Expanding Family of Litharge-Derived Sulfate Minerals and Synthetic Compounds: Preparation and Crystal Structures of [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub> and [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy and Ho)
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 derivativ...
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| Format: | Article |
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MDPI AG
2020-10-01
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| Series: | Minerals |
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| Online Access: | https://www.mdpi.com/2075-163X/10/10/887 |
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| author | Oleg Siidra Dmitri Charkin Igor Plokhikh Evgeny Nazarchuk Astrid Holzheid Georgy Akimov |
| author_facet | Oleg Siidra Dmitri Charkin Igor Plokhikh Evgeny Nazarchuk Astrid Holzheid Georgy Akimov |
| author_sort | Oleg Siidra |
| collection | DOAJ |
| description | 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, [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy, Ho), which belong indeed to the grandreefite family, and a novel compound [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub>, which belongs to a new structure type and demonstrates the second example of Cu<sup>2+</sup> incorporation into litharge-type slabs. Crystals of [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub> were obtained under high-pressure/high-temperature (HP/HT) conditions, whereas polycrystalline samples of [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy, Ho) compounds were prepared via an exchange solid-state reaction. The crystal structure of [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub> is based on alternation of continuous [Bi<sub>2</sub>CuO<sub>3</sub>]<sup>2+</sup> layers of edge-sharing OBi<sub>2</sub>Cu<sub>2</sub> and OBi<sub>3</sub>Cu tetrahedra and sheets of sulfate groups. Cu<sup>2+</sup> cations are in <i>cis</i> position in O5Bi<sub>2</sub>Cu<sub>2</sub> and O6Bi<sub>2</sub>Cu<sub>2</sub> oxocentered tetrahedra in litharge slab. The crystal structure of [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy, Ho) is completely analogous to those of grandreefite and oxysulfates of La, Sm, Eu, and Bi. |
| first_indexed | 2024-03-10T15:48:41Z |
| format | Article |
| id | doaj.art-4d2e066b2dc345d6bf518296890bebc9 |
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| issn | 2075-163X |
| language | English |
| last_indexed | 2024-03-10T15:48:41Z |
| publishDate | 2020-10-01 |
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| series | Minerals |
| spelling | doaj.art-4d2e066b2dc345d6bf518296890bebc92023-11-20T16:15:08ZengMDPI AGMinerals2075-163X2020-10-01101088710.3390/min10100887Expanding Family of Litharge-Derived Sulfate Minerals and Synthetic Compounds: Preparation and Crystal Structures of [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub> and [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy and Ho)Oleg Siidra0Dmitri Charkin1Igor Plokhikh2Evgeny Nazarchuk3Astrid Holzheid4Georgy Akimov5Department of Crystallography, Saint-Petersburg State University, University emb. 7/9, 199034 St. Petersburg, RussiaDepartment of Chemistry, Moscow State University, GSP-1, 119991 Moscow, RussiaInstitut für Anorganische Chemie der Universität Regensburg, Universitätsstr. 31, D-93040 Regensburg, GermanyDepartment of Crystallography, Saint-Petersburg State University, University emb. 7/9, 199034 St. Petersburg, RussiaInstitut für Geowissenschaften der Universität Kiel, Olshausenstr. 40, D-24098 Kiel, GermanyDepartment of Chemistry, Moscow State University, GSP-1, 119991 Moscow, RussiaDuring 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, [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy, Ho), which belong indeed to the grandreefite family, and a novel compound [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub>, which belongs to a new structure type and demonstrates the second example of Cu<sup>2+</sup> incorporation into litharge-type slabs. Crystals of [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub> were obtained under high-pressure/high-temperature (HP/HT) conditions, whereas polycrystalline samples of [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy, Ho) compounds were prepared via an exchange solid-state reaction. The crystal structure of [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub> is based on alternation of continuous [Bi<sub>2</sub>CuO<sub>3</sub>]<sup>2+</sup> layers of edge-sharing OBi<sub>2</sub>Cu<sub>2</sub> and OBi<sub>3</sub>Cu tetrahedra and sheets of sulfate groups. Cu<sup>2+</sup> cations are in <i>cis</i> position in O5Bi<sub>2</sub>Cu<sub>2</sub> and O6Bi<sub>2</sub>Cu<sub>2</sub> oxocentered tetrahedra in litharge slab. The crystal structure of [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy, Ho) is completely analogous to those of grandreefite and oxysulfates of La, Sm, Eu, and Bi.https://www.mdpi.com/2075-163X/10/10/887sulfateslithargelayered structurescopperlanthanidescrystal structure |
| spellingShingle | Oleg Siidra Dmitri Charkin Igor Plokhikh Evgeny Nazarchuk Astrid Holzheid Georgy Akimov Expanding Family of Litharge-Derived Sulfate Minerals and Synthetic Compounds: Preparation and Crystal Structures of [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub> and [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy and Ho) Minerals sulfates litharge layered structures copper lanthanides crystal structure |
| title | Expanding Family of Litharge-Derived Sulfate Minerals and Synthetic Compounds: Preparation and Crystal Structures of [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub> and [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy and Ho) |
| title_full | Expanding Family of Litharge-Derived Sulfate Minerals and Synthetic Compounds: Preparation and Crystal Structures of [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub> and [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy and Ho) |
| title_fullStr | Expanding Family of Litharge-Derived Sulfate Minerals and Synthetic Compounds: Preparation and Crystal Structures of [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub> and [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy and Ho) |
| title_full_unstemmed | Expanding Family of Litharge-Derived Sulfate Minerals and Synthetic Compounds: Preparation and Crystal Structures of [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub> and [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy and Ho) |
| title_short | Expanding Family of Litharge-Derived Sulfate Minerals and Synthetic Compounds: Preparation and Crystal Structures of [Bi<sub>2</sub>CuO<sub>3</sub>]SO<sub>4</sub> and [<i>Ln</i><sub>2</sub>O<sub>2</sub>]SO<sub>4</sub> (<i>Ln</i> = Dy and Ho) |
| title_sort | expanding family of litharge derived sulfate minerals and synthetic compounds preparation and crystal structures of bi sub 2 sub cuo sub 3 sub so sub 4 sub and i ln i sub 2 sub o sub 2 sub so sub 4 sub i ln i dy and ho |
| topic | sulfates litharge layered structures copper lanthanides crystal structure |
| url | https://www.mdpi.com/2075-163X/10/10/887 |
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