Ca2SnS4 crystallizes in the orthorhombic Pnma space group. Ca(1) is bonded to two equivalent S(1), two equivalent S(2), and three equivalent S(3) atoms to form distorted CaS7 pentagonal bipyramids that share corners with six equivalent Ca(1)S7 pentagonal bipyramids, corners with three equivalent Sn(1)S4 tetrahedra, edges with three equivalent Ca(1)S7 pentagonal bipyramids, edges with two equivalent Sn(1)S4 tetrahedra, and faces with two equivalent Ca(1)S7 pentagonal bipyramids. Sn(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form SnS4 tetrahedra that share corners with six equivalent Ca(1)S7 pentagonal bipyramids and edges with four equivalent Ca(1)S7 pentagonal bipyramids. There are three inequivalent S sites. In the first S site, S(1) is bonded to four equivalent Ca(1) and one Sn(1) atom to form a mixture of distorted corner and edge-sharing SCa4Sn trigonal bipyramids. In the second S site, S(2) is bonded to four equivalent Ca(1) and one Sn(1) atom to form a mixture of distorted corner and edge-sharing SCa4Sn trigonal bipyramids. In the third S site, S(3) is bonded in a see-saw-like geometry to three equivalent Ca(1) and one Sn(1) atom.
Ca2SnS4 crystallizes in the orthorhombic Pnma space group. Ca(1) is bonded to two equivalent S(1), two equivalent S(2), and three equivalent S(3) atoms to form distorted CaS7 pentagonal bipyramids that share corners with six equivalent Ca(1)S7 pentagonal bipyramids, corners with three equivalent Sn(1)S4 tetrahedra, edges with three equivalent Ca(1)S7 pentagonal bipyramids, edges with two equivalent Sn(1)S4 tetrahedra, and faces with two equivalent Ca(1)S7 pentagonal bipyramids. There is one shorter (2.93 Å) and one longer (3.02 Å) Ca(1)-S(1) bond length. There is one shorter (2.97 Å) and one longer (3.03 Å) Ca(1)-S(2) bond length. There are a spread of Ca(1)-S(3) bond distances ranging from 2.89-2.93 Å. Sn(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form SnS4 tetrahedra that share corners with six equivalent Ca(1)S7 pentagonal bipyramids and edges with four equivalent Ca(1)S7 pentagonal bipyramids. The Sn(1)-S(1) bond length is 2.43 Å. The Sn(1)-S(2) bond length is 2.42 Å. Both Sn(1)-S(3) bond lengths are 2.42 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to four equivalent Ca(1) and one Sn(1) atom to form a mixture of distorted corner and edge-sharing SCa4Sn trigonal bipyramids. In the second S site, S(2) is bonded to four equivalent Ca(1) and one Sn(1) atom to form a mixture of distorted corner and edge-sharing SCa4Sn trigonal bipyramids. In the third S site, S(3) is bonded in a see-saw-like geometry to three equivalent Ca(1) and one Sn(1) atom.