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During the last decades, layered structures have attracted particular and increasing interest due to the multitude of outstanding properties exhibited by their representatives. Particularly common among their archetypes, with a significant number of mineral and synthetic species structural derivatives, is that of litharge. In the current paper, we report the structural studies of two later rare-earth oxysulfates, [Ln2O2]SO4 (Ln = Dy, Ho), which belong indeed to the grandreefite family, and a novel compound [Bi2CuO3]SO4, which belongs to a new structure type and demonstrates the second example of Cu2+ incorporation into litharge-type slabs. Crystals of [Bi2CuO3]SO4 were obtained under high-pressure/high-temperature (HP/HT) conditions, whereas polycrystalline samples of [Ln2O2]SO4 (Ln = Dy, Ho) compounds were prepared via an exchange solid-state reaction. The crystal structure of [Bi2CuO3]SO4 is based on alternation of continuous [Bi2CuO3]2+ layers of edge-sharing OBi2Cu2 and OBi3Cu tetrahedra and sheets of sulfate groups. Cu2+ cations are in cis position in O5Bi2Cu2 and O6Bi2Cu2 oxocentered tetrahedra in litharge slab. The crystal structure of [Ln2O2]SO4 (Ln = Dy, Ho) is completely analogous to those of grandreefite and oxysulfates of La, Sm, Eu, and Bi.

minerals

Expanding Family of Litharge-Derived Sulfate Minerals and Synthetic Compounds: Preparation and Crystal Structures of [Bi2CuO3]SO4 and [Ln2O2]SO4 (Ln = Dy and Ho)