Abstract
Crystal structures of Hg4As2Br3(I) and Hg7.4As4Cl6(II), which was prepared for the first time, have been refined based on the X-ray single crystal experiments. Both phases crystallize in the cubic space groupPa3. Crystal data: I,a= 12.610(1),Z= 8,R1= 0.0602; II,a= 12.178(1),Z= 4,R1= 0.0584. Characteristic of both structures are the As2Hg6octahedra having an As–As separation of ca. 2.38 Å. Such octahedra share vertices with AsHg4tetrahedra in I, while in II they compose a perovskite-like three-dimensional network by sharing all vertices. Part of the mercury atoms in II have no neighbors up to 3.53 Å and are considered to possess a zero oxidation state. An idealized path for the I to II structure transformation, which is based on the difference of halogen radii, is suggested.
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