Quaternary Rb2Cu2SnS4, A2Cu2Sn2S6 (A = Na, K, Rb, Cs), A2Cu2Sn2Se6 (A = K, Rb), K2Au2SnS4, and K2Au2Sn2S6. Syntheses, structures, and properties of new solid-state ...

Ju Hsiou Liao, Mercouri G Kanatzidis

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Abstract

Full title: Quaternary Rb2Cu2SnS4, A2Cu2Sn2S6 (A = Na, K, Rb, Cs), A2Cu2Sn2Se6 (A = K, Rb), K2Au2SnS4, and K2Au2Sn2S6. Syntheses, structures, and properties of new solid-state chalcogenides based on tetrahedral [SnS4]4- units. Rb2Cu2SnS4 (I) and Rb2Cu2Sn2S6 (II) were synthesized by heating a mixture of Sn, Cu, Rb2S, and S in the ratios of 1:4:4:16 and 1:1-2:4:16, respectively, at 400°C for 4 days. K2Au2SnS4 (III) and K2Au2Sn2S6 (IV) were synthesized by heating mixtures of Sn, Au, K2S, and S in the ratios of 1:2:4:16 and 1:1.5:2:16, respectively, at 350°C for 4 days. The structures were characterized by single-crystal X-ray diffraction techniques, infrared spectroscopy and UV-vis-near-IR reflectance spectroscopy. Crystal data for I: space group Ibam (No. 72); a = 5.528(4) Å, b = 11.418(6) Å, c = 13.700(6) Å; Z = 4; V = 865(2) Å3; dcalc = 4.185 g/cm3; number of data collected 468; number of data observed (I > 3σ(I)) 221; number of variables 23; final R/RW = 6.9/8.1. Crystal data for II: space group C2/c (No. 15); a = 11.026(2) Å, b = 11.019(3) Å, c = 20.299(4) Å, β = 97.79(2)°; Z = 8; V = 2444(1) Å3; dcalc = 3.956 g/cm3; number of data collected 11 691; number of data observed (I > 3σ(I)) 1756; number of variables 111; final R/Rw = 6.3/6.4. Crystal data for III: space group P1 (No. 2); a = 8.212(4) Å, b = 9.110(4) Å, c = 7.314(2) Å, α = 97.82(3)°, β = 111.72(2)°, γ = 72.00(2)°, V = 483.2(7) Å3; Z = 2; dcalc = 4.941 g/cm3; number of data collected: 1832; number of data observed (I > 3σ(I)) 1447; number of variables 83; final R/RW = 4.8/6.0. Crystal data for IV: space group P4/mcc (No. 124); a = b = 7.968(2) Å, c = 19.200(6) Å, V = 1219(1) Å3, Z = 4; dcalc = 4.914 g/cm3; number of data collected 911; number of data observed (I > 3σ(I)) 459; number of variables 34; final R/RW = 4.1/3.9. I has a two-dimensional structure which contains CuS4 and SnS4 tetrahedra in the ratio of 2:1 as building blocks. The [Cu2SnS4]2- layers are best described as an ordered defect anti-PbO type structure. The rubidium cations are found between the layers. II is a layered structure which contains corner-sharing SnS4 and CuS4 tetrahedra and can be viewed as a derivative of adamantine type structure. Both III and IV have one-dimensional structures. The anionic chains of III contain linear AuS2 and SnS4 tetrahedra in the ratio of 2:1, while IV contains linear AuS2 and Sn2S6 edge-sharing bitetrahedra also in the ratio of 2:1. The charges are balanced by potassium cations located between the chains. Infrared spectra for I-IV are reported. I-IV are semiconductors with optical bandgaps of 2.08, 1.44, 2.75, and 2.30 eV, respectively.

Original languageEnglish
Pages (from-to)1561-1569
Number of pages9
JournalChemistry of Materials
Volume5
Issue number10
Publication statusPublished - 1993

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Crystals
Cations
Positive ions
Rubidium
Heating
Chalcogenides
Optical band gaps
Potassium
Infrared spectroscopy
Single crystals
Spectroscopy
Semiconductor materials
Infrared radiation
Derivatives
X ray diffraction
Defects

ASJC Scopus subject areas

  • Materials Chemistry
  • Materials Science(all)

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@article{853784d27f774987800da975011a7aea,
title = "Quaternary Rb2Cu2SnS4, A2Cu2Sn2S6 (A = Na, K, Rb, Cs), A2Cu2Sn2Se6 (A = K, Rb), K2Au2SnS4, and K2Au2Sn2S6. Syntheses, structures, and properties of new solid-state ...",
abstract = "Full title: Quaternary Rb2Cu2SnS4, A2Cu2Sn2S6 (A = Na, K, Rb, Cs), A2Cu2Sn2Se6 (A = K, Rb), K2Au2SnS4, and K2Au2Sn2S6. Syntheses, structures, and properties of new solid-state chalcogenides based on tetrahedral [SnS4]4- units. Rb2Cu2SnS4 (I) and Rb2Cu2Sn2S6 (II) were synthesized by heating a mixture of Sn, Cu, Rb2S, and S in the ratios of 1:4:4:16 and 1:1-2:4:16, respectively, at 400°C for 4 days. K2Au2SnS4 (III) and K2Au2Sn2S6 (IV) were synthesized by heating mixtures of Sn, Au, K2S, and S in the ratios of 1:2:4:16 and 1:1.5:2:16, respectively, at 350°C for 4 days. The structures were characterized by single-crystal X-ray diffraction techniques, infrared spectroscopy and UV-vis-near-IR reflectance spectroscopy. Crystal data for I: space group Ibam (No. 72); a = 5.528(4) {\AA}, b = 11.418(6) {\AA}, c = 13.700(6) {\AA}; Z = 4; V = 865(2) {\AA}3; dcalc = 4.185 g/cm3; number of data collected 468; number of data observed (I > 3σ(I)) 221; number of variables 23; final R/RW = 6.9/8.1. Crystal data for II: space group C2/c (No. 15); a = 11.026(2) {\AA}, b = 11.019(3) {\AA}, c = 20.299(4) {\AA}, β = 97.79(2)°; Z = 8; V = 2444(1) {\AA}3; dcalc = 3.956 g/cm3; number of data collected 11 691; number of data observed (I > 3σ(I)) 1756; number of variables 111; final R/Rw = 6.3/6.4. Crystal data for III: space group P1 (No. 2); a = 8.212(4) {\AA}, b = 9.110(4) {\AA}, c = 7.314(2) {\AA}, α = 97.82(3)°, β = 111.72(2)°, γ = 72.00(2)°, V = 483.2(7) {\AA}3; Z = 2; dcalc = 4.941 g/cm3; number of data collected: 1832; number of data observed (I > 3σ(I)) 1447; number of variables 83; final R/RW = 4.8/6.0. Crystal data for IV: space group P4/mcc (No. 124); a = b = 7.968(2) {\AA}, c = 19.200(6) {\AA}, V = 1219(1) {\AA}3, Z = 4; dcalc = 4.914 g/cm3; number of data collected 911; number of data observed (I > 3σ(I)) 459; number of variables 34; final R/RW = 4.1/3.9. I has a two-dimensional structure which contains CuS4 and SnS4 tetrahedra in the ratio of 2:1 as building blocks. The [Cu2SnS4]2- layers are best described as an ordered defect anti-PbO type structure. The rubidium cations are found between the layers. II is a layered structure which contains corner-sharing SnS4 and CuS4 tetrahedra and can be viewed as a derivative of adamantine type structure. Both III and IV have one-dimensional structures. The anionic chains of III contain linear AuS2 and SnS4 tetrahedra in the ratio of 2:1, while IV contains linear AuS2 and Sn2S6 edge-sharing bitetrahedra also in the ratio of 2:1. The charges are balanced by potassium cations located between the chains. Infrared spectra for I-IV are reported. I-IV are semiconductors with optical bandgaps of 2.08, 1.44, 2.75, and 2.30 eV, respectively.",
author = "Liao, {Ju Hsiou} and Kanatzidis, {Mercouri G}",
year = "1993",
language = "English",
volume = "5",
pages = "1561--1569",
journal = "Chemistry of Materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - Quaternary Rb2Cu2SnS4, A2Cu2Sn2S6 (A = Na, K, Rb, Cs), A2Cu2Sn2Se6 (A = K, Rb), K2Au2SnS4, and K2Au2Sn2S6. Syntheses, structures, and properties of new solid-state ...

AU - Liao, Ju Hsiou

AU - Kanatzidis, Mercouri G

PY - 1993

Y1 - 1993

N2 - Full title: Quaternary Rb2Cu2SnS4, A2Cu2Sn2S6 (A = Na, K, Rb, Cs), A2Cu2Sn2Se6 (A = K, Rb), K2Au2SnS4, and K2Au2Sn2S6. Syntheses, structures, and properties of new solid-state chalcogenides based on tetrahedral [SnS4]4- units. Rb2Cu2SnS4 (I) and Rb2Cu2Sn2S6 (II) were synthesized by heating a mixture of Sn, Cu, Rb2S, and S in the ratios of 1:4:4:16 and 1:1-2:4:16, respectively, at 400°C for 4 days. K2Au2SnS4 (III) and K2Au2Sn2S6 (IV) were synthesized by heating mixtures of Sn, Au, K2S, and S in the ratios of 1:2:4:16 and 1:1.5:2:16, respectively, at 350°C for 4 days. The structures were characterized by single-crystal X-ray diffraction techniques, infrared spectroscopy and UV-vis-near-IR reflectance spectroscopy. Crystal data for I: space group Ibam (No. 72); a = 5.528(4) Å, b = 11.418(6) Å, c = 13.700(6) Å; Z = 4; V = 865(2) Å3; dcalc = 4.185 g/cm3; number of data collected 468; number of data observed (I > 3σ(I)) 221; number of variables 23; final R/RW = 6.9/8.1. Crystal data for II: space group C2/c (No. 15); a = 11.026(2) Å, b = 11.019(3) Å, c = 20.299(4) Å, β = 97.79(2)°; Z = 8; V = 2444(1) Å3; dcalc = 3.956 g/cm3; number of data collected 11 691; number of data observed (I > 3σ(I)) 1756; number of variables 111; final R/Rw = 6.3/6.4. Crystal data for III: space group P1 (No. 2); a = 8.212(4) Å, b = 9.110(4) Å, c = 7.314(2) Å, α = 97.82(3)°, β = 111.72(2)°, γ = 72.00(2)°, V = 483.2(7) Å3; Z = 2; dcalc = 4.941 g/cm3; number of data collected: 1832; number of data observed (I > 3σ(I)) 1447; number of variables 83; final R/RW = 4.8/6.0. Crystal data for IV: space group P4/mcc (No. 124); a = b = 7.968(2) Å, c = 19.200(6) Å, V = 1219(1) Å3, Z = 4; dcalc = 4.914 g/cm3; number of data collected 911; number of data observed (I > 3σ(I)) 459; number of variables 34; final R/RW = 4.1/3.9. I has a two-dimensional structure which contains CuS4 and SnS4 tetrahedra in the ratio of 2:1 as building blocks. The [Cu2SnS4]2- layers are best described as an ordered defect anti-PbO type structure. The rubidium cations are found between the layers. II is a layered structure which contains corner-sharing SnS4 and CuS4 tetrahedra and can be viewed as a derivative of adamantine type structure. Both III and IV have one-dimensional structures. The anionic chains of III contain linear AuS2 and SnS4 tetrahedra in the ratio of 2:1, while IV contains linear AuS2 and Sn2S6 edge-sharing bitetrahedra also in the ratio of 2:1. The charges are balanced by potassium cations located between the chains. Infrared spectra for I-IV are reported. I-IV are semiconductors with optical bandgaps of 2.08, 1.44, 2.75, and 2.30 eV, respectively.

AB - Full title: Quaternary Rb2Cu2SnS4, A2Cu2Sn2S6 (A = Na, K, Rb, Cs), A2Cu2Sn2Se6 (A = K, Rb), K2Au2SnS4, and K2Au2Sn2S6. Syntheses, structures, and properties of new solid-state chalcogenides based on tetrahedral [SnS4]4- units. Rb2Cu2SnS4 (I) and Rb2Cu2Sn2S6 (II) were synthesized by heating a mixture of Sn, Cu, Rb2S, and S in the ratios of 1:4:4:16 and 1:1-2:4:16, respectively, at 400°C for 4 days. K2Au2SnS4 (III) and K2Au2Sn2S6 (IV) were synthesized by heating mixtures of Sn, Au, K2S, and S in the ratios of 1:2:4:16 and 1:1.5:2:16, respectively, at 350°C for 4 days. The structures were characterized by single-crystal X-ray diffraction techniques, infrared spectroscopy and UV-vis-near-IR reflectance spectroscopy. Crystal data for I: space group Ibam (No. 72); a = 5.528(4) Å, b = 11.418(6) Å, c = 13.700(6) Å; Z = 4; V = 865(2) Å3; dcalc = 4.185 g/cm3; number of data collected 468; number of data observed (I > 3σ(I)) 221; number of variables 23; final R/RW = 6.9/8.1. Crystal data for II: space group C2/c (No. 15); a = 11.026(2) Å, b = 11.019(3) Å, c = 20.299(4) Å, β = 97.79(2)°; Z = 8; V = 2444(1) Å3; dcalc = 3.956 g/cm3; number of data collected 11 691; number of data observed (I > 3σ(I)) 1756; number of variables 111; final R/Rw = 6.3/6.4. Crystal data for III: space group P1 (No. 2); a = 8.212(4) Å, b = 9.110(4) Å, c = 7.314(2) Å, α = 97.82(3)°, β = 111.72(2)°, γ = 72.00(2)°, V = 483.2(7) Å3; Z = 2; dcalc = 4.941 g/cm3; number of data collected: 1832; number of data observed (I > 3σ(I)) 1447; number of variables 83; final R/RW = 4.8/6.0. Crystal data for IV: space group P4/mcc (No. 124); a = b = 7.968(2) Å, c = 19.200(6) Å, V = 1219(1) Å3, Z = 4; dcalc = 4.914 g/cm3; number of data collected 911; number of data observed (I > 3σ(I)) 459; number of variables 34; final R/RW = 4.1/3.9. I has a two-dimensional structure which contains CuS4 and SnS4 tetrahedra in the ratio of 2:1 as building blocks. The [Cu2SnS4]2- layers are best described as an ordered defect anti-PbO type structure. The rubidium cations are found between the layers. II is a layered structure which contains corner-sharing SnS4 and CuS4 tetrahedra and can be viewed as a derivative of adamantine type structure. Both III and IV have one-dimensional structures. The anionic chains of III contain linear AuS2 and SnS4 tetrahedra in the ratio of 2:1, while IV contains linear AuS2 and Sn2S6 edge-sharing bitetrahedra also in the ratio of 2:1. The charges are balanced by potassium cations located between the chains. Infrared spectra for I-IV are reported. I-IV are semiconductors with optical bandgaps of 2.08, 1.44, 2.75, and 2.30 eV, respectively.

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