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

Ju Hsiou Liao, Mercouri G. Kanatzidis

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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 > 3σx(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)o; 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 PI (No. 2); a = 8.212(4) Å, b = 9.110(4) Å, c = 7.314(2) Å, α = 97.82(3)o, β = 111.72(2)o, γ = 72.00(2)o, 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
Issue number10
Publication statusPublished - Jan 1 1993

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Fingerprint Dive into the research topics of 'Quaternary Rb<sub>2</sub>Cu<sub>2</sub>SnS<sub>4</sub>, A<sub>2</sub>Cu<sub>2</sub>Sn<sub>2</sub>S<sub>6</sub> (A = Na, K, Rb, Cs), A<sub>2</sub>Cu<sub>2</sub>Sn<sub>2</sub>Se<sub>6</sub> (A = K, Rb), K<sub>2</sub>Au<sub>2</sub>SnS<sub>4</sub>, and K<sub>2</sub>Au<sub>2</sub>Sn<sub>2</sub>S<sub>6</sub>. Syntheses, Structures, and Properties of New Solid-State Chalcogenides Based on Tetrahedral [SnS<sub>4</sub>]<sup>4−</sup> Units'. Together they form a unique fingerprint.

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