• Mangelsen, Sebastian

Abstract

<jats:title>Abstract</jats:title><jats:p>The title compounds were prepared by precipitation from acidic solutions of the reactants in acetone/water. Bi(S<jats:sub>2</jats:sub>CNH<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>Cl (<jats:bold>1</jats:bold>) crystallizes in the non-centrosymmetric trigonal space group <jats:italic>P</jats:italic>3<jats:sub>2</jats:sub> with <jats:italic>a</jats:italic> = 8.6121(3) and <jats:italic>c</jats:italic> = 11.1554(4) Å, <jats:italic>Z</jats:italic> = 3; Bi(S<jats:sub>2</jats:sub>NH<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>SCN (<jats:bold>2</jats:bold>) in <jats:italic>P</jats:italic>2<jats:sub>1</jats:sub>/<jats:italic>c</jats:italic> (monoclinic) with <jats:italic>a</jats:italic> = 5.5600(2), <jats:italic>b</jats:italic> = 14.3679(5), <jats:italic>c</jats:italic> = 12.8665(4) Å, and <jats:italic>β</jats:italic> = 90.37(3)°. In the crystal structure of <jats:bold>1</jats:bold> Bi<jats:sup>3+</jats:sup> is in a sevenfold coordination of two bidentate and one monodentate S<jats:sub>2</jats:sub>CHNH<jats:sub>2</jats:sub><jats:sup>−</jats:sup> anions with an asymmetric coordination pattern of five Bi–S and two Bi–Cl<jats:sup>−</jats:sup> bonds. The linkage of these polyhedra via common Cl–S edges leads to a 1D polymeric structure with undulated chains propagating in the direction [001]. These chains are linked by strong and medium strong hydrogen bonds forming the 3D crystal structure. In the crystal structure of <jats:bold>2</jats:bold> the Bi<jats:sup>3+</jats:sup> cation is in an eightfold coordination. The polyhedron can be described as a significantly distorted tetragonal anti-prism, capped by an additional S atom. Two of these prisms share a common quadrilateral face to form a <jats:italic>“prism-double”</jats:italic> (Bi<jats:sub>2</jats:sub>S<jats:sub>10</jats:sub>N<jats:sub>2</jats:sub>). These building units are linked by common edges, and the resulting 1D infinite <jats:italic>angulated chains</jats:italic> propagate along [100]. By contrast to organo-dithiocarbamate compounds, where <jats:bold>C–</jats:bold>H···X bridges are dominant, the interchain connections in the crystal structures of <jats:bold>1</jats:bold> and <jats:bold>2</jats:bold> are formed exclusively via N–H···S, N–H···Cl, and N–H···N interactions, generating the 3D networks. A significant eccentricity of the Bi<jats:sup>3+</jats:sup> cation in the crystal structures of both complexes is observed. Both compounds emit light in the orange range of the electromagnetic spectrum.</jats:p>

Topics

• impedance spectroscopy
• compound
• Hydrogen
• precipitation
• forming
• space group
• Bismuth