CaSn3S7 crystallizes in the orthorhombic Pnma space group. Ca(1) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 5-coordinate geometry to one S(1), two equivalent S(3), and two equivalent S(4) atoms. In the second Sn site, Sn(2) is bonded in a 5-coordinate geometry to one S(2), two equivalent S(3), and two equivalent S(4) atoms. There are four inequivalent S sites. In the first S site, S(4) is bonded to one Ca(1), one Sn(1), and two equivalent Sn(2) atoms to form a mixture of corner and edge-sharing SCaSn3 tetrahedra. In the second S site, S(1) is bonded in a bent 120 degrees geometry to one Ca(1) and one Sn(1) atom. In the third S site, S(2) is bonded in a bent 120 degrees geometry to one Ca(1) and one Sn(2) atom. In the fourth S site, S(3) is bonded to one Ca(1), one Sn(1), and two equivalent Sn(2) atoms to form a mixture of distorted corner and edge-sharing SCaSn3 tetrahedra.
CaSn3S7 crystallizes in the orthorhombic Pnma space group. Ca(1) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. The Ca(1)-S(1) bond length is 2.82 Å. Both Ca(1)-S(2) bond lengths are 2.74 Å. Both Ca(1)-S(3) bond lengths are 3.27 Å. Both Ca(1)-S(4) bond lengths are 3.10 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 5-coordinate geometry to one S(1), two equivalent S(3), and two equivalent S(4) atoms. The Sn(1)-S(1) bond length is 2.32 Å. Both Sn(1)-S(3) bond lengths are 2.63 Å. Both Sn(1)-S(4) bond lengths are 2.67 Å. In the second Sn site, Sn(2) is bonded in a 5-coordinate geometry to one S(2), two equivalent S(3), and two equivalent S(4) atoms. The Sn(2)-S(2) bond length is 2.32 Å. There is one shorter (2.60 Å) and one longer (2.62 Å) Sn(2)-S(3) bond length. There is one shorter (2.60 Å) and one longer (2.61 Å) Sn(2)-S(4) bond length. There are four inequivalent S sites. In the first S site, S(4) is bonded to one Ca(1), one Sn(1), and two equivalent Sn(2) atoms to form a mixture of corner and edge-sharing SCaSn3 tetrahedra. In the second S site, S(1) is bonded in a bent 120 degrees geometry to one Ca(1) and one Sn(1) atom. In the third S site, S(2) is bonded in a bent 120 degrees geometry to one Ca(1) and one Sn(2) atom. In the fourth S site, S(3) is bonded to one Ca(1), one Sn(1), and two equivalent Sn(2) atoms to form a mixture of distorted corner and edge-sharing SCaSn3 tetrahedra.