Pseudosymmetry and cation ordering in heterophyllosilicates. 2. Refinement of the crystal structure of Ca-bearing mineral of the perraultite series
https://doi.org/10.24930/1681-9004-2025-25-2-221-237
EDN: YIZYIC
Abstract
Object of Study. The symmetry and the choice of the space group (sp. gr.) for the structures of perraultite and related minerals – bafertisite-like Mn/Fe-Ti heterophyllosilicates with ordered alkali and alkaline earth cations is still under discussion. In the present work, the crystal structure of the Ca-containing member of the perraultite series is studied.
Materials and Methods. The mineral perraultite used in this research was collected from the Oktyabrsky alkaline massif (Northern Azov Sea region). The crystal structure of the sample was studied using single crystal X-ray diffraction analysis. The parameters of the monoclinic unit cell are: a = 10.7230(3) Å, b = 13.8313(4) Å, c = 20.8178(7) Å, β = 95.0348(3)°, V = 3075.638(15) Å3.
Results. The crystal structure of perraultite was refined within two space groups, C2 and C2/m, using data sets for 5120 and 2948 independent reflections with I > 3σ(I), respectively. The final R-factor values were 4.66 % for the sp. gr. C2 and 4.84 % for sp. gr. C2/m. For the structural model refined using the sp. gr. C2 the crystal chemical formula is (Z = 2): A1(Ba) A2(Ba0.64K0.36)2 A3(K0.87Ba0.13) B1(Na0.70Ca0.30) B2(Na0.70Ca0.30) B3(Na0.90Ca0.10)2 [M1(Mn0.50Fe2+0.40Zn0.10) M2(Mn0.60Fe2+0.30Zn0.10) M3(Mn0.50Fe2+0.50) M4(Mn0.70Fe2+0.30) M5(Mn0.50Fe2+0.50) M6(Mn0.60Fe2+0.40) M7(Mn0.60Fe2+0.40) M8(Mn0.70Fe2+0.30) (OH)4]2 [Ti1(Ti0.91Nb0.09) Ti2(Ti0.91Nb0.09) Ti3(Ti0.77Nb0.13Zr0.10) Ti4(Ti0.91Nb0.09) (Si2O7)4O4F2]2, where square brackets denote the main structural fragments.
Conclusions. The sp. gr. C2 is proposed as more suitable for describing the perrotite-type structure, since it allows better identification of the features of the occupancy of positions within the HOH modules. The studied mineral from the Oktyabrsky massif is a F-dominant analogue of perraultite, differing from the latter also by the presence of calcium, a high iron content and a low niobium content.
Keywords
pseudosymmetry,
cationic ordering,
crystal structure,
perraultite,
surkhobite,
bafertisite group,
heterophyllosilicate,
Oktyabrskiy alkaline massif
Supporting agencies: This work supported by the Russian Science Foundation, grant No. 20-77-10065-П (X-ray structural and topological analysis and refinement of crystal structures. Mineralogical investigations were performed in accordance with the state tasks Nos. 124013100858-3 and 121061600049-4. Crystal chemical analysis of minerals was carried out partially within were performed in accordance with the state tasks of the NRC Kurchatov Institute
About the Authors
G. S. Ilyin
Federal Research Center “Kola Science Center RAS”
Russian Federation
Russian Federation
Grigory S. Ilyin
Laboratory of Arctic Mineralogy and Material Sciences
184209; 14 Fersman st.; Apatity
N. V. Chukanov
Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, RAS
Russian Federation
Russian Federation
Nikita V. Chukanov
142432; 1 Academician Semenov av.; Chernogolovka
I. V. Pekov
Moscow State University
Russian Federation
Russian Federation
Igor V. Pekov
Faculty of Geology
119991; 1 Leninskie Gory; Moscow
N. A. Yamnova
Moscow State University
Russian Federation
Russian Federation
Natalia A. Yamnova
Faculty of Geology
119991; 1 Leninskie Gory; Moscow
R. K. Rastsvetaeva
Kurchatov Complex of Crystallography and Photonics, NRC Kurchatov Institute
Russian Federation
Russian Federation
Ramiza K. Rastsvetaeva
199333; 59 Leninskii av.; Mosсow
V. O. Yapaskurt
Moscow State University
Russian Federation
Russian Federation
Vasiliy O. Yapaskurt
Faculty of Geology
119991; 1 Leninskie Gory; Moscow
S. M. Aksenov
Federal Research Center “Kola Science Center RAS”; Kurchatov Complex of Crystallography and Photonics, NRC Kurchatov Institute
Russian Federation
Russian Federation
Sergey M. Aksenov
Laboratory of Arctic Mineralogy and Material Sciences
184209; 14 Fersman st.; Apatity; 199333; 59 Leninskii av.; Mosсow
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Review
For citations:
Ilyin G.S., Chukanov N.V., Pekov I.V., Yamnova N.A., Rastsvetaeva R.K., Yapaskurt V.O., Aksenov S.M. Pseudosymmetry and cation ordering in heterophyllosilicates. 2. Refinement of the crystal structure of Ca-bearing mineral of the perraultite series. LITHOSPHERE (Russia). 2025;25(2):221-237. (In Russ.) https://doi.org/10.24930/1681-9004-2025-25-2-221-237. EDN: YIZYIC
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