The Crystal Structure and Crystal Chemistry of Mineral-like Cd<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>, a Novel Isomorph of Arsenoclasite and Gatehouseite
The pentacadmium bis(vanadate(V)) tetrahydroxide Cd<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub> was synthesized under hydrothermal conditions, and its crystal structure was determined with single-crystal X-ray diffraction. The investigated...
| Main Authors: | , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2022-12-01
|
| Series: | Minerals |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2075-163X/12/12/1601 |
| _version_ | 1797456157574430720 |
|---|---|
| author | Ljiljana Karanović Tamara Ðorđević |
| author_facet | Ljiljana Karanović Tamara Ðorđević |
| author_sort | Ljiljana Karanović |
| collection | DOAJ |
| description | The pentacadmium bis(vanadate(V)) tetrahydroxide Cd<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub> was synthesized under hydrothermal conditions, and its crystal structure was determined with single-crystal X-ray diffraction. The investigated compound is the second known compound next to Cd(VO<sub>3</sub>)<sub>2</sub>·4H<sub>2</sub>O synthesized in the CdO–V<sub>2</sub>O<sub>5</sub>–H<sub>2</sub>O system and crystallizes isotypically to the minerals gatehouseite, Mn<sub>5</sub>(PO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>, and its As analog arsenoclasite, Mn<sub>5</sub>(AsO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>. Its symmetry is orthorhombic, with a space group of <i>P</i>2<sub>1</sub>2<sub>1</sub>2<sub>1</sub> and unit cell parameters of <i>a</i> = 19.011(4), <i>b</i> = 6.0133(12), <i>c</i> = 9.5411(19) Å, <i>V</i> = 1090.7(4) Å<sup>3</sup>, and <i>Z</i> = 4. The structure consists of double ribbons of <i>M</i>(O,OH)<sub>6</sub>-octahedra (<i>M</i> = Cd2, Cd3, Cd4) extending along [010] interconnected by edge- and corner-shared <i>M</i>(O,OH)<sub>6</sub>-octahedra (<i>M</i> = Cd1, Cd5) and discrete, slightly distorted VO<sub>4</sub> tetrahedra, which form double chains of coupled polyhedra [V1O<sub>4</sub>–Cd5O<sub>4</sub>(OH)<sub>2</sub>–Cd1O<sub>5</sub>(OH)–V2O<sub>4</sub>]<sub>n</sub> running along the same direction. The interesting feature is the existence of V–Cd distances (3.0934(7) and 3.1081(7) Å for V1–Cd5 and V2–Cd1, respectively), which are shorter than the sum of the van der Waals radii of 3.71 Å. The V1–V2 distances of 4.1214(9) Å are also shorter than the sum of the van der Waals radii of 4.26 Å. The O–H···O hydrogen bonds additionally link the two subunits, ribbons, and chains into a three-dimensional structure. Raman spectra confirmed the presence of the hydrogen bonds and mutually isolated VO<sub>4</sub> groups. |
| first_indexed | 2024-03-09T16:03:20Z |
| format | Article |
| id | doaj.art-7cc2943fb7174d2087e6396da6327678 |
| institution | Directory Open Access Journal |
| issn | 2075-163X |
| language | English |
| last_indexed | 2024-03-09T16:03:20Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Minerals |
| spelling | doaj.art-7cc2943fb7174d2087e6396da63276782023-11-24T16:52:33ZengMDPI AGMinerals2075-163X2022-12-011212160110.3390/min12121601The Crystal Structure and Crystal Chemistry of Mineral-like Cd<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>, a Novel Isomorph of Arsenoclasite and GatehouseiteLjiljana Karanović0Tamara Ðorđević1Faculty of Mining and Geology, University of Belgrade, Ðušina 7, 11000 Belgrade, SerbiaInstitut für Mineralogie und Kristallographie, Universität Wien, Josef-Holaubek-Platz 2, 1090 Wien, AustriaThe pentacadmium bis(vanadate(V)) tetrahydroxide Cd<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub> was synthesized under hydrothermal conditions, and its crystal structure was determined with single-crystal X-ray diffraction. The investigated compound is the second known compound next to Cd(VO<sub>3</sub>)<sub>2</sub>·4H<sub>2</sub>O synthesized in the CdO–V<sub>2</sub>O<sub>5</sub>–H<sub>2</sub>O system and crystallizes isotypically to the minerals gatehouseite, Mn<sub>5</sub>(PO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>, and its As analog arsenoclasite, Mn<sub>5</sub>(AsO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>. Its symmetry is orthorhombic, with a space group of <i>P</i>2<sub>1</sub>2<sub>1</sub>2<sub>1</sub> and unit cell parameters of <i>a</i> = 19.011(4), <i>b</i> = 6.0133(12), <i>c</i> = 9.5411(19) Å, <i>V</i> = 1090.7(4) Å<sup>3</sup>, and <i>Z</i> = 4. The structure consists of double ribbons of <i>M</i>(O,OH)<sub>6</sub>-octahedra (<i>M</i> = Cd2, Cd3, Cd4) extending along [010] interconnected by edge- and corner-shared <i>M</i>(O,OH)<sub>6</sub>-octahedra (<i>M</i> = Cd1, Cd5) and discrete, slightly distorted VO<sub>4</sub> tetrahedra, which form double chains of coupled polyhedra [V1O<sub>4</sub>–Cd5O<sub>4</sub>(OH)<sub>2</sub>–Cd1O<sub>5</sub>(OH)–V2O<sub>4</sub>]<sub>n</sub> running along the same direction. The interesting feature is the existence of V–Cd distances (3.0934(7) and 3.1081(7) Å for V1–Cd5 and V2–Cd1, respectively), which are shorter than the sum of the van der Waals radii of 3.71 Å. The V1–V2 distances of 4.1214(9) Å are also shorter than the sum of the van der Waals radii of 4.26 Å. The O–H···O hydrogen bonds additionally link the two subunits, ribbons, and chains into a three-dimensional structure. Raman spectra confirmed the presence of the hydrogen bonds and mutually isolated VO<sub>4</sub> groups.https://www.mdpi.com/2075-163X/12/12/1601vanadiumcadmiumhydrothermal synthesiscrystal structurecrystal chemistry |
| spellingShingle | Ljiljana Karanović Tamara Ðorđević The Crystal Structure and Crystal Chemistry of Mineral-like Cd<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>, a Novel Isomorph of Arsenoclasite and Gatehouseite Minerals vanadium cadmium hydrothermal synthesis crystal structure crystal chemistry |
| title | The Crystal Structure and Crystal Chemistry of Mineral-like Cd<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>, a Novel Isomorph of Arsenoclasite and Gatehouseite |
| title_full | The Crystal Structure and Crystal Chemistry of Mineral-like Cd<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>, a Novel Isomorph of Arsenoclasite and Gatehouseite |
| title_fullStr | The Crystal Structure and Crystal Chemistry of Mineral-like Cd<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>, a Novel Isomorph of Arsenoclasite and Gatehouseite |
| title_full_unstemmed | The Crystal Structure and Crystal Chemistry of Mineral-like Cd<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>, a Novel Isomorph of Arsenoclasite and Gatehouseite |
| title_short | The Crystal Structure and Crystal Chemistry of Mineral-like Cd<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>, a Novel Isomorph of Arsenoclasite and Gatehouseite |
| title_sort | crystal structure and crystal chemistry of mineral like cd sub 5 sub vo sub 4 sub sub 2 sub oh sub 4 sub a novel isomorph of arsenoclasite and gatehouseite |
| topic | vanadium cadmium hydrothermal synthesis crystal structure crystal chemistry |
| url | https://www.mdpi.com/2075-163X/12/12/1601 |
| work_keys_str_mv | AT ljiljanakaranovic thecrystalstructureandcrystalchemistryofminerallikecdsub5subvosub4subsub2subohsub4subanovelisomorphofarsenoclasiteandgatehouseite AT tamaraðorđevic thecrystalstructureandcrystalchemistryofminerallikecdsub5subvosub4subsub2subohsub4subanovelisomorphofarsenoclasiteandgatehouseite AT ljiljanakaranovic crystalstructureandcrystalchemistryofminerallikecdsub5subvosub4subsub2subohsub4subanovelisomorphofarsenoclasiteandgatehouseite AT tamaraðorđevic crystalstructureandcrystalchemistryofminerallikecdsub5subvosub4subsub2subohsub4subanovelisomorphofarsenoclasiteandgatehouseite |