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 two equivalent S(3), two equivalent S(4), two equivalent S(5), and three equivalent S(1) atoms. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(3), one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. Ge(1) is bonded to one S(3), one S(4), and two equivalent S(2) atoms to form corner-sharing GeS4 tetrahedra. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent La(2) and three equivalent La(1) atoms to form distorted SLa5 trigonal bipyramids that share corners with four equivalent S(2)La2Ge2 tetrahedra, corners with four equivalent S(1)La5 trigonal bipyramids, corners with two equivalent S(3)La3Ge trigonal pyramids, edges with two equivalent S(1)La5 trigonal bipyramids, and edges with three equivalent S(3)La3Ge trigonal pyramids. In the second S site, S(2) is bonded to two equivalent La(2) and two equivalent Ge(1) atoms to form distorted SLa2Ge2 tetrahedra that share corners with two equivalent S(2)La2Ge2 tetrahedra, corners with four equivalent S(1)La5 trigonal bipyramids, corners with two equivalent S(3)La3Ge trigonal pyramids,  an edgeedge with one S(2)La2Ge2 tetrahedra, and  an edgeedge with one S(3)La3Ge trigonal pyramid. In the third S site, S(3) is bonded to one La(2), two equivalent La(1), and one Ge(1) atom to form SLa3Ge trigonal pyramids that share corners with two equivalent S(2)La2Ge2 tetrahedra, corners with two equivalent S(1)La5 trigonal bipyramids, corners with two equivalent S(3)La3Ge trigonal pyramids,  an edgeedge with one S(2)La2Ge2 tetrahedra, and edges with three equivalent S(1)La5 trigonal bipyramids. In the fourth S site, S(4) is bonded in a distorted bent 120 degrees geometry to one La(2), two equivalent La(1), and one Ge(1) atom. In the fifth S site, S(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent La(1) and two equivalent La(2) atoms.
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 two equivalent S(3), two equivalent S(4), two equivalent S(5), and three equivalent S(1) atoms. There is one shorter (2.97 Å) and one longer (3.12 Å) La(1)-S(3) bond length. There is one shorter (3.57 Å) and one longer (3.69 Å) La(1)-S(4) bond length. There is one shorter (2.78 Å) and one longer (2.82 Å) La(1)-S(5) bond length. There are a spread of La(1)-S(1) bond distances ranging from 2.91-3.39 Å. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(3), one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. The La(2)-S(3) bond length is 2.85 Å. The La(2)-S(4) bond length is 2.87 Å. There is one shorter (2.79 Å) and one longer (3.18 Å) La(2)-S(1) bond length. There is one shorter (3.13 Å) and one longer (3.46 Å) La(2)-S(2) bond length. There is one shorter (2.87 Å) and one longer (3.29 Å) La(2)-S(5) bond length. Ge(1) is bonded to one S(3), one S(4), and two equivalent S(2) atoms to form corner-sharing GeS4 tetrahedra. The Ge(1)-S(3) bond length is 2.22 Å. The Ge(1)-S(4) bond length is 2.16 Å. There is one shorter (2.37 Å) and one longer (2.44 Å) Ge(1)-S(2) bond length. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent La(2) and three equivalent La(1) atoms to form distorted SLa5 trigonal bipyramids that share corners with four equivalent S(2)La2Ge2 tetrahedra, corners with four equivalent S(1)La5 trigonal bipyramids, corners with two equivalent S(3)La3Ge trigonal pyramids, edges with two equivalent S(1)La5 trigonal bipyramids, and edges with three equivalent S(3)La3Ge trigonal pyramids. In the second S site, S(2) is bonded to two equivalent La(2) and two equivalent Ge(1) atoms to form distorted SLa2Ge2 tetrahedra that share corners with two equivalent S(2)La2Ge2 tetrahedra, corners with four equivalent S(1)La5 trigonal bipyramids, corners with two equivalent S(3)La3Ge trigonal pyramids,  an edgeedge with one S(2)La2Ge2 tetrahedra, and  an edgeedge with one S(3)La3Ge trigonal pyramid. In the third S site, S(3) is bonded to one La(2), two equivalent La(1), and one Ge(1) atom to form SLa3Ge trigonal pyramids that share corners with two equivalent S(2)La2Ge2 tetrahedra, corners with two equivalent S(1)La5 trigonal bipyramids, corners with two equivalent S(3)La3Ge trigonal pyramids,  an edgeedge with one S(2)La2Ge2 tetrahedra, and edges with three equivalent S(1)La5 trigonal bipyramids. In the fourth S site, S(4) is bonded in a distorted bent 120 degrees geometry to one La(2), two equivalent La(1), and one Ge(1) atom. In the fifth S site, S(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent La(1) and two equivalent La(2) atoms.