Zhitova, E.S.; Sheveleva, R.M.; Zolotarev, A.A.; Nuzhdaev, A.A. Atomic Arrangement, Hydrogen Bonding and Structural Complexity of Alunogen, Al2(SO4)3·17H2O, from Kamchatka Geothermal Field, Russia. Crystals2023, 13, 963.
Zhitova, E.S.; Sheveleva, R.M.; Zolotarev, A.A.; Nuzhdaev, A.A. Atomic Arrangement, Hydrogen Bonding and Structural Complexity of Alunogen, Al2(SO4)3·17H2O, from Kamchatka Geothermal Field, Russia. Crystals 2023, 13, 963.
Zhitova, E.S.; Sheveleva, R.M.; Zolotarev, A.A.; Nuzhdaev, A.A. Atomic Arrangement, Hydrogen Bonding and Structural Complexity of Alunogen, Al2(SO4)3·17H2O, from Kamchatka Geothermal Field, Russia. Crystals2023, 13, 963.
Zhitova, E.S.; Sheveleva, R.M.; Zolotarev, A.A.; Nuzhdaev, A.A. Atomic Arrangement, Hydrogen Bonding and Structural Complexity of Alunogen, Al2(SO4)3·17H2O, from Kamchatka Geothermal Field, Russia. Crystals 2023, 13, 963.
Abstract
Alunogen, Al2(SO4)3·17H2O, occurs as an efflorescent in acid mine drainage, low-temperature fumarolic or pseudofumarolic (at coal fires) terrestrial environments. It is considered as one of the main Al-sulfates of Martian soils demanding comprehensive crystal chemical data of natural terrestrial samples. However, structural studies of natural alunogen were carried out in 1970s without localization of H atoms and have not previously been performed for samples from geothermal fields, despite the fact that these environments are considered as proxies of the Martian conditions. The studied alunogen sample comes from Verkhne-Koshelevsky geothermal field (Koshelev volcano, Kamchatka, Russia). Its chemical formula is somewhat dehydrated, Al2(SO4)3×15.8 H2O. The crystal structure was solved and refined to R1 = 0.068 based on 5112 unique observed reflections with I > 2σ(I). Alunogen crystalizes in P-1 space group, a = 7.4194(3), b = 26.9763(9), c = 6.0549(2) Å, α = 90.043(3), β = 97.703(3), γ = 91.673(3) °, V = 1200.41(7) Å3, Z = 2. The crystal structure consists of isolated SO4 tetrahedra, Al(H2O)6 octahedra and H2O molecules connected by hydrogen bonds. The structure refinement includes Al, S and O positions that are similar to previous structure determinations and thirty-four H positions localized for the natural sample first. The study also shows the absence of isomorphic substitutions in the composition of alunogen despite the iron-enriched environment of mineral crystallization. The variability of the alunogen crystal structure is reflected in the number of “zeolite” H2O molecules and their splitting. The structure complexity of alunogen and its modifications ranges from 333-346 bits/cell for models with non-localized H atoms to 783-828 bits/cell for models with localized H atoms. The higher values correspond to higher hydration state of alunogen.
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