Abstract

Gold intermetallics are known for their unusual structures and bonding patterns. Two new compounds have been discovered in the cation-poor part of the Cs–Au–Ga system. Both compounds were obtained directly by heating the elements at elevated temperatures. Structure determinations based on single-crystal X-ray diffraction analyses revealed two structurally and compositionally related formations: CsAu1.4Ga2.8 (I) and CsAu2Ga2.6 (II) crystallize in their own structure types (I: R3, a = 11.160(2) A, c = 21.706(4) A, Z = 18; II: R3, a = 11.106(1) A, A, c = 77.243(9) A, Z = 54) and contain hexagonal cationic layers of cesium. This is a unique structural motif, which has never been observed for the other (lighter) alkali metals in combination with Au and post transition elements. The polyanionic part is characterized in contrast by Au/Ga tetrahedral stars, a structural feature that is characteristic for light alkali metal representatives, and disordered sites with mixed Au/Ga occupancies that occur in both str...

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