CaSnS3 crystallizes in the trigonal R-3m space group. There are two 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 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 six equivalent S(2) atoms to form face-sharing SnS6 octahedra. In the second Sn site, Sn(2) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form a mixture of face and corner-sharing SnS6 octahedra. The corner-sharing octahedra are not tilted. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(1), two equivalent Ca(2), and two equivalent Sn(2) 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 2-coordinate geometry to one Sn(1) and one Sn(2) atom.
CaSnS3 crystallizes in the trigonal R-3m space group. There are two 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 3.42 Å. In the second Ca site, Ca(2) is bonded in a 3-coordinate geometry to three equivalent S(1) atoms. All Ca(2)-S(1) bond lengths are 2.92 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to six equivalent S(2) atoms to form face-sharing SnS6 octahedra. All Sn(1)-S(2) bond lengths are 2.62 Å. In the second Sn site, Sn(2) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form a mixture of face and corner-sharing SnS6 octahedra. The corner-sharing octahedra are not tilted. All Sn(2)-S(1) bond lengths are 2.59 Å. All Sn(2)-S(2) bond lengths are 2.47 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(1), two equivalent Ca(2), and two equivalent Sn(2) 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 2-coordinate geometry to one Sn(1) and one Sn(2) atom.