CaSnS3 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a hexagonal planar geometry to six equivalent S(1) atoms. In the second Ca site, Ca(2) is bonded in a hexagonal planar geometry to six equivalent S(2) atoms. In the third Ca site, Ca(3) is bonded in a 3-coordinate geometry to three equivalent S(1) 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(3) atoms to form a mixture of face and corner-sharing SnS6 octahedra. The corner-sharing octahedra are not tilted. In the second Sn site, Sn(2) is bonded to three equivalent S(2) and three equivalent S(3) atoms to form face-sharing SnS6 octahedra. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(1), two equivalent Ca(3), and two equivalent Sn(1) atoms to form a mixture of face and corner-sharing SCa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to two equivalent Ca(2) and two equivalent Sn(2) atoms. In the third S site, S(3) is bonded in a 2-coordinate geometry to one Sn(1) and one Sn(2) atom.
CaSnS3 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a hexagonal planar geometry to six equivalent S(1) atoms. All Ca(1)-S(1) bond lengths are 3.40 Å. In the second Ca site, Ca(2) is bonded in a hexagonal planar geometry to six equivalent S(2) atoms. All Ca(2)-S(2) bond lengths are 3.40 Å. In the third Ca site, Ca(3) is bonded in a 3-coordinate geometry to three equivalent S(1) atoms. All Ca(3)-S(1) bond lengths are 2.94 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(3) atoms to form a mixture of face and corner-sharing SnS6 octahedra. The corner-sharing octahedra are not tilted. All Sn(1)-S(1) bond lengths are 2.59 Å. All Sn(1)-S(3) bond lengths are 2.48 Å. In the second Sn site, Sn(2) is bonded to three equivalent S(2) and three equivalent S(3) atoms to form face-sharing SnS6 octahedra. All Sn(2)-S(2) bond lengths are 2.53 Å. All Sn(2)-S(3) bond lengths are 2.63 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(1), two equivalent Ca(3), and two equivalent Sn(1) atoms to form a mixture of face and corner-sharing SCa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to two equivalent Ca(2) and two equivalent Sn(2) atoms. In the third S site, S(3) is bonded in a 2-coordinate geometry to one Sn(1) and one Sn(2) atom.