Four isotypic compounds Hg3AsS4Cl, Hg3AsS4Br, Hg3AsSe4Br, and Hg3AsSe4I were synthesized in the quaternary system mercury/arsenic/chalcogen/halogen by vapor transport reactions from As, Hg(II) halide, Hg(II) chalcogenide, and elemental chalcogen at temperatures between 250 and 310 °C. Their structures were solved by single-crystal X-ray diffraction analyses. The compounds crystallize in the hexagonal system with the acentric space group P63mc and the following lattice parameters:  a = 7.431(5) A, c = 9.003(8) A for Hg3AsS4Cl, a = 7.430(5) A, c = 9.364(5) A for Hg3AsS4Br, a = 7.707(8) A, c = 9.47(2) A for Hg3AsSe4Br, and a = 7.6902(7) A, c = 9.968(1) A for Hg3AsSe4I, and Z = 2. All compounds are air-stable and form hexagonal prismatic crystals. The colors vary from yellow (Hg3AsS4Cl) to red (Hg3AsSe4I). The structures consist of [Hg3AsE4]+ polycationic layers built of six-membered Hg3E3 and Hg2AsE3 rings in chair and boat conformations. Alternatively, the structure of the layers can be described as compose...

Hg3AsE4X (E = S, Se; X = Cl, Br, I), a Family of Isotypic Compounds with an Acentric, Layered Structure

Publisher Summary The aim of this review is to discuss the modern, solid-state chemistry of the members of a well-defined class of compounds with respect to their preparative methods, structural features, and physical properties. The thio-, seleno-, and tellurohalides of the metallic elements seem to be well suited for this purpose. In contrast to such binary compounds as oxides and halides, they fit into the frame of the restricted space available, and with the exception of alkaline and alkaline-earth elements, examples are found in all groups of the periodic system. The large group of oxyhalides, as well as the chalcogenide fluorides, have been excluded. Oxyhalides have been extensively reviewed, and the properties of the fluorides are closely related to this group; in addition, the behavior differs in some respects from that of the chalcogenide halides treated here. A typical feature of the compounds under consideration is that of nonstoichiometry.

Solid-State Chemistry of Thio-, Seleno-, and Tellurohalides of Representative and Transition Elements

Expanded polycationic mercury–chalcogen networks in the layered compounds Hg3E2[MX6] (E=S, Se; M=Zr, Hf; X=Cl, Br)

The structures of mercury chalcogenhalogenides Hg3X2Hal2

Die rontgenographische Strukturbestimmung an Einkristallen (WEISSENBERG-Methode) zeigte, das in beiden Verbindungen Hg-Atome und RS≤-Gruppen zu gewinkelten Ketten verknupft sind. Diese sind uber Acetatgruppen zu Schichten verbunden.



Die Deutung der IR- und Raman-Spektren steht im Einklang mit diesen Ergebnissen.



The Structure of Propyl- and Butylmercaptomercuric Acetate



The X-ray structural analysis of the title compounds showed that the Hg atoms and the RS< groups are connected in angular chains. The chains are bridged to layers through the acetate group.



The IR and Raman data are consistent with these results.

Klaus-Peter Hoop

Papers

Polymorphie bei Quecksilberschwefel-Halogeniden