Hydrothermally synthesized first acentric apatite (Bi5Na5)[PO4]6Cl2 with wide Bi–Na isomorphism and doubled c-axis

Elena L. Belokoneva; Anatoly S. Volkov; Olga V. Dimitrova; Sergey Yu. Stefanovich; Nadezhda B. Govorko

doi:10.1039/D4NJ00480A

Hydrothermally synthesized first acentric apatite (Bi₅Na₅)[PO₄]₆Cl₂ with wide Bi–Na isomorphism and doubled c-axis†

Elena L. Belokoneva,

*^a Anatoly S. Volkov,

^b Olga V. Dimitrova,

^a Sergey Yu. Stefanovich^c and Nadezhda B. Govorko^a

Author affiliations

* Corresponding authors

^a Department of Crystallography and Crystal Chemistry, Geological Faculty, Lomonosov Moscow State University, Moscow, Russia
E-mail: elbel@geol.msu.ru
Tel: +7-495-939-4926

^b Skolkovo Institute of Science and Technology, Moscow, Russia

^c Laboratory of Functional Materials, Chemical Faculty, Lomonosov Moscow State University, Moscow, Russia

Abstract

New acentric bismuth-sodium apatite (Bi₅Na₅)[PO₄]₆Cl₂ with doubled c-axis and space group P [6 with combining macron] is obtained first under mild hydrothermal conditions in excess of NaCl in solution. Structural solution was carried out on single crystal. The new apatite demonstrated wide heterovalence isomorphic substitution of Bi³⁺–Na⁺ in large cation positions, which allowed the final chemical formula to be established. This fact determines the doubling of the c-axis and the new space group P [6 with combining macron] compared with other widely known apatites. Non-centrosymmetry of the structure agrees with a distinct effect of optical second harmonic generation, but the SHG intensity is small due to proximity to the parent centrosymmetric apatite structure as well as lack of phase matching for SHG and YAG:Nd laser emission. From a structural viewpoint, optical nonlinearity is determined by the difference in the isomorphic occupation of positions by large cations, with a slight deviation from the centrosymmetry of the whole structure. Disordered structural variants of isomorphic apatites are predicted, and a group–subgroup relation is found for three apatite variants: one well known and two new.

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Article information

DOI: https://doi.org/10.1039/D4NJ00480A
Article type: Paper
Submitted: 29 Jan 2024
Accepted: 21 Mar 2024
First published: 10 Apr 2024

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New J. Chem., 2024,48, 7940-7945

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Hydrothermally synthesized first acentric apatite (Bi₅Na₅)[PO₄]₆Cl₂ with wide Bi–Na isomorphism and doubled c-axis

E. L. Belokoneva, A. S. Volkov, O. V. Dimitrova, S. Yu. Stefanovich and N. B. Govorko, New J. Chem., 2024, 48, 7940 DOI: 10.1039/D4NJ00480A

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