Syntheses and crystal structures of the quaternary thiogermanates Cu4FeGe2S7 and Cu4CoGe2S7

Citation for published article

Craig, A. J., Stoyko, S. S., Bonnoni, A., & Aitken, J. A. (2020). Syntheses and crystal structures of the quaternary thio­germanates Cu4FeGe2S7 and Cu4CoGe2S7. Acta Crystallographica Section E: Crystallographic Communications, 76(7), 1117–1121. https://doi.org/10.1107/S2056989020007872

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DOI

10.1107/S2056989020007872

Peer Reviewed

1

Document Type

Journal Article

Publication Date

7-1-2020

Publication Title

Acta Crystallographica Section E: Crystallographic Communications

Keywords

crystal structure, diamond-like, Division of Materials Research 1611198 CHE-0234872 DUE-0511444 Jennifer A. Aitken, quaternary sulfide National Science Foundation, thiogermanate

School

Bayer School of Natural and Environmental Sciences

Primary Author Department

Chemistry and Biochemistry

Abstract

© 2020. The quaternary thiogermanates Cu4FeGe2S7 (tetracopper iron digermanium heptasulfide) and Cu4CoGe2S7 (tetracopper cobalt digermanium heptasulfide) were prepared in evacuated fused-silica ampoules via high-temperature, solid-state synthesis using stoichiometric amounts of the elements at 1273K. These isostructural compounds crystallize in the Cu4NiSi2S7 structure type, which can be considered as a superstructure of cubic diamond or sphalerite. The monovalent (Cu+), divalent (Fe2+ or Co2+) and tetravalent (Ge4+) cations adopt tetrahedral geometries, each being surrounded by four S2- anions. The divalent cation and one of the sulfide ions lie on crystallographic twofold axes. These tetrahedra share corners to create a three-dimensional framework structure. All of the tetrahedra align along the same crystallographic direction, rendering the structure non-centrosymmetric and polar (space group C2). Analysis of X-ray powder diffraction data revealed that the structures are the major phase of the reaction products. Thermal analysis indicated relatively high melting temperatures, near 1273K.

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© 2020

Open Access

Gold

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