TY - GEN A1 - Pabst, Falk A1 - Chang, Jen‐Hui A1 - Finzel, Kati A1 - Kohout, Miroslav A1 - Schmidt, Peer A1 - Ruck, Michael T1 - The Subbromide Bi5Br4 – On the Existence of a Hidden Phase T2 - Zeitschrift für Anorganische und Allgemeine Chemie N2 - Black and irregularly shaped crystals of the bismuth‐rich bromide Bi5Br4 were obtained as a by‐product of the reaction of CsBr, Bi, and BiBr3. X‐ray diffraction on a single‐crystal revealed its orthorhombic structure with the space group Pmmn (no. 59) and lattice parameters a = 1800.0(2) pm, b = 1476.1(1) pm, and c = 924.5(2) pm at 296 K. The structure is composed of Bi82+ and Bi95+ polycations and bromidobismuthate(III) anions according to the structured formula Bi5Br4 = Bi20Br16 = Bi82+Bi95+[BiBr5]2–[Bi2Br11]5–. Bi5Br4 is the bismuth‐richest among the bismuth subhalides containing isolated polycations. Extensive differential scanning calorimetry studies indicate that Bi5Br4 decomposes at 262 °C, i.e. one degree below the bismuth‐rich eutectic at 263 °C. All attempts towards a rational synthesis yielded predominantly the neighboring phases BiBr and Bi6Br7. KW - Bromine KW - Bismuth KW - Cluster KW - Phase Diagrams KW - Polycations KW - Crystal structure Y1 - 2020 UR - https://onlinelibrary.wiley.com/doi/10.1002/zaac.201800149 U6 - https://doi.org/10.1002/zaac.201800149 VL - 646 IS - 3 SP - 149 EP - 155 ER -