NaCo7.38(PO4)4Cl4 in a series of homeotype compounds with stable cationic substructures derived from the sulphohalite archetype

Yakubovich, O.; Kiriukhina, G.; Simonov, S.; Volkov, A.; Dimitrova, O.

Авторы: Yakubovich Olga, Kiriukhina Galina, Simonov Sergei, Volkov Anatoliy, Dimitrova Olga
Журнал: CrystEngComm
Том: 25
Номер: 43
Год издания: 2023
Издательство: Royal Society of Chemistry
Местоположение издательства: United Kingdom
Первая страница: 6006
Последняя страница: 6016
DOI: 10.1039/D3CE00819C
Аннотация: In this paper, we present the synthesis and characterization of a Cl-bearing member of the phosphate family of compounds with a tetragonal crystal structure and similar topology in the basic projection. The title compound was obtained under hydrothermal conditions and its crystal structure was determined by single crystal low temperature X-ray diffraction. The structure of NaCo7.38(PO4)4Cl4 is formed with CoO4Cl2octahedra sharing faces and assembled into eight-component ring clusters with a very short Co–Co distance of 3.014 Å. These clusters are linked in a three-periodic network via vertex-bridge contacts of adjacent octahedra and PO4 tetrahedra. Na atoms occupy the open channels of the framework. Thestructure is discussed as a derivative of cubic sulphohalite, Na6(SO4)2ClF, with the symmetry lowering from the widespread Fm3¯m space group of sulphohalite to the tetragonal acentric space group I-42m in our case; these space groups are symmetrically related by subordination “group → subgroup”. Theoreticalcalculations of possible pathways of Na migration through the framework showed that although the structure contains a sufficient number of voids for sodium ions, their migration is limited by the size of the channels. However, the obtained results indicated that the migration of Li+ ions is very likely through a two-periodic network parallel to the ab plane, which means that Li-containing structural varieties of NaCo7.38PO4)Cl4 with possible formulae Li5Co2+Co3+3PO4)Cl4 or Li4Co3+4PO44Cl4 canpossess ionic conductivity. The angle of intracluster Co–O–Co bonds of 105.4° allows us to assume that there is an antiferromagnetic exchange interaction between the Co atoms, and we assume that the intercluster exchange interactions between Co2+/3+ ions through the intermediate PO4 groups are also probable.
Добавил в систему: Якубович Ольга Всеволодовна

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NaCo7.38(PO4)4Cl4 in a series of homeotype compounds with stable cationic substructures derived from the sulphohalite archetypeстатья

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