Li4GeS4 is Aluminum carbonitride-like structured and crystallizes in the orthorhombic Pnma space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form LiS4 tetrahedra that share corners with two equivalent Li(3)S6 octahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with eight equivalent Li(2)S4 trigonal pyramids, edges with two equivalent Li(3)S6 octahedra, and  an edgeedge with one Ge(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. In the second Li site, Li(2) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted LiS4 trigonal pyramids that share corners with three equivalent Li(3)S6 octahedra, corners with four equivalent Li(1)S4 tetrahedra, corners with four equivalent Ge(1)S4 tetrahedra, corners with four equivalent Li(2)S4 trigonal pyramids, and  a faceface with one Li(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 19-53°. In the third Li site, Li(3) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted LiS6 octahedra that share corners with two equivalent Li(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with six equivalent Li(2)S4 trigonal pyramids, edges with two equivalent Li(3)S6 octahedra, edges with two equivalent Li(1)S4 tetrahedra, edges with two equivalent Ge(1)S4 tetrahedra, and faces with two equivalent Li(2)S4 trigonal pyramids. Ge(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form GeS4 tetrahedra that share corners with two equivalent Li(3)S6 octahedra, corners with two equivalent Li(1)S4 tetrahedra, corners with eight equivalent Li(2)S4 trigonal pyramids, edges with two equivalent Li(3)S6 octahedra, and  an edgeedge with one Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. There are three inequivalent S sites. In the first S site, S(3) is bonded in a 6-coordinate geometry to one Li(1), two equivalent Li(2), two equivalent Li(3), and one Ge(1) atom. In the second S site, S(1) is bonded to one Li(1), two equivalent Li(2), two equivalent Li(3), and one Ge(1) atom to form distorted SLi5Ge pentagonal pyramids that share corners with two equivalent S(1)Li5Ge pentagonal pyramids, corners with four equivalent S(2)Li4Ge trigonal bipyramids, and edges with four equivalent S(2)Li4Ge trigonal bipyramids. In the third S site, S(2) is bonded to one Li(1), one Li(3), two equivalent Li(2), and one Ge(1) atom to form distorted SLi4Ge trigonal bipyramids that share corners with two equivalent S(1)Li5Ge pentagonal pyramids, corners with five equivalent S(2)Li4Ge trigonal bipyramids, and edges with two equivalent S(1)Li5Ge pentagonal pyramids.
Li4GeS4 is Aluminum carbonitride-like structured and crystallizes in the orthorhombic Pnma space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form LiS4 tetrahedra that share corners with two equivalent Li(3)S6 octahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with eight equivalent Li(2)S4 trigonal pyramids, edges with two equivalent Li(3)S6 octahedra, and  an edgeedge with one Ge(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. The Li(1)-S(1) bond length is 2.46 Å. The Li(1)-S(3) bond length is 2.48 Å. Both Li(1)-S(2) bond lengths are 2.45 Å. In the second Li site, Li(2) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted LiS4 trigonal pyramids that share corners with three equivalent Li(3)S6 octahedra, corners with four equivalent Li(1)S4 tetrahedra, corners with four equivalent Ge(1)S4 tetrahedra, corners with four equivalent Li(2)S4 trigonal pyramids, and  a faceface with one Li(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 19-53°. The Li(2)-S(1) bond length is 2.53 Å. The Li(2)-S(3) bond length is 2.40 Å. There is one shorter (2.40 Å) and one longer (2.53 Å) Li(2)-S(2) bond length. In the third Li site, Li(3) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted LiS6 octahedra that share corners with two equivalent Li(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with six equivalent Li(2)S4 trigonal pyramids, edges with two equivalent Li(3)S6 octahedra, edges with two equivalent Li(1)S4 tetrahedra, edges with two equivalent Ge(1)S4 tetrahedra, and faces with two equivalent Li(2)S4 trigonal pyramids. Both Li(3)-S(1) bond lengths are 2.56 Å. Both Li(3)-S(2) bond lengths are 2.57 Å. Both Li(3)-S(3) bond lengths are 2.90 Å. Ge(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form GeS4 tetrahedra that share corners with two equivalent Li(3)S6 octahedra, corners with two equivalent Li(1)S4 tetrahedra, corners with eight equivalent Li(2)S4 trigonal pyramids, edges with two equivalent Li(3)S6 octahedra, and  an edgeedge with one Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. The Ge(1)-S(1) bond length is 2.25 Å. The Ge(1)-S(3) bond length is 2.21 Å. Both Ge(1)-S(2) bond lengths are 2.21 Å. There are three inequivalent S sites. In the first S site, S(3) is bonded in a 6-coordinate geometry to one Li(1), two equivalent Li(2), two equivalent Li(3), and one Ge(1) atom. In the second S site, S(1) is bonded to one Li(1), two equivalent Li(2), two equivalent Li(3), and one Ge(1) atom to form distorted SLi5Ge pentagonal pyramids that share corners with two equivalent S(1)Li5Ge pentagonal pyramids, corners with four equivalent S(2)Li4Ge trigonal bipyramids, and edges with four equivalent S(2)Li4Ge trigonal bipyramids. In the third S site, S(2) is bonded to one Li(1), one Li(3), two equivalent Li(2), and one Ge(1) atom to form distorted SLi4Ge trigonal bipyramids that share corners with two equivalent S(1)Li5Ge pentagonal pyramids, corners with five equivalent S(2)Li4Ge trigonal bipyramids, and edges with two equivalent S(1)Li5Ge pentagonal pyramids.