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 9-coordinate geometry to nine equivalent S(2) 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 corner and face-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 in a square co-planar geometry to two equivalent Ca(1) and two equivalent Sn(2) atoms. In the second S site, S(2) is bonded in a 2-coordinate geometry to three equivalent Ca(2), 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 3.38 Å. In the second Ca site, Ca(2) is bonded in a 9-coordinate geometry to nine equivalent S(2) atoms. There are six shorter (3.39 Å) and three longer (3.51 Å) Ca(2)-S(2) bond lengths. 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 2.56 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 corner and face-sharing SnS6 octahedra. The corner-sharing octahedra are not tilted. All Sn(2)-S(1) bond lengths are 2.52 Å. All Sn(2)-S(2) bond lengths are 2.57 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a square co-planar geometry to two equivalent Ca(1) and two equivalent Sn(2) atoms. In the second S site, S(2) is bonded in a 2-coordinate geometry to three equivalent Ca(2), one Sn(1), and one Sn(2) atom.