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Silesiaite, ideally Ca2Fe3+Sn(Si2O7)(Si2O6OH), a new species in the kristiansenite group: crystal chemistry and structure of holotype silesiaite from Szklarska Poręba, Poland, and Sc-free silesiaite from Häiviäntien, Finland

Published online by Cambridge University Press:  25 January 2023

Adam Pieczka Open the ORCID record for Adam Pieczka [Opens in a new window] ,
Sylwia Zelek-Pogudz Open the ORCID record for Sylwia Zelek-Pogudz [Opens in a new window] ,
Bożena Gołębiowska Open the ORCID record for Bożena Gołębiowska [Opens in a new window] ,
Katarzyna M. Stadnicka Open the ORCID record for Katarzyna M. Stadnicka [Opens in a new window]  and
Roy Kristiansen
Adam Pieczka*
Affiliation:
Department of Mineralogy, Petrography and Geochemistry, AGH University of Science and Technology, Mickiewicza 30, 30-059 Kraków, Poland
Sylwia Zelek-Pogudz
Affiliation:
Department of Mineralogy, Petrography and Geochemistry, AGH University of Science and Technology, Mickiewicza 30, 30-059 Kraków, Poland
Bożena Gołębiowska
Affiliation:
Department of Mineralogy, Petrography and Geochemistry, AGH University of Science and Technology, Mickiewicza 30, 30-059 Kraków, Poland
Katarzyna M. Stadnicka
Affiliation:
Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Kraków, Poland
Roy Kristiansen
Affiliation:
Retired chemical engineer, N-1650 Sellebakk, Norway
*
*Author for correspondence: Adam Pieczka, Email: pieczka@agh.edu.pl
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Abstract

Two silesiaite crystals, one from Szklarska Poręba, Poland (type locality), and the other from Häiviäntien, Finland, were studied with electron-probe microanalysis, Raman spectroscopy and single-crystal X-ray diffraction. The crystals have the following compositions normalised to 13 O2– + 1 (OH)– anions: Ca2.001(2)[(Sn1.105(6)Zr0.009(1))Σ1.114(Fe3+0.523(78)Sc0.185(62)Al0.070(14))Σ0.779(Fe2+0.065(12)Mn2+0.041(5)Mg0.003(3))Σ0.110]Σ2.003(Si3.997(2)O13OH), and Ca2.006(8)[(Sn1.110(18)Ti0.006(3))Σ1.107(Fe3+0.648(50)Al0.063(11))Σ0.710(Fe2+0.140(30)Mn2+0.011(3)Mg0.005(2))Σ0.155(Nb0.020(6)Ta0.011(3))Σ0.040]Σ2.009(Si3.991(14)O13OH), respectively. The structure of the crystals was refined in the triclinic system with unconventional space-group symmetry C1 to R1 = 2.02% and 3.56%, respectively. The unit cells were found to be a = 10.0080(2), b = 8.3622(1), c = 13.2994(2) Å, α = 89.987(1), β = 109.095(2), γ = 89.978(1)° and V = 1051.77(3) Å3 for silesiaite from Szklarska Poręba, and a = 9.9985(3), b = 8.3446(2), c = 13.2760(4) Å, α = 89.986(3), β = 109.122(2), γ = 90.020(2)° and V = 1046.55(5) Å3 for silesiaite from Häiviäntien. In both crystals, the Ca sites are occupied solely by calcium and Si sites by silicon atoms. Optimised occupancies of the four M sites indicated slightly different site fillings. In the Szklarska Poręba silesiaite, the M1 site is predominantly occupied by trivalent Fe + Sc and the M2–M4 sites by Sn. In contrast, in the Häiviäntien silesiaite, the M1–M3 sites are Sn-dominant, while Fe3+ predominantly occupies the M4 site. The differences can be considered a result of an evolution of the M1–M4 site occupancies following a decrease of the <M–O> distance. Among the minerals of the kristiansenite group, Sc-free silesiaite from the Häiviäntien pegmatite has the smallest average radius of M-site cations and a unit-cell volume that increases proportionally to the (Fe2+ ± Sc) content. The hydrogen atoms form moderate hydrogen bonds between disilicate groups (Si2O7 and Si2O6OH) linked in rows along [101], indicating the presence of one hydroxyl in the formula calculated for Z = 4. All three kristiansenite-group species, i.e. silesiaite, kozłowskiite and kristiansenite, are isostructural.

Keywords

silesiaitekristiansenite groupcrystal chemistrysingle-crystal structure determination
Type
Article
Information
Mineralogical Magazine , Volume 87 , Issue 2 , April 2023 , pp. 271 - 283
Copyright
Copyright © The Author(s), 2023. Published by Cambridge University Press on behalf of The Mineralogical Society of Great Britain and Ireland

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Footnotes

Associate Editor: Ian Terence Graham

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