Rb₆In₂S₆ und Rb₄In₂S₅, zwei neue Thioindate mit isolierten und verknüpften [In₂S₆]^6- Anionen / Rb₆In₂Se₆ and Rb₄ln₂S₅, Two NEW Thioindates with Isolated and Connected [In₂S₆]^6- Anions Respectively

Abstract

<jats:title>Abstract</jats:title><jats:p> The hitherto unknown title compounds were prepared by a disproportionation reaction starting from elementary rubidium and indium monosulfide. Rb<jats:sub>4</jats:sub>ln<jats:sub>2</jats:sub>S<jats:sub>5</jats:sub> crystallizes in the triclinic system (P1̄) with the lattice constants a = 931.7(2); b = 1097.6(3);c = 761.2(2)pm; a = 111.32°(2); β = 94.70°(2); γ = 103.70°(2) (Z = 2) and Rb<jats:sub>6</jats:sub>In<jats:sub>2</jats:sub>S<jats:sub>6</jats:sub> in the monoclinic system (C2/m) with the lattice constants a = 895.3(2); b = 1356.9(2); c = 791.8(2) pm; β = 101.53°(2) (Z = 2). The quasi molecular [In<jats:sub>2</jats:sub>Se<jats:sub>6</jats:sub>]<jats:sup>6-</jats:sup> group which is isoelectronic with the gas phase molecule In<jats:sub>2</jats:sub>Cl<jats:sub>6</jats:sub> consists of two edge sharing InS<jats:sub>4</jats:sub> tetrahedra and is the basic unit of Rb<jats:sub>6</jats:sub>ln<jats:sub>2</jats:sub>S<jats:sub>6</jats:sub> as well as of Rb<jats:sub>6</jats:sub>In<jats:sub>2</jats:sub>S<jats:sub>6</jats:sub>. The formation process, structural relationships between the two compounds and their possible role in the phase diagram of the components Rb<jats:sub>2</jats:sub>S and In<jats:sub>2</jats:sub>S<jats:sub>3</jats:sub> are discussed.</jats:p>