Re‐investigation of Barium‐Gold(I)‐Tetra‐Thiostannate(IV), Ba[Au 2 SnS 4 ], with Short Au I ···Au I Separation Showing Luminescence Properties

New investigations combining single crystal‐ and synchrotron‐based powder X‐ray diffraction data revealed that Ba[Au 2 SnS 4 ] crystallizes in the orthorhombic crystal system in space group C 222 1 instead of P 2 1 2 1 2 as reported earlier. While the principle crystal structure is not altered, there are significant differences of the interatomic distances Au‐S and Sn‐S. A salient property of this crystal structure is the partial framework composed of AuS 2 dumbbells and SnS 4 tetrahedra to form chains [(Au 2 SnS 4 ) 2– ] ∞ propagating in the [100] direction. Within the chains a short Au ··· Au separation of 2.9538(13) Å is observed, while the interchain Au ··· Au separation is longer at 3.383 Å. The Ba 2+ cation is eightfold coordinated by S 2– anions in a distorted bicapped trigonal prismatic environment BaS 8 . These polyhedra share all S 2– anions thus generating a three‐dimensional network. This connection Scheme generates voids along [100] hosting [(Au 2 SnS 4 ) 2– ] ∞ chains. In addition, the compound has been shown to be luminescent at the blue‐green spectral range with emission maximum at approximately 21000 cm –1 .