TY - JOUR

T1 - Expanding Family of Litharge-Derived Sulfate Minerals and Synthetic Compounds: Preparation and Crystal Structures of [Bi2CuO3]SO4 and [Ln2O2]SO4 (Ln = Dy and Ho)

AU - Siidra, Oleg

AU - Charkin, Dmitri

AU - Plokhikh, Igor V.

AU - Nazarchuk, Evgeny

AU - Holzheid , Astrid

AU - Akimov, Georgy

N1 - Funding Information: Funding: This work was financially supported by the Russian Science Foundation through the grant 16-17-10085. E.N. was supported by the internal SPbSU travel grant to the University of Kiel. Funding Information: Acknowledgments: Technical support by the SPbSU X-ray Diffraction and Microscopy and Microanalysis Resource Centers is gratefully acknowledged.

PY - 2020/10/7

Y1 - 2020/10/7

N2 - 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.

AB - 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.

KW - Copper

KW - Crystal structure

KW - Lanthanides

KW - Layered structures

KW - Litharge

KW - Sulfates

KW - Synthesis

UR - http://www.scopus.com/inward/record.url?scp=85092359398&partnerID=8YFLogxK

U2 - 10.3390/min10100887

DO - 10.3390/min10100887

M3 - Article

VL - 10

SP - 1

EP - 10

JO - Minerals

JF - Minerals

SN - 2075-163X

IS - 10

M1 - 887

ER -