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article
Structure and bonding of Bi4Ir
Abstract
<p>Crystals of Bi<sub>4</sub>Ir, a new intermetallic compound, were obtained by the reaction of an iridium-containing intermetallic precursor with liquid bismuth. X-ray diffraction on a single crystal revealed a rhombohedral structure [R3¯m, a = 2656.7(2) pm, and c = 701.6(4) pm]. Bi<sub>4</sub>Ir is not isostructural to Bi<sub>4</sub>Rh but combines motifs of the metastable superconductor Bi<sub>14</sub>Rh<sub>3</sub> with those found in the weak topological insulator Bi<sub>14</sub>Rh<sub>3</sub>I<sub>9</sub>. The two crystallographically independent iridium sites in Bi<sub>4</sub>Ir have square-prismatic and skewed-square-antiprismatic bismuth coordination with Bi-Ir distances of 283-287 pm. By sharing common edges, the two types of [IrBi<sub>8</sub>] units constitute a complex three-dimensional network of rings and helices. The bonding in the heterometallic framework is dominated by pairwise Bi-Ir interactions. In addition, three-center bonds are found in the bismuth triangles formed by adjacent [IrBi<sub>8</sub>] polyhedra. Density functional theory based band-structure calculations suggest metallic properties.</p>