La2SnS5 crystallizes in the orthorhombic Pbam space group. La(1) is bonded in a 9-coordinate geometry to two equivalent S(3), three equivalent S(1), and four equivalent S(2) atoms. Sn(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form edge-sharing SnS6 octahedra. There are three inequivalent S sites. In the first S site, S(1) is bonded to three equivalent La(1) and two equivalent Sn(1) atoms to form distorted SLa3Sn2 trigonal bipyramids that share corners with four equivalent S(2)La4Sn square pyramids, corners with eight equivalent S(1)La3Sn2 trigonal bipyramids, edges with six equivalent S(2)La4Sn square pyramids, and edges with two equivalent S(1)La3Sn2 trigonal bipyramids. In the second S site, S(2) is bonded to four equivalent La(1) and one Sn(1) atom to form distorted SLa4Sn square pyramids that share corners with five equivalent S(2)La4Sn square pyramids, corners with four equivalent S(1)La3Sn2 trigonal bipyramids, edges with four equivalent S(2)La4Sn square pyramids, and edges with six equivalent S(1)La3Sn2 trigonal bipyramids. In the third S site, S(3) is bonded in a square co-planar geometry to four equivalent La(1) atoms.
La2SnS5 crystallizes in the orthorhombic Pbam space group. La(1) is bonded in a 9-coordinate geometry to two equivalent S(3), three equivalent S(1), and four equivalent S(2) atoms. Both La(1)-S(3) bond lengths are 2.84 Å. There is one shorter (3.10 Å) and two longer (3.30 Å) La(1)-S(1) bond lengths. There are two shorter (3.03 Å) and two longer (3.04 Å) La(1)-S(2) bond lengths. Sn(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form edge-sharing SnS6 octahedra. Both Sn(1)-S(2) bond lengths are 2.55 Å. All Sn(1)-S(1) bond lengths are 2.62 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to three equivalent La(1) and two equivalent Sn(1) atoms to form distorted SLa3Sn2 trigonal bipyramids that share corners with four equivalent S(2)La4Sn square pyramids, corners with eight equivalent S(1)La3Sn2 trigonal bipyramids, edges with six equivalent S(2)La4Sn square pyramids, and edges with two equivalent S(1)La3Sn2 trigonal bipyramids. In the second S site, S(2) is bonded to four equivalent La(1) and one Sn(1) atom to form distorted SLa4Sn square pyramids that share corners with five equivalent S(2)La4Sn square pyramids, corners with four equivalent S(1)La3Sn2 trigonal bipyramids, edges with four equivalent S(2)La4Sn square pyramids, and edges with six equivalent S(1)La3Sn2 trigonal bipyramids. In the third S site, S(3) is bonded in a square co-planar geometry to four equivalent La(1) atoms.