Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub>—An Anthropogenic Phase from Burnt Mine Dumps of the Chelyabinsk Coal Basin: Crystal Structure Refinement, Spectroscopic Study and Thermal Evolution
The mineral-like phase Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub>, an anthropogenic anhydrous calcium chlorine-silicate from the Chelyabinsk coal basin has been investigated using single-crystal and high-temperature powder X-ray diffraction and Raman spectroscopy...
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MDPI AG
2023-05-01
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| author | Anastasia S. Brazhnikova Margarita S. Avdontceva Andrey A. Zolotarev Maria G. Krzhizhanovskaya Vladimir N. Bocharov Vladimir V. Shilovskikh Mikhail A. Rassomakhin Vladislav V. Gurzhiy Sergey V. Krivovichev |
| author_facet | Anastasia S. Brazhnikova Margarita S. Avdontceva Andrey A. Zolotarev Maria G. Krzhizhanovskaya Vladimir N. Bocharov Vladimir V. Shilovskikh Mikhail A. Rassomakhin Vladislav V. Gurzhiy Sergey V. Krivovichev |
| author_sort | Anastasia S. Brazhnikova |
| collection | DOAJ |
| description | The mineral-like phase Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub>, an anthropogenic anhydrous calcium chlorine-silicate from the Chelyabinsk coal basin has been investigated using single-crystal and high-temperature powder X-ray diffraction and Raman spectroscopy. The empirical formula of this phase was calculated as Ca<sub>2.96</sub>[(Si<sub>0.98</sub>P<sub>0.03</sub>)<sub>Σ1.01</sub>O<sub>4</sub>]Cl<sub>2</sub>, in good agreement with its ideal formula. Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub> is monoclinic, space group <i>P</i>2<sub>1</sub>/<i>c</i>, Z = 4, <i>a</i> = 9.8367(6) Å, <i>b</i> = 6.7159(4) Å, <i>c</i> = 10.8738(7) Å, <i>β</i> = 105.735(6)°, <i>V</i> = 691.43(8) Å<sup>3</sup>. The crystal structure is based upon the pseudo-layers formed by Ca–O and Si–O bonds separated by Cl atoms. The pseudo-layers are parallel to the (100) plane. The crystal structure of Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub> was refined (R<sub>1</sub> = 0.037) and stable up to 660 °C; it expands anisotropically with the direction of the strongest thermal expansion close to parallel to the [−101] direction, which can be explained by the combination of thermal expansion and shear deformations that involves the ‘gliding’ of the Ca silicate layers relative to each other. The Raman spectrum of the compound contains the following bands (cm<sup>–1</sup>): 950 (ν<sub>3</sub>), 848 (ν<sub>1</sub>), 600 (ν<sub>4</sub>), 466 (ν<sub>2</sub>), 372 (ν<sub>2</sub>). The bands near 100–200 cm<sup>−1</sup> can be described as lattice modes. The compound had also been found under natural conditions in association with chlorellestadite. |
| first_indexed | 2024-03-11T03:27:50Z |
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| language | English |
| last_indexed | 2024-03-11T03:27:50Z |
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| spelling | doaj.art-e010c519da884176a8788ca26cec340c2023-11-18T02:36:52ZengMDPI AGMinerals2075-163X2023-05-0113566810.3390/min13050668Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub>—An Anthropogenic Phase from Burnt Mine Dumps of the Chelyabinsk Coal Basin: Crystal Structure Refinement, Spectroscopic Study and Thermal EvolutionAnastasia S. Brazhnikova0Margarita S. Avdontceva1Andrey A. Zolotarev2Maria G. Krzhizhanovskaya3Vladimir N. Bocharov4Vladimir V. Shilovskikh5Mikhail A. Rassomakhin6Vladislav V. Gurzhiy7Sergey V. Krivovichev8Department of Crystallography, Institute of Earth Sciences, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, RussiaDepartment of Crystallography, Institute of Earth Sciences, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, RussiaDepartment of Crystallography, Institute of Earth Sciences, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, RussiaDepartment of Crystallography, Institute of Earth Sciences, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, RussiaCentre for Geo-Environmental Research and Modelling, St. Petersburg State University, Ulyanovskaya St., 1, 198504 St. Petersburg, RussiaCentre for Geo-Environmental Research and Modelling, St. Petersburg State University, Ulyanovskaya St., 1, 198504 St. Petersburg, RussiaSouth Urals Federal Research Center of Mineralogy and Geoecology of Ural Branch of the Russian Academy of Sciences, 456317 Miass, RussiaDepartment of Crystallography, Institute of Earth Sciences, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, RussiaDepartment of Crystallography, Institute of Earth Sciences, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, RussiaThe mineral-like phase Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub>, an anthropogenic anhydrous calcium chlorine-silicate from the Chelyabinsk coal basin has been investigated using single-crystal and high-temperature powder X-ray diffraction and Raman spectroscopy. The empirical formula of this phase was calculated as Ca<sub>2.96</sub>[(Si<sub>0.98</sub>P<sub>0.03</sub>)<sub>Σ1.01</sub>O<sub>4</sub>]Cl<sub>2</sub>, in good agreement with its ideal formula. Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub> is monoclinic, space group <i>P</i>2<sub>1</sub>/<i>c</i>, Z = 4, <i>a</i> = 9.8367(6) Å, <i>b</i> = 6.7159(4) Å, <i>c</i> = 10.8738(7) Å, <i>β</i> = 105.735(6)°, <i>V</i> = 691.43(8) Å<sup>3</sup>. The crystal structure is based upon the pseudo-layers formed by Ca–O and Si–O bonds separated by Cl atoms. The pseudo-layers are parallel to the (100) plane. The crystal structure of Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub> was refined (R<sub>1</sub> = 0.037) and stable up to 660 °C; it expands anisotropically with the direction of the strongest thermal expansion close to parallel to the [−101] direction, which can be explained by the combination of thermal expansion and shear deformations that involves the ‘gliding’ of the Ca silicate layers relative to each other. The Raman spectrum of the compound contains the following bands (cm<sup>–1</sup>): 950 (ν<sub>3</sub>), 848 (ν<sub>1</sub>), 600 (ν<sub>4</sub>), 466 (ν<sub>2</sub>), 372 (ν<sub>2</sub>). The bands near 100–200 cm<sup>−1</sup> can be described as lattice modes. The compound had also been found under natural conditions in association with chlorellestadite.https://www.mdpi.com/2075-163X/13/5/668Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub>anthropogenic mineralcrystal structureRamanthermal behavior |
| spellingShingle | Anastasia S. Brazhnikova Margarita S. Avdontceva Andrey A. Zolotarev Maria G. Krzhizhanovskaya Vladimir N. Bocharov Vladimir V. Shilovskikh Mikhail A. Rassomakhin Vladislav V. Gurzhiy Sergey V. Krivovichev Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub>—An Anthropogenic Phase from Burnt Mine Dumps of the Chelyabinsk Coal Basin: Crystal Structure Refinement, Spectroscopic Study and Thermal Evolution Minerals Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub> anthropogenic mineral crystal structure Raman thermal behavior |
| title | Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub>—An Anthropogenic Phase from Burnt Mine Dumps of the Chelyabinsk Coal Basin: Crystal Structure Refinement, Spectroscopic Study and Thermal Evolution |
| title_full | Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub>—An Anthropogenic Phase from Burnt Mine Dumps of the Chelyabinsk Coal Basin: Crystal Structure Refinement, Spectroscopic Study and Thermal Evolution |
| title_fullStr | Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub>—An Anthropogenic Phase from Burnt Mine Dumps of the Chelyabinsk Coal Basin: Crystal Structure Refinement, Spectroscopic Study and Thermal Evolution |
| title_full_unstemmed | Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub>—An Anthropogenic Phase from Burnt Mine Dumps of the Chelyabinsk Coal Basin: Crystal Structure Refinement, Spectroscopic Study and Thermal Evolution |
| title_short | Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub>—An Anthropogenic Phase from Burnt Mine Dumps of the Chelyabinsk Coal Basin: Crystal Structure Refinement, Spectroscopic Study and Thermal Evolution |
| title_sort | ca sub 3 sub sio sub 4 sub cl sub 2 sub an anthropogenic phase from burnt mine dumps of the chelyabinsk coal basin crystal structure refinement spectroscopic study and thermal evolution |
| topic | Ca<sub>3</sub>SiO<sub>4</sub>Cl<sub>2</sub> anthropogenic mineral crystal structure Raman thermal behavior |
| url | https://www.mdpi.com/2075-163X/13/5/668 |
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