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Wahl, Bernhard
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article
Ag3Bi14Br21
Abstract
<p>Black crystals of Ag<sub>3</sub>Bi<sub>14</sub>Br<sub>21</sub> = (Bi <sub>9</sub><sup>5+</sup>)[Ag<sub>3</sub>Bi<sub>3</sub>Br<sub>15</sub> <sup>3-</sup>]-(Bi<sub>2</sub>Br<sub>6</sub><sup>2-</sup>), the first argentiferous bismuth subhalide, were obtained from a stoichiometric melt of Ag, Bi, and BiBr<sub>3</sub>. The compound crystallizes in the monoclinic space group P2<sub>1</sub>/m with lattice parameters a = 1277.78(5) pm, b = 1466.87(6) pm, c = 1342.62(5) pm, and β = 108.47(1)° at 110(5) K. In contrast to all other bismuth subhalides that contain an electron-rich transition metal, the silver atoms are not bonded to bismuth atoms. Instead they are integrated into the anionic bromometallate network, which consists of [MBr<sub>6</sub>]- octahedra (M = Ag, Bi) that share edges and vertices. These corrugated <sub>∞</sub><sup>2</sup>[Ag<sub>3</sub>Bi<sub>3</sub>Br<sub>15</sub>] <sup>3-</sup> sheets alternate with tessellated layers formed by Bi <sub>9</sub><sup>5+</sup> polycations and hitherto unknown (Bi<sup>II</sup> <sub>2</sub>Br<sub>6</sub>)<sup>2-</sup> groups. The latter anions contain Bi<sub>2</sub><sup>4+</sup> dumbbells (299 pm) and can be represented by the structured formula [Br<sub>2</sub>Bi<sup>II</sup>(μBr)<sub>2</sub>Bi <sup>II</sup>Br<sub>2</sub>]<sup>2-</sup>. The multi-center bonding within the Bi<sub>9</sub><sup>5+</sup> cluster and the bent single-bond in the Bi <sub>2</sub> dumbbell can be visualized using the electron localization indicator (ELI-D).</p>