Li4GeS4 is Chalcostibite-like structured and crystallizes in the orthorhombic Pna2_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), one S(3), and one S(4) atom to form LiS4 tetrahedra that share corners with two equivalent Li(3)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, corners with four equivalent Ge(1)S4 tetrahedra, and  an edgeedge with one Li(3)S4 tetrahedra. In the second Li site, Li(2) 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 Li(3)S4 tetrahedra, corners with four equivalent Li(1)S4 tetrahedra, corners with four equivalent Ge(1)S4 tetrahedra, and  an edgeedge with one Li(3)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 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 Ge(1)S4 tetrahedra,  an edgeedge with one Li(1)S4 tetrahedra, and  an edgeedge with one Li(2)S4 tetrahedra. In the fourth Li site, Li(4) is bonded in a distorted trigonal non-coplanar geometry to one S(1), one S(2), and one S(4) atom. 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 four equivalent Li(1)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, and corners with four equivalent Li(3)S4 tetrahedra. There are four inequivalent S sites. In the first S site, S(4) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one Ge(1) atom. In the second S site, S(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one Ge(1) atom. In the third S site, S(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one Ge(1) atom. In the fourth S site, S(3) is bonded in a tetrahedral geometry to one Li(1), one Li(2), one Li(3), and one Ge(1) atom.
Li4GeS4 is Chalcostibite-like structured and crystallizes in the orthorhombic Pna2_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), one S(3), and one S(4) atom to form LiS4 tetrahedra that share corners with two equivalent Li(3)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, corners with four equivalent Ge(1)S4 tetrahedra, and  an edgeedge with one Li(3)S4 tetrahedra. The Li(1)-S(1) bond length is 2.50 Å. The Li(1)-S(2) bond length is 2.44 Å. The Li(1)-S(3) bond length is 2.33 Å. The Li(1)-S(4) bond length is 2.35 Å. In the second Li site, Li(2) 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 Li(3)S4 tetrahedra, corners with four equivalent Li(1)S4 tetrahedra, corners with four equivalent Ge(1)S4 tetrahedra, and  an edgeedge with one Li(3)S4 tetrahedra. The Li(2)-S(1) bond length is 2.46 Å. The Li(2)-S(2) bond length is 2.42 Å. The Li(2)-S(3) bond length is 2.36 Å. The Li(2)-S(4) bond length is 2.39 Å. 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 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 Ge(1)S4 tetrahedra,  an edgeedge with one Li(1)S4 tetrahedra, and  an edgeedge with one Li(2)S4 tetrahedra. The Li(3)-S(1) bond length is 2.60 Å. The Li(3)-S(2) bond length is 2.57 Å. The Li(3)-S(3) bond length is 2.39 Å. The Li(3)-S(4) bond length is 2.47 Å. In the fourth Li site, Li(4) is bonded in a distorted trigonal non-coplanar geometry to one S(1), one S(2), and one S(4) atom. The Li(4)-S(1) bond length is 2.59 Å. The Li(4)-S(2) bond length is 2.60 Å. The Li(4)-S(4) bond length is 2.46 Å. 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 four equivalent Li(1)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, and corners with four equivalent Li(3)S4 tetrahedra. The Ge(1)-S(1) bond length is 2.26 Å. The Ge(1)-S(2) bond length is 2.26 Å. The Ge(1)-S(3) bond length is 2.22 Å. The Ge(1)-S(4) bond length is 2.24 Å. There are four inequivalent S sites. In the first S site, S(4) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one Ge(1) atom. In the second S site, S(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one Ge(1) atom. In the third S site, S(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one Ge(1) atom. In the fourth S site, S(3) is bonded in a tetrahedral geometry to one Li(1), one Li(2), one Li(3), and one Ge(1) atom.