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Abstract

The concerted experimental and computational study reports on the polymorphic behavior of RuBr3. Highly-resolved X-ray powder diffraction measurements of the modification lt-RuBr3 give direct evidence for peak splitting substantiating an orthorhombic unit cell with additional weak intensities confirming a primitive lattice. The crystal structure of lt-RuBr3 is determined using the intensities of a “Drilling” individuum. For lt-RuBr3, findings of density functional theory calculations suggest that the deviation from hexagonal symmetry is mainly driven by electronic correlations. Reinvestigation of the recently reported high-pressure modification hp-RuBr3 essentially confirms the rhombohedral BiI3-type crystal structure (space group R (Formula presented.)). Simulations of the atomic arrangement of hp-RuBr3 indicate that spin-orbit coupling and corrections for the van-der-Waals dispersive forces are mandatory to reach a reasonable agreement with the experimentally determined crystal structure. © 2023 The Authors. Zeitschrift für anorganische und allgemeine Chemie published by Wiley-VCH GmbH.