Abstract
AbstractSb2Hg3GaBr4 is a new air stable transparent reddish solid that crystallizes in space group Pnma (No. 62, Z = 8) with the lattice constants a = 1375.49(8) pm, b = 1269.0(1) pm, c = 1478.19(9) pm. The title compound represents a new structure type based on a cationic framework $^{3}_{\infty}\rm [Sb_{2}Hg_{3}]^{+}$ of a significantly modified Millons base type. Structural building blocks of the cationic partial structure are well known tetrahedral [SbHg4/2]+ groups and unprecedented formally neutral [Sb2Hg4/2]±0 units in a 2:1 ratio. The [Sb2Hg4/2]±0 units contain covalent Sb‐Sb bonds (d = 285.6 pm) and are isosteric with Distibane Sb2H4 in a staggered conformation. Structural consequences of the lone pairs located at the Sb atoms of the [Sb2Hg4/2]±0 units are discussed. The charge of the cationic framework is balanced by disordered anions in suitable cavities. They appear as tetrahedral [GaBr4]− but correspond most likely to a superposition of bitetrahedral apex sharing [Ga2Br7]− and isolated Br−.
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