La2GeS5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 9-coordinate geometry to one S(5), two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(2), one S(3), two equivalent S(1), two equivalent S(4), and two equivalent S(5) atoms. Ge(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(5) atom. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent La(1), two equivalent La(2), and one Ge(1) atom to form distorted SLa4Ge trigonal bipyramids that share corners with five equivalent S(5)La3Ge tetrahedra, corners with three equivalent S(4)La4 trigonal pyramids,  an edgeedge with one S(5)La3Ge tetrahedra, edges with two equivalent S(1)La4Ge trigonal bipyramids,  an edgeedge with one S(4)La4 trigonal pyramid, and  a faceface with one S(4)La4 trigonal pyramid. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one La(2), two equivalent La(1), and one Ge(1) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to one La(2), two equivalent La(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded to two equivalent La(1) and two equivalent La(2) atoms to form SLa4 trigonal pyramids that share corners with four equivalent S(5)La3Ge tetrahedra, corners with three equivalent S(1)La4Ge trigonal bipyramids, corners with two equivalent S(4)La4 trigonal pyramids,  an edgeedge with one S(5)La3Ge tetrahedra,  an edgeedge with one S(1)La4Ge trigonal bipyramid,  an edgeedge with one S(4)La4 trigonal pyramid, and  a faceface with one S(1)La4Ge trigonal bipyramid. In the fifth S site, S(5) is bonded to one La(1), two equivalent La(2), and one Ge(1) atom to form distorted SLa3Ge tetrahedra that share corners with five equivalent S(1)La4Ge trigonal bipyramids, corners with four equivalent S(4)La4 trigonal pyramids,  an edgeedge with one S(5)La3Ge tetrahedra,  an edgeedge with one S(1)La4Ge trigonal bipyramid, and  an edgeedge with one S(4)La4 trigonal pyramid.
La2GeS5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 9-coordinate geometry to one S(5), two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. The La(1)-S(5) bond length is 2.94 Å. There is one shorter (3.13 Å) and one longer (3.25 Å) La(1)-S(1) bond length. There is one shorter (3.09 Å) and one longer (3.21 Å) La(1)-S(2) bond length. There is one shorter (3.10 Å) and one longer (3.35 Å) La(1)-S(3) bond length. There is one shorter (2.92 Å) and one longer (2.99 Å) La(1)-S(4) bond length. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(2), one S(3), two equivalent S(1), two equivalent S(4), and two equivalent S(5) atoms. The La(2)-S(2) bond length is 2.97 Å. The La(2)-S(3) bond length is 3.18 Å. There is one shorter (3.04 Å) and one longer (3.07 Å) La(2)-S(1) bond length. There is one shorter (2.85 Å) and one longer (2.87 Å) La(2)-S(4) bond length. There is one shorter (2.93 Å) and one longer (2.99 Å) La(2)-S(5) bond length. Ge(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(5) atom. 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 2.19 Å. The Ge(1)-S(5) bond length is 2.19 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent La(1), two equivalent La(2), and one Ge(1) atom to form distorted SLa4Ge trigonal bipyramids that share corners with five equivalent S(5)La3Ge tetrahedra, corners with three equivalent S(4)La4 trigonal pyramids,  an edgeedge with one S(5)La3Ge tetrahedra, edges with two equivalent S(1)La4Ge trigonal bipyramids,  an edgeedge with one S(4)La4 trigonal pyramid, and  a faceface with one S(4)La4 trigonal pyramid. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one La(2), two equivalent La(1), and one Ge(1) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to one La(2), two equivalent La(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded to two equivalent La(1) and two equivalent La(2) atoms to form SLa4 trigonal pyramids that share corners with four equivalent S(5)La3Ge tetrahedra, corners with three equivalent S(1)La4Ge trigonal bipyramids, corners with two equivalent S(4)La4 trigonal pyramids,  an edgeedge with one S(5)La3Ge tetrahedra,  an edgeedge with one S(1)La4Ge trigonal bipyramid,  an edgeedge with one S(4)La4 trigonal pyramid, and  a faceface with one S(1)La4Ge trigonal bipyramid. In the fifth S site, S(5) is bonded to one La(1), two equivalent La(2), and one Ge(1) atom to form distorted SLa3Ge tetrahedra that share corners with five equivalent S(1)La4Ge trigonal bipyramids, corners with four equivalent S(4)La4 trigonal pyramids,  an edgeedge with one S(5)La3Ge tetrahedra,  an edgeedge with one S(1)La4Ge trigonal bipyramid, and  an edgeedge with one S(4)La4 trigonal pyramid.