfide Cs₂Sn₄S₉crystallizes in the orthorhombicPnmaspace group, the new ternary sulfide Rb₂Sn₄S₉crystallizes in the orthorhombic P2₁2₁2₁space group, and the new ternary sulfide K₂Sn₄S₉appears to be isostructural with Rb₂Sn₄S₉, as determined through X-ray powder diffraction. The structures of Cs₂Sn₄S₉, Rb₂Sn₄S₉, and K₂Sn₄S₉consist of nearly identical [Sn₄S₉]^2-layers which are stacked in two different arrangements. Alkali metal Cs⁺, Rb⁺, and K⁺cations are located between the layers. Raman and far-IR spectroscopic data confirm the presence of the [Sn₄S₉]^2-layer in all three compounds. Single crystal optical spectra indicate that Cs₂Sn₄S₉, Rb₂Sn₄S₉, and K₂Sn₄S₉are wide band-gap semiconductors with bandgaps of 2.66 eV, 2.65 eV, and 2.66 eV, respectively.

Original language	English (US)
Pages (from-to)	17-28
Number of pages	12
Journal	Journal of Solid State Chemistry
Volume	141
Issue number	1
DOIs	https://doi.org/10.1006/jssc.1998.7889
State	Published - Nov 15 1998

Funding

Financial support from the National Science Foundation DMR-9527347 and from Rockwell International Corporation is gratefully acknowledged. This work made use of the SEM facilities of the Center for Electron Optics, Michigan State University. We thank Jason Hanko for critically reading the manuscript. M.G.K. is an A.P. Sloan Foundation, and a Camille and Henry Dreyfus Teacher Scholar 1993—1998. V.P. thanks the Universite de Nantes, IMN for financial support during his stay at IMN and the Grant Agency of the Czech Republic for Grant 202/1996/0085.

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Ceramics and Composites
Condensed Matter Physics
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1006/jssc.1998.7889

Cite this

@article{55c4077d86ef4c5aa8bde014974890db,

title = "New Layered Compounds through Polysulfide Flux Synthesis;A2Sn4S9(A=K, Rb, Cs) Present a New Form of the [Sn4S9]2-Network",

abstract = "Crystals of Cs2Sn4S9, Rb2Sn4S9, and K2Sn4S9were synthesized by reacting Sn with Cs2Sx, Rb2Sx, or K2Sxfluxes at 500°°C. They can also be prepared as microcrystalline products through direct combination reactions at temperatures ranging from 720 to 750°C. The new ternary sulfide Cs2Sn4S9crystallizes in the orthorhombicPnmaspace group, the new ternary sulfide Rb2Sn4S9crystallizes in the orthorhombic P212121space group, and the new ternary sulfide K2Sn4S9appears to be isostructural with Rb2Sn4S9, as determined through X-ray powder diffraction. The structures of Cs2Sn4S9, Rb2Sn4S9, and K2Sn4S9consist of nearly identical [Sn4S9]2-layers which are stacked in two different arrangements. Alkali metal Cs+, Rb+, and K+cations are located between the layers. Raman and far-IR spectroscopic data confirm the presence of the [Sn4S9]2-layer in all three compounds. Single crystal optical spectra indicate that Cs2Sn4S9, Rb2Sn4S9, and K2Sn4S9are wide band-gap semiconductors with bandgaps of 2.66 eV, 2.65 eV, and 2.66 eV, respectively.",

author = "Marking, {Gregory A.} and M. Evain and V. Petricek and Kanatzidis, {Mercouri G.}",

note = "Funding Information: Financial support from the National Science Foundation DMR-9527347 and from Rockwell International Corporation is gratefully acknowledged. This work made use of the SEM facilities of the Center for Electron Optics, Michigan State University. We thank Jason Hanko for critically reading the manuscript. M.G.K. is an A.P. Sloan Foundation, and a Camille and Henry Dreyfus Teacher Scholar 1993—1998. V.P. thanks the Universite de Nantes, IMN for financial support during his stay at IMN and the Grant Agency of the Czech Republic for Grant 202/1996/0085.",

year = "1998",

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day = "15",

doi = "10.1006/jssc.1998.7889",

language = "English (US)",

volume = "141",

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journal = "Journal of Solid State Chemistry",

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T1 - New Layered Compounds through Polysulfide Flux Synthesis;A2Sn4S9(A=K, Rb, Cs) Present a New Form of the [Sn4S9]2-Network

AU - Marking, Gregory A.

AU - Evain, M.

AU - Petricek, V.

AU - Kanatzidis, Mercouri G.

N1 - Funding Information: Financial support from the National Science Foundation DMR-9527347 and from Rockwell International Corporation is gratefully acknowledged. This work made use of the SEM facilities of the Center for Electron Optics, Michigan State University. We thank Jason Hanko for critically reading the manuscript. M.G.K. is an A.P. Sloan Foundation, and a Camille and Henry Dreyfus Teacher Scholar 1993—1998. V.P. thanks the Universite de Nantes, IMN for financial support during his stay at IMN and the Grant Agency of the Czech Republic for Grant 202/1996/0085.

PY - 1998/11/15

Y1 - 1998/11/15

N2 - Crystals of Cs2Sn4S9, Rb2Sn4S9, and K2Sn4S9were synthesized by reacting Sn with Cs2Sx, Rb2Sx, or K2Sxfluxes at 500°°C. They can also be prepared as microcrystalline products through direct combination reactions at temperatures ranging from 720 to 750°C. The new ternary sulfide Cs2Sn4S9crystallizes in the orthorhombicPnmaspace group, the new ternary sulfide Rb2Sn4S9crystallizes in the orthorhombic P212121space group, and the new ternary sulfide K2Sn4S9appears to be isostructural with Rb2Sn4S9, as determined through X-ray powder diffraction. The structures of Cs2Sn4S9, Rb2Sn4S9, and K2Sn4S9consist of nearly identical [Sn4S9]2-layers which are stacked in two different arrangements. Alkali metal Cs+, Rb+, and K+cations are located between the layers. Raman and far-IR spectroscopic data confirm the presence of the [Sn4S9]2-layer in all three compounds. Single crystal optical spectra indicate that Cs2Sn4S9, Rb2Sn4S9, and K2Sn4S9are wide band-gap semiconductors with bandgaps of 2.66 eV, 2.65 eV, and 2.66 eV, respectively.

AB - Crystals of Cs2Sn4S9, Rb2Sn4S9, and K2Sn4S9were synthesized by reacting Sn with Cs2Sx, Rb2Sx, or K2Sxfluxes at 500°°C. They can also be prepared as microcrystalline products through direct combination reactions at temperatures ranging from 720 to 750°C. The new ternary sulfide Cs2Sn4S9crystallizes in the orthorhombicPnmaspace group, the new ternary sulfide Rb2Sn4S9crystallizes in the orthorhombic P212121space group, and the new ternary sulfide K2Sn4S9appears to be isostructural with Rb2Sn4S9, as determined through X-ray powder diffraction. The structures of Cs2Sn4S9, Rb2Sn4S9, and K2Sn4S9consist of nearly identical [Sn4S9]2-layers which are stacked in two different arrangements. Alkali metal Cs+, Rb+, and K+cations are located between the layers. Raman and far-IR spectroscopic data confirm the presence of the [Sn4S9]2-layer in all three compounds. Single crystal optical spectra indicate that Cs2Sn4S9, Rb2Sn4S9, and K2Sn4S9are wide band-gap semiconductors with bandgaps of 2.66 eV, 2.65 eV, and 2.66 eV, respectively.

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