CaSnS3 is Esseneite-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to one S(1), one S(3), one S(6), one S(7), two equivalent S(4), and two equivalent S(5) atoms. In the second Ca site, Ca(2) is bonded in a 4-coordinate geometry to one S(1), one S(5), one S(8), one S(9), and two equivalent S(2) atoms. In the third Ca site, Ca(3) is bonded to one S(1), one S(2), one S(4), one S(7), and two equivalent S(8) atoms to form distorted CaS6 octahedra that share  a cornercorner with one Sn(2)S4 tetrahedra, corners with two equivalent Sn(1)S4 tetrahedra, corners with three equivalent Sn(3)S4 tetrahedra, and  an edgeedge with one Ca(3)S6 octahedra. There are three 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(9) atom to form SnS4 tetrahedra that share corners with two equivalent Ca(3)S6 octahedra,  a cornercorner with one Sn(2)S4 tetrahedra, and  a cornercorner with one Sn(3)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 68-69°. In the second Sn site, Sn(2) is bonded to one S(3), one S(4), one S(5), and one S(6) atom to form SnS4 tetrahedra that share  a cornercorner with one Ca(3)S6 octahedra,  a cornercorner with one Sn(1)S4 tetrahedra, and  a cornercorner with one Sn(3)S4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. In the third Sn site, Sn(3) is bonded to one S(6), one S(7), one S(8), and one S(9) atom to form SnS4 tetrahedra that share corners with three equivalent Ca(3)S6 octahedra,  a cornercorner with one Sn(1)S4 tetrahedra, and  a cornercorner with one Sn(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-68°. There are nine inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Ca(2), one Ca(3), and one Sn(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ca(3), two equivalent Ca(2), and one Sn(1) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Ca(1), one Sn(1), and one Sn(2) atom. In the fourth S site, S(4) is bonded to one Ca(3), two equivalent Ca(1), and one Sn(2) atom to form a mixture of corner and edge-sharing SCa3Sn tetrahedra. In the fifth S site, S(5) is bonded to one Ca(2), two equivalent Ca(1), and one Sn(2) atom to form a mixture of distorted corner and edge-sharing SCa3Sn tetrahedra. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Ca(1), one Sn(2), and one Sn(3) atom. In the seventh S site, S(7) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Ca(3), and one Sn(3) atom. In the eighth S site, S(8) is bonded to one Ca(2), two equivalent Ca(3), and one Sn(3) atom to form a mixture of distorted corner and edge-sharing SCa3Sn tetrahedra. In the ninth S site, S(9) is bonded in a distorted water-like geometry to one Ca(2), one Sn(1), and one Sn(3) atom.
CaSnS3 is Esseneite-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to one S(1), one S(3), one S(6), one S(7), two equivalent S(4), and two equivalent S(5) atoms. The Ca(1)-S(1) bond length is 2.92 Å. The Ca(1)-S(3) bond length is 3.05 Å. The Ca(1)-S(6) bond length is 3.09 Å. The Ca(1)-S(7) bond length is 2.95 Å. There is one shorter (3.08 Å) and one longer (3.17 Å) Ca(1)-S(4) bond length. There is one shorter (3.20 Å) and one longer (3.21 Å) Ca(1)-S(5) bond length. In the second Ca site, Ca(2) is bonded in a 4-coordinate geometry to one S(1), one S(5), one S(8), one S(9), and two equivalent S(2) atoms. The Ca(2)-S(1) bond length is 3.43 Å. The Ca(2)-S(5) bond length is 2.79 Å. The Ca(2)-S(8) bond length is 2.85 Å. The Ca(2)-S(9) bond length is 3.43 Å. There is one shorter (2.85 Å) and one longer (2.90 Å) Ca(2)-S(2) bond length. In the third Ca site, Ca(3) is bonded to one S(1), one S(2), one S(4), one S(7), and two equivalent S(8) atoms to form distorted CaS6 octahedra that share  a cornercorner with one Sn(2)S4 tetrahedra, corners with two equivalent Sn(1)S4 tetrahedra, corners with three equivalent Sn(3)S4 tetrahedra, and  an edgeedge with one Ca(3)S6 octahedra. The Ca(3)-S(1) bond length is 2.87 Å. The Ca(3)-S(2) bond length is 2.97 Å. The Ca(3)-S(4) bond length is 2.96 Å. The Ca(3)-S(7) bond length is 2.87 Å. There is one shorter (2.91 Å) and one longer (2.95 Å) Ca(3)-S(8) bond length. There are three 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(9) atom to form SnS4 tetrahedra that share corners with two equivalent Ca(3)S6 octahedra,  a cornercorner with one Sn(2)S4 tetrahedra, and  a cornercorner with one Sn(3)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 68-69°. The Sn(1)-S(1) bond length is 2.38 Å. The Sn(1)-S(2) bond length is 2.40 Å. The Sn(1)-S(3) bond length is 2.43 Å. The Sn(1)-S(9) bond length is 2.44 Å. In the second Sn site, Sn(2) is bonded to one S(3), one S(4), one S(5), and one S(6) atom to form SnS4 tetrahedra that share  a cornercorner with one Ca(3)S6 octahedra,  a cornercorner with one Sn(1)S4 tetrahedra, and  a cornercorner with one Sn(3)S4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. The Sn(2)-S(3) bond length is 2.46 Å. The Sn(2)-S(4) bond length is 2.36 Å. The Sn(2)-S(5) bond length is 2.37 Å. The Sn(2)-S(6) bond length is 2.47 Å. In the third Sn site, Sn(3) is bonded to one S(6), one S(7), one S(8), and one S(9) atom to form SnS4 tetrahedra that share corners with three equivalent Ca(3)S6 octahedra,  a cornercorner with one Sn(1)S4 tetrahedra, and  a cornercorner with one Sn(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-68°. The Sn(3)-S(6) bond length is 2.45 Å. The Sn(3)-S(7) bond length is 2.38 Å. The Sn(3)-S(8) bond length is 2.40 Å. The Sn(3)-S(9) bond length is 2.44 Å. There are nine inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Ca(2), one Ca(3), and one Sn(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ca(3), two equivalent Ca(2), and one Sn(1) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Ca(1), one Sn(1), and one Sn(2) atom. In the fourth S site, S(4) is bonded to one Ca(3), two equivalent Ca(1), and one Sn(2) atom to form a mixture of corner and edge-sharing SCa3Sn tetrahedra. In the fifth S site, S(5) is bonded to one Ca(2), two equivalent Ca(1), and one Sn(2) atom to form a mixture of distorted corner and edge-sharing SCa3Sn tetrahedra. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Ca(1), one Sn(2), and one Sn(3) atom. In the seventh S site, S(7) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Ca(3), and one Sn(3) atom. In the eighth S site, S(8) is bonded to one Ca(2), two equivalent Ca(3), and one Sn(3) atom to form a mixture of distorted corner and edge-sharing SCa3Sn tetrahedra. In the ninth S site, S(9) is bonded in a distorted water-like geometry to one Ca(2), one Sn(1), and one Sn(3) atom.