Synthesis, crystal structure, and electronic structure of Li2PbSiS4: a quaternary thiosilicate with a compressed chalcopyrite‐like structure

The new quaternary thio­silicate, Li2PbSiS4 (dilithium lead silicon tetra­sulfide), was prepared in an evacuated fused-silica tube via high-temperature, solid-state synthesis at 800 °C, followed by slow cooling. The crystal structure was solved and refined using single-crystal X-ray diffraction data. By strict definition, the title compound crystallizes in the stannite structure type; however, this type of structure can also be described as a compressed chalcopyrite-like structure. The Li+ cation lies on a crystallographic fourfold rotoinversion axis, while the Pb2+ and Si4+ cations reside at the inter­section of the fourfold rotoinversion axis with a twofold axis and a mirror plane. The Li+ and Si4+ cations in this structure are tetra­hedrally coordinated, while the larger Pb2+ cation adopts a distorted eight-coordinate dodeca­hedral coordination. These units join together via corner- and edge-sharing to create a dense, three-dimensional structure. Powder X-ray diffraction indicates that the title compound is the major phase of the reaction product. Electronic structure calculations, performed using the full potential linearized augmented plane wave method within density functional theory (DFT), indicate that Li2PbSiS4 is a semiconductor with an indirect bandgap of 2.22 eV, which compares well with the measured optical bandgap of 2.51 eV. The noncentrosymmetric crystal structure and relatively wide bandgap designate this compound to be of inter­est for IR nonlinear optics.