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Hydrothermal Single Crystal Growth and Structural Investigation of the Nepheline and Kalsilite Stuffed Tridymite Species

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Abstract

A series of high-quality single crystals of the formula NaxK1−xAlSiO4 were synthesized using a high temperature hydrothermal method. This enabled the detailed single crystal study of four examples of this class of compounds, namely KAlSiO4, Na0.10K0.90AlSiO4 Na3KAl4Si4O16 and NaAlSiO4. The potassium-containing species all had fully ordered AlO4 and SiO4 tetrahedral sites that led to formation of polar acentric structures. In contrast NaAlSiO4 displayed the unusual feature of an exceptionally large and complex unit cell along with complete disordering of the Al and Si sites. This led to the formation of a centrosymmetric structure, that is also a new polymorph of the NaAlSiO4 composition. The polymorphism of hydrothermal KAlSiO4 was also examined in light of the crystal’s synthetic and thermal histories. The study also revealed a structural sensitivity toward the degree of Na/K substitution in the lattice. The strong tendency to form polar acentric structures makes understanding these structures of great interest. These detailed structures resolved a considerable degree of previous structural ambiguity within this nominally simple class of compounds.

Graphical Abstract

Structural subtleties are examined in the nepheline–kalsilite series of NaxK1−xAlSiO4, revealing changes in the resulting structure according to synthetic method, thermal history, and alkali metal substitution.

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Data Availability

CCDC 2106945–2106948 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre and FIZ Karlsruhe via www.ccdc.cam.ac.uk/data_request/cif. The authors declare that all other data supporting the findings of this study are available within the article and its Supplementary Information files.

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Acknowledgements

We are indebted to the National Science Foundation NSF-DMR1808371 for financial support of the synthesis and crystal growth.

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Authors and Affiliations

  1. Department of Chemistry, Clemson University, Clemson, SC, 29634-0973, USA

    Rylan J. Terry, Colin D. McMillen & Joseph W. Kolis

  2. Center for Optical Materials Science and Engineering Technologies (COMSET), Clemson University, Clemson, SC, 29634-0973, USA

    Rylan J. Terry, Colin D. McMillen & Joseph W. Kolis

  3. 485 H.L. Hunter Laboratories, Clemson, SC, 29634, USA

    Joseph W. Kolis

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Correspondence to Joseph W. Kolis.

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Terry, R.J., McMillen, C.D. & Kolis, J.W. Hydrothermal Single Crystal Growth and Structural Investigation of the Nepheline and Kalsilite Stuffed Tridymite Species. J Chem Crystallogr 53, 25–37 (2023). https://doi.org/10.1007/s10870-022-00940-6

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