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The new ternary sulfide Sn 2 SiS 4 has been synthesized via high-temperature solid state reaction. It crystallizes in the centrosymmetric space group P2 1 / c of the monoclinic system. In the structure, the Sn 2+ cations are coordinated to a heavily-distorted octahedron of six S atoms or a pentagonal pyramid of six S atoms, both geometries clearly demonstrating the effect of the stereo-chemically active electron lone pair on the Sn coordination environment. These SnS 6 polyhedra and the SiS 4 tetrahedra are connected to each other via corner and edge-sharing to generate a three-dimensional framework. Based on the diffuse reflectance measurement and the electronic structure calculation, Sn 2 SiS 4 has an indirect band gap of 2.00 eV. Interestingly, Sn 2 SiS 4 exhibits an efficient visible-light-driven photocatalytic activity pertaining to Rhodamine B (RhB) degradation, which is superior to the important photocatalyst C 3 N 4 . Moreover, the photocatalytic mechanism was also elucidated based on the active species trapping experiments. [ABSTRACT FROM AUTHOR]