DOE OSTI2020
LiSi3 is Uranium Silicide-like structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. Li is bonded to twelve Si atoms to form LiSi12 cuboctahedra that share corners with four equivalent LiSi12 cuboctahedra, edges with eight equivalent LiSi12 cuboctahedra, edges with sixteen equivalent SiLi4Si8 cuboctahedra, faces with four equivalent LiSi12 cuboctahedra, and faces with eight equivalent SiLi4Si8 cuboctahedra. There are four shorter (2.65 Å) and eight longer (2.75 Å) Li–Si bond lengths. There are two inequivalent Si sites. In the first Si site, Si is bonded to four equivalent Li and eight Si atoms to form distorted SiLi4Si8 cuboctahedra that share corners with twelve equivalent SiLi4Si8 cuboctahedra, edges with eight equivalent LiSi12 cuboctahedra, edges with eight equivalent SiLi4Si8 cuboctahedra, faces with four equivalent LiSi12 cuboctahedra, and faces with ten equivalent SiLi4Si8 cuboctahedra. There are four shorter (2.65 Å) and four longer (2.75 Å) Si–Si bond lengths. In the second Si site, Si is bonded in a square co-planar geometry to four equivalent Li and eight equivalent Si atoms.