CaSnS3 is Spinel-like structured and crystallizes in the cubic P2_13 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted hexagonal planar geometry to three equivalent S(1) and three equivalent S(2) atoms. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to three equivalent S(1) and three equivalent S(2) atoms. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted corner-sharing SnS6 pentagonal pyramids. In the second Sn site, Sn(2) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted corner-sharing SnS6 pentagonal pyramids. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Ca(1), one Ca(2), one Sn(1), and one Sn(2) atom to form edge-sharing SCa2Sn2 tetrahedra. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one Ca(2), one Sn(1), and one Sn(2) atom.
CaSnS3 is Spinel-like structured and crystallizes in the cubic P2_13 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted hexagonal planar geometry to three equivalent S(1) and three equivalent S(2) atoms. All Ca(1)-S(1) bond lengths are 2.86 Å. All Ca(1)-S(2) bond lengths are 2.92 Å. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to three equivalent S(1) and three equivalent S(2) atoms. All Ca(2)-S(1) bond lengths are 2.85 Å. All Ca(2)-S(2) bond lengths are 3.03 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted corner-sharing SnS6 pentagonal pyramids. All Sn(1)-S(1) bond lengths are 2.65 Å. All Sn(1)-S(2) bond lengths are 2.56 Å. In the second Sn site, Sn(2) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted corner-sharing SnS6 pentagonal pyramids. All Sn(2)-S(1) bond lengths are 2.58 Å. All Sn(2)-S(2) bond lengths are 2.69 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Ca(1), one Ca(2), one Sn(1), and one Sn(2) atom to form edge-sharing SCa2Sn2 tetrahedra. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one Ca(2), one Sn(1), and one Sn(2) atom.