Li2Si crystallizes in the trigonal R-3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal non-coplanar geometry to six equivalent Si(1) atoms. In the second Li site, Li(2) is bonded to four equivalent Si(1) atoms to form a mixture of distorted edge and corner-sharing LiSi4 tetrahedra. Si(1) is bonded in a 11-coordinate geometry to four equivalent Li(2), six equivalent Li(1), and one Si(1) atom.
Li2Si crystallizes in the trigonal R-3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal non-coplanar geometry to six equivalent Si(1) atoms. There are three shorter (2.59 Å) and three longer (2.98 Å) Li(1)-Si(1) bond lengths. In the second Li site, Li(2) is bonded to four equivalent Si(1) atoms to form a mixture of distorted edge and corner-sharing LiSi4 tetrahedra. There is one shorter (2.64 Å) and three longer (2.79 Å) Li(2)-Si(1) bond lengths. Si(1) is bonded in a 11-coordinate geometry to four equivalent Li(2), six equivalent Li(1), and one Si(1) atom. The Si(1)-Si(1) bond length is 2.26 Å.