A new type of copper-oxide cluster in the crystal structure of NaCu12(Si2O7)4Cl, a new representative of the alkali copper disilicate family

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Abstract

A new compound NaCu12(Si2O7)4Cl was synthesized by chemical deposition from gases. Using X-ray diffraction analysis, its crystal structure was established as containing 0-dimensional copper-oxide clusters Cu12O24 of a new type, which can be described as a truncated tetragonal bipyramid built from CuO4 square groups connected by sharing common edges and vertices. The complexes are combined through the Si2O7 disilicate groups into a three-dimensional electroneutral framework [[Cu12(Si2O7)4]0, built on the principle of the bcc grid (body-centered cubic lattice). In the cavities of the framework disordered Na+ and Cl– ions are located. The structure of the 12-nucleated copper-oxide clusters is similar to those of the CunO2n polyoxocuprates found in various minerals and inorganic compounds.

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About the authors

I. V. Kornyakov

Kola Science Centre, Russian Academy of Sciences; St. Petersburg State University

Email: s.krivovichev@ksc.ru

Nanomaterials Research Centre, Kola Science Centre, Russian Academy of Sciences; Institute of Earth Sciences, St. Petersburg State University

Russian Federation, Apatity; St. Petersburg

S. V. Krivovichev

Kola Science Centre, Russian Academy of Sciences; St. Petersburg State University

Author for correspondence.
Email: s.krivovichev@ksc.ru

Nanomaterials Research Centre, Kola Science Centre, Russian Academy of Sciences; Institute of Earth Sciences, St. Petersburg State University

Russian Federation, Apatity; St. Petersburg

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Supplementary files

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2. Fig. 1. Island complex of CuO4 squares (a), the mode of attachment of disilicate groups to the copper-oxygen complex (b) and the crystal structure of NaCu12(Si2O7)4Cl (c). Ellipsoids of thermal displacements of atoms are shown at the 50% probability level.

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3. Fig. 2. Difference maps of electron density in cavities inside the copper-oxygen complex (a) and between disilicate groups (b).

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4. Fig. 3. Types of polyoxocuprate clusters observed in the structures: a – NaCu12(Si2O7)4Cl, b – chertnerite, c – boleite, d – kumengeite. Oxygen atoms are indicated by balls, copper squares are shown.

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