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.