Ca2SnS4 crystallizes in the orthorhombic Cmmm space group. Ca(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form CaS6 octahedra that share corners with six equivalent Ca(1)S6 octahedra, edges with four equivalent Ca(1)S6 octahedra, and edges with four equivalent Sn(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. Sn(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form SnS6 octahedra that share edges with two equivalent Sn(1)S6 octahedra and edges with eight equivalent Ca(1)S6 octahedra. There are two inequivalent S sites. In the first S site, S(2) is bonded in a rectangular see-saw-like geometry to two equivalent Ca(1) and two equivalent Sn(1) atoms. In the second S site, S(1) is bonded to four equivalent Ca(1) and one Sn(1) atom to form a mixture of corner and edge-sharing SCa4Sn square pyramids.
Ca2SnS4 crystallizes in the orthorhombic Cmmm space group. Ca(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form CaS6 octahedra that share corners with six equivalent Ca(1)S6 octahedra, edges with four equivalent Ca(1)S6 octahedra, and edges with four equivalent Sn(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. Both Ca(1)-S(2) bond lengths are 2.84 Å. All Ca(1)-S(1) bond lengths are 2.82 Å. Sn(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form SnS6 octahedra that share edges with two equivalent Sn(1)S6 octahedra and edges with eight equivalent Ca(1)S6 octahedra. Both Sn(1)-S(1) bond lengths are 2.59 Å. All Sn(1)-S(2) bond lengths are 2.62 Å. There are two inequivalent S sites. In the first S site, S(2) is bonded in a rectangular see-saw-like geometry to two equivalent Ca(1) and two equivalent Sn(1) atoms. In the second S site, S(1) is bonded to four equivalent Ca(1) and one Sn(1) atom to form a mixture of corner and edge-sharing SCa4Sn square pyramids.