Abstract

White opaque single crystals of Na6Ge2S6O were obtained serendipitously during the preparation of Na4GeS4. Then, pure glass and ceramic Na6Ge2S6O samples were synthesized from Na2S, GeS2, and GeO2 reagents. The crystal structure was determined from powder and single crystal X-ray diffraction data. The physical properties were characterized by TG-DTA, SEM-EDX, Raman spectroscopy and electrochemical impedance spectroscopy. Na6Ge2S6O crystallizes with a new type of structure in the non-centro-symmetric space group P212121, a = 6.96882 (6) Å, b = 7.04159 (6) Å, c = 26.7069 (2) Å, V = 1310.55 (2) Å3 and Z = 4. The asymmetric unit is built up of six Na+ cations surrounding a bi-tetrahedral complex anion, [S3GeOGeS3]6−, which adopts a staggered conformation. The strongly distorted sodium polyhedra share edges and/or faces. The electrical conductivities of Na6Ge2S6O glass and ceramic at 25 °C are 2.9 × 10−5 S cm−1 (Ea = 0.47 eV) and 1.8 × 10−7 S cm−1 (Ea = 0.43 eV), respectively.

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