Li4GeS4 is Aluminum carbonitride-like structured and crystallizes in the orthorhombic P2_12_12_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(2), and two equivalent S(4) atoms to form distorted LiS4 tetrahedra that share corners with two equivalent Li(1)S4 tetrahedra, corners with two equivalent Li(2)S4 tetrahedra, corners with four equivalent Li(3)S4 tetrahedra, and corners with four equivalent Ge(1)S4 tetrahedra. In the second Li site, Li(2) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form distorted LiS4 tetrahedra that share corners with two equivalent Li(1)S4 tetrahedra, corners with two equivalent Li(2)S4 tetrahedra, corners with four equivalent Li(3)S4 tetrahedra, and corners with four equivalent Ge(1)S4 tetrahedra. In the third Li site, Li(3) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form LiS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with four equivalent Li(1)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, and  an edgeedge with one Ge(1)S4 tetrahedra. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms. Ge(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form GeS4 tetrahedra that share corners with two equivalent Li(3)S4 tetrahedra, corners with four equivalent Li(1)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, and  an edgeedge with one Li(3)S4 tetrahedra. There are four inequivalent S sites. In the first S site, S(4) is bonded to one Li(3), one Li(4), two equivalent Li(1), and one Ge(1) atom to form distorted corner-sharing SLi4Ge trigonal bipyramids. In the second S site, S(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), two equivalent Li(4), and one Ge(1) atom. In the third S site, S(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), two equivalent Li(4), and one Ge(1) atom. In the fourth S site, S(3) is bonded to one Li(3), one Li(4), two equivalent Li(2), and one Ge(1) atom to form distorted corner-sharing SLi4Ge trigonal bipyramids.
Li4GeS4 is Aluminum carbonitride-like structured and crystallizes in the orthorhombic P2_12_12_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(2), and two equivalent S(4) atoms to form distorted LiS4 tetrahedra that share corners with two equivalent Li(1)S4 tetrahedra, corners with two equivalent Li(2)S4 tetrahedra, corners with four equivalent Li(3)S4 tetrahedra, and corners with four equivalent Ge(1)S4 tetrahedra. The Li(1)-S(1) bond length is 2.55 Å. The Li(1)-S(2) bond length is 2.40 Å. There is one shorter (2.41 Å) and one longer (2.51 Å) Li(1)-S(4) bond length. In the second Li site, Li(2) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form distorted LiS4 tetrahedra that share corners with two equivalent Li(1)S4 tetrahedra, corners with two equivalent Li(2)S4 tetrahedra, corners with four equivalent Li(3)S4 tetrahedra, and corners with four equivalent Ge(1)S4 tetrahedra. The Li(2)-S(1) bond length is 2.53 Å. The Li(2)-S(2) bond length is 2.40 Å. There is one shorter (2.40 Å) and one longer (2.52 Å) Li(2)-S(3) bond length. In the third Li site, Li(3) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form LiS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with four equivalent Li(1)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, and  an edgeedge with one Ge(1)S4 tetrahedra. The Li(3)-S(1) bond length is 2.46 Å. The Li(3)-S(2) bond length is 2.47 Å. The Li(3)-S(3) bond length is 2.45 Å. The Li(3)-S(4) bond length is 2.46 Å. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms. The Li(4)-S(3) bond length is 2.59 Å. The Li(4)-S(4) bond length is 2.56 Å. There is one shorter (2.55 Å) and one longer (2.56 Å) Li(4)-S(1) bond length. There is one shorter (2.78 Å) and one longer (3.03 Å) Li(4)-S(2) bond length. Ge(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form GeS4 tetrahedra that share corners with two equivalent Li(3)S4 tetrahedra, corners with four equivalent Li(1)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, and  an edgeedge with one Li(3)S4 tetrahedra. The Ge(1)-S(1) bond length is 2.25 Å. The Ge(1)-S(2) bond length is 2.21 Å. The Ge(1)-S(3) bond length is 2.21 Å. The Ge(1)-S(4) bond length is 2.21 Å. There are four inequivalent S sites. In the first S site, S(4) is bonded to one Li(3), one Li(4), two equivalent Li(1), and one Ge(1) atom to form distorted corner-sharing SLi4Ge trigonal bipyramids. In the second S site, S(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), two equivalent Li(4), and one Ge(1) atom. In the third S site, S(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), two equivalent Li(4), and one Ge(1) atom. In the fourth S site, S(3) is bonded to one Li(3), one Li(4), two equivalent Li(2), and one Ge(1) atom to form distorted corner-sharing SLi4Ge trigonal bipyramids.