First attempts to synthesize a lanthanoid(III) oxide fluoride sulfide were successful by reacting DyF3 and Dy2O3 with dysprosium and sulfur in a 2 : 5 : 1 : 3 molar ratio at 850 ◦C in tightly sealed tantalum ampoules. In analogy to the dysprosium compound Dy3OF5S, the other representatives of the M3OF5S series with M = Nd, Sm, Gd-Ho could be prepared as well. Almost phase-pure samples were obtained under similar flux-assisted (NaCl) conditions according to 2M +5MF3 +M2O3 + 3S →3M3OF5S. In the hexagonal crystal structure (space group: P63/m; a ≈ 961 - 939 pm, c ≈ 378 - 367 pm; c/a≈0.39,Vm ≈91 - 84 cm3 mol−1, Z = 2), the M3+ cations reside in ninefold anionic coordination realized as tricapped trigonal prisms formed by seven light (O2−/F−) and two heavier S2− anions. One light-anion position exhibits the exclusive character of F− in trigonal non-planar coordination (CN = 3), while the other position with a tetrahedral cationic environment (CN = 4) is mixed occupied by F− and O2− in a 2 : 1 ratio. The S2− anions are coordinated in a trigonal prismatic way by six M3+ cations. From the data of single-crystal X-ray structure analyses, no indication of any ordering for the O2− and F− anions could be obtained, but bond-valence and MAPLE calculations confirmed the results of electron-beam microanalyses carried out earlier to reveal ordered models for Dy3OF5S.
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