CaSnS3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to one S(3), one S(5), two equivalent S(2), and two equivalent S(6) atoms. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form corner-sharing SnS4 tetrahedra. In the second Sn site, Sn(2) is bonded to one S(1), one S(4), one S(5), and one S(6) atom to form corner-sharing SnS4 tetrahedra. There are six inequivalent S sites. In the first S site, S(5) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Ca(2), and one Sn(2) atom. In the second S site, S(6) is bonded in a 4-coordinate geometry to one Ca(2), two equivalent Ca(1), and one Sn(2) atom. In the third S site, S(1) is bonded in a distorted trigonal planar geometry to one Ca(2), one Sn(1), and one Sn(2) atom. In the fourth S site, S(2) is bonded in a 4-coordinate geometry to one Ca(2), two equivalent Ca(1), and one Sn(1) atom. In the fifth S site, S(3) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(2), and one Sn(1) atom. In the sixth S site, S(4) is bonded in a trigonal planar geometry to one Ca(2), one Sn(1), and one Sn(2) atom.
CaSnS3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to one S(3), one S(5), two equivalent S(2), and two equivalent S(6) atoms. The Ca(1)-S(3) bond length is 2.83 Å. The Ca(1)-S(5) bond length is 2.82 Å. There is one shorter (3.09 Å) and one longer (3.44 Å) Ca(1)-S(2) bond length. There is one shorter (2.94 Å) and one longer (3.40 Å) Ca(1)-S(6) bond length. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom. The Ca(2)-S(1) bond length is 2.95 Å. The Ca(2)-S(2) bond length is 2.95 Å. The Ca(2)-S(3) bond length is 2.88 Å. The Ca(2)-S(4) bond length is 2.86 Å. The Ca(2)-S(5) bond length is 2.91 Å. The Ca(2)-S(6) bond length is 2.86 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form corner-sharing SnS4 tetrahedra. The Sn(1)-S(1) bond length is 2.46 Å. The Sn(1)-S(2) bond length is 2.38 Å. The Sn(1)-S(3) bond length is 2.39 Å. The Sn(1)-S(4) bond length is 2.44 Å. In the second Sn site, Sn(2) is bonded to one S(1), one S(4), one S(5), and one S(6) atom to form corner-sharing SnS4 tetrahedra. The Sn(2)-S(1) bond length is 2.44 Å. The Sn(2)-S(4) bond length is 2.43 Å. The Sn(2)-S(5) bond length is 2.37 Å. The Sn(2)-S(6) bond length is 2.35 Å. There are six inequivalent S sites. In the first S site, S(5) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Ca(2), and one Sn(2) atom. In the second S site, S(6) is bonded in a 4-coordinate geometry to one Ca(2), two equivalent Ca(1), and one Sn(2) atom. In the third S site, S(1) is bonded in a distorted trigonal planar geometry to one Ca(2), one Sn(1), and one Sn(2) atom. In the fourth S site, S(2) is bonded in a 4-coordinate geometry to one Ca(2), two equivalent Ca(1), and one Sn(1) atom. In the fifth S site, S(3) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(2), and one Sn(1) atom. In the sixth S site, S(4) is bonded in a trigonal planar geometry to one Ca(2), one Sn(1), and one Sn(2) atom.