CaSn3S7 crystallizes in the orthorhombic Pmmn space group. Ca(1) is bonded in a 6-coordinate geometry to two equivalent S(2) and four equivalent S(3) atoms. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 5-coordinate geometry to one S(2) and four equivalent S(3) atoms. In the second Sn site, Sn(2) is bonded in a 5-coordinate geometry to one S(1) and four equivalent S(3) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded in a single-bond geometry to one Sn(2) atom. In the second S site, S(2) is bonded in a bent 120 degrees geometry to one Ca(1) and one Sn(1) atom. In the third S site, S(3) is bonded to one Ca(1), one Sn(2), and two equivalent Sn(1) atoms to form a mixture of distorted corner and edge-sharing SCaSn3 tetrahedra.
CaSn3S7 crystallizes in the orthorhombic Pmmn space group. Ca(1) is bonded in a 6-coordinate geometry to two equivalent S(2) and four equivalent S(3) atoms. Both Ca(1)-S(2) bond lengths are 2.73 Å. All Ca(1)-S(3) bond lengths are 3.14 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 5-coordinate geometry to one S(2) and four equivalent S(3) atoms. The Sn(1)-S(2) bond length is 2.33 Å. There are two shorter (2.59 Å) and two longer (2.61 Å) Sn(1)-S(3) bond lengths. In the second Sn site, Sn(2) is bonded in a 5-coordinate geometry to one S(1) and four equivalent S(3) atoms. The Sn(2)-S(1) bond length is 2.33 Å. All Sn(2)-S(3) bond lengths are 2.65 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a single-bond geometry to one Sn(2) atom. In the second S site, S(2) is bonded in a bent 120 degrees geometry to one Ca(1) and one Sn(1) atom. In the third S site, S(3) is bonded to one Ca(1), one Sn(2), and two equivalent Sn(1) atoms to form a mixture of distorted corner and edge-sharing SCaSn3 tetrahedra.