CaSnS3 crystallizes in the orthorhombic Amm2 space group. Ca(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form distorted CaS6 octahedra that share corners with two equivalent Ca(1)S6 octahedra, corners with six equivalent Sn(1)S6 octahedra, edges with two equivalent Ca(1)S6 octahedra, and faces with two equivalent Sn(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-86°. Sn(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form distorted SnS6 octahedra that share corners with six equivalent Ca(1)S6 octahedra, corners with six equivalent Sn(1)S6 octahedra, and faces with two equivalent Ca(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 7-86°. 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(1) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Ca(1), two equivalent Sn(1), and one S(2) atom.
CaSnS3 crystallizes in the orthorhombic Amm2 space group. Ca(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form distorted CaS6 octahedra that share corners with two equivalent Ca(1)S6 octahedra, corners with six equivalent Sn(1)S6 octahedra, edges with two equivalent Ca(1)S6 octahedra, and faces with two equivalent Sn(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-86°. There is one shorter (2.84 Å) and one longer (2.86 Å) Ca(1)-S(1) bond length. All Ca(1)-S(2) bond lengths are 2.94 Å. Sn(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form distorted SnS6 octahedra that share corners with six equivalent Ca(1)S6 octahedra, corners with six equivalent Sn(1)S6 octahedra, and faces with two equivalent Ca(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 7-86°. Both Sn(1)-S(1) bond lengths are 2.70 Å. There are two shorter (2.72 Å) and two longer (2.93 Å) Sn(1)-S(2) bond lengths. 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(1) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Ca(1), two equivalent Sn(1), and one S(2) atom. The S(2)-S(2) bond length is 2.29 Å.