Zn[sub.2]Cl[sub.2], 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

• Published in: Minerals (Basel) Vol. 13; no. 8
• Main Authors: Zolotarev, Andrey A, Avdontceva, Margarita S, Sheveleva, Rezeda M, Pekov, Igor V, Vlasenko, Natalia S, Bocharov, Vladimir N, Krzhizhanovskaya, Maria G, Zolotarev, Anatoly A, Rassomakhin, Mikhail A, Krivovichev, Sergey V
• Format: Journal Article
• Language: English
• Published: MDPI AG 01.08.2023
• Subjects: Crystals; Structure; Zinc; Russia
• ISSN: 2075-163X; 2075-163X
• DOI: 10.3390/min13081109

The mineral-like anthropogenic phase Zn(NH[sub.3])[sub.2]Cl[sub.2], with ammine (NH[sub.3] [sup.0]) 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(NH[sub.3])[sub.2]Cl[sub.2] is orthorhombic, Imma, a = 7.7399(6), b = 8.0551(5), c = 8.4767(8) Å, V = 528.49(7) Å[sup.3], R[sub.1] = 0.0388 at −73 °C. Its crystal structure is based upon isolated ZnN[sub.2]Cl[sub.2] tetrahedra connected by hydrogen bonds (between NH[sub.3] groups and Cl atoms) into a three-dimensional network. Upon heating, the Zn(NH[sub.3])[sub.2]Cl[sub.2] 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(NH[sub.3])Cl[sub.2] 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, CuCl[sub.2](NH[sub.3])[sub.2]. The studied anthropogenic phase, formed in the unique conditions of burned coal dumps, is identical to the synthetic Zn(NH[sub.3])[sub.2]Cl[sub.2].