Zn(NH3)2Cl2, a Mineral-like Anthropogenic Phase with Ammine Complexes from the Burned Dumps of the Chelyabinsk Coal Basin, South Urals, Russia: Crystal Structure, Spectroscopy and Thermal Evolution
Author:
Zolotarev Andrey A.1ORCID, Avdontceva Margarita S.1ORCID, Sheveleva Rezeda M.1ORCID, Pekov Igor V.2, Vlasenko Natalia S.3, Bocharov Vladimir N.3ORCID, Krzhizhanovskaya Maria G.1, Zolotarev Anatoly A.1, Rassomakhin Mikhail A.4ORCID, Krivovichev Sergey V.15ORCID
Affiliation:
1. Institute of Earth Sciences, St. Petersburg State University, 199034 St. Petersburg, Russia 2. Faculty of Geology, Moscow State University, 119991 Moscow, Russia 3. Centre for Geo-Environmental Research and Modelling, St. Petersburg State University, 199034 St. Petersburg, Russia 4. South Urals Federal Research Center of Mineralogy and Geoecology of UB RAS, 456317 Miass, Russia 5. Nanomaterials Research Centre, Kola Science Center, Russian Academy of Sciences, 184209 Apatity, Russia
Abstract
The mineral-like anthropogenic phase Zn(NH3)2Cl2, with ammine (NH30) complexes from the burned dumps of the Chelyabinsk coal basin (South Urals, Russia), has been investigated using single-crystal and high-temperature powder X-ray diffraction, and Raman and infrared (IR) spectroscopy. The anthropogenic Zn(NH3)2Cl2 is orthorhombic, Imma, a = 7.7399(6), b = 8.0551(5), c = 8.4767(8) Å, V = 528.49(7) Å3, R1 = 0.0388 at −73 °C. Its crystal structure is based upon isolated ZnN2Cl2 tetrahedra connected by hydrogen bonds (between NH3 groups and Cl atoms) into a three-dimensional network. Upon heating, the Zn(NH3)2Cl2 phase is stable up to about 150 °C, which is in good agreement with the data on the temperature of its formation. The crystal structure of Zn(NH3)Cl2 expands anisotropically with the strongest thermal expansion observed along the a axis. The thermal expansion of the structure is controlled by the changes in the hydrogen bonding system. The Raman and IR spectroscopic characteristics of this phase are close to those of the mineral ammineite, CuCl2(NH3)2. The studied anthropogenic phase, formed in the unique conditions of burned coal dumps, is identical to the synthetic Zn(NH3)2Cl2.
Funder
Russian Science Foundation
Subject
Geology,Geotechnical Engineering and Engineering Geology
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