CaSn6S13 crystallizes in the triclinic P-1 space group. Ca(1) is bonded in a 5-coordinate geometry to one S(10), one S(13), one S(3), one S(4), and one S(8) atom. There are six inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to one S(10), one S(2), one S(5), one S(6), one S(7), and one S(9) atom to form SnS6 octahedra that share corners with two equivalent Sn(3)S6 octahedra, corners with two equivalent Sn(5)S6 octahedra, corners with two equivalent Sn(6)S6 octahedra,  an edgeedge with one Sn(4)S6 octahedra, and  an edgeedge with one Sn(2)S5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 49-64°. In the second Sn site, Sn(2) is bonded to one S(1), one S(11), one S(4), one S(6), and one S(9) atom to form a mixture of corner and edge-sharing SnS5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 54-73°. In the third Sn site, Sn(3) is bonded to one S(1), one S(10), one S(2), one S(4), and two equivalent S(12) atoms to form distorted SnS6 octahedra that share  a cornercorner with one Sn(4)S6 octahedra, corners with two equivalent Sn(1)S6 octahedra, corners with two equivalent Sn(2)S5 trigonal bipyramids,  an edgeedge with one Sn(3)S6 octahedra, and  a faceface with one Sn(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 51-64°. In the fourth Sn site, Sn(4) is bonded to one S(1), one S(11), one S(12), one S(13), one S(2), and one S(7) atom to form SnS6 octahedra that share  a cornercorner with one Sn(3)S6 octahedra, corners with two equivalent Sn(5)S6 octahedra, corners with two equivalent Sn(6)S6 octahedra,  an edgeedge with one Sn(1)S6 octahedra,  an edgeedge with one Sn(2)S5 trigonal bipyramid, and  a faceface with one Sn(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. In the fifth Sn site, Sn(5) is bonded to one S(13), one S(7), one S(8), one S(9), and two equivalent S(3) atoms to form SnS6 octahedra that share corners with two equivalent Sn(1)S6 octahedra, corners with two equivalent Sn(4)S6 octahedra,  a cornercorner with one Sn(2)S5 trigonal bipyramid,  an edgeedge with one Sn(5)S6 octahedra, and edges with two equivalent Sn(6)S6 octahedra. The corner-sharing octahedral tilt angles range from 49-60°. In the sixth Sn site, Sn(6) is bonded to one S(11), one S(13), one S(3), one S(8), and two equivalent S(5) atoms to form SnS6 octahedra that share corners with two equivalent Sn(1)S6 octahedra, corners with two equivalent Sn(4)S6 octahedra,  a cornercorner with one Sn(2)S5 trigonal bipyramid,  an edgeedge with one Sn(6)S6 octahedra, and edges with two equivalent Sn(5)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-59°. There are thirteen inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Sn(2), one Sn(3), and one Sn(4) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Sn(1), one Sn(3), and one Sn(4) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Sn(6), and two equivalent Sn(5) atoms. In the fourth S site, S(4) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Sn(2), and one Sn(3) atom. In the fifth S site, S(5) is bonded in a distorted trigonal planar geometry to one Sn(1) and two equivalent Sn(6) atoms. In the sixth S site, S(6) is bonded in an L-shaped geometry to one Sn(1) and one Sn(2) atom. In the seventh S site, S(7) is bonded in a trigonal planar geometry to one Sn(1), one Sn(4), and one Sn(5) atom. In the eighth S site, S(8) is bonded in a trigonal non-coplanar geometry to one Ca(1), one Sn(5), and one Sn(6) atom. In the ninth S site, S(9) is bonded in a distorted trigonal planar geometry to one Sn(1), one Sn(2), and one Sn(5) atom. In the tenth S site, S(10) is bonded in a distorted trigonal planar geometry to one Ca(1), one Sn(1), and one Sn(3) atom. In the eleventh S site, S(11) is bonded in a distorted trigonal planar geometry to one Sn(2), one Sn(4), and one Sn(6) atom. In the twelfth S site, S(12) is bonded in a distorted T-shaped geometry to one Sn(4) and two equivalent Sn(3) atoms. In the thirteenth S site, S(13) is bonded in a tetrahedral geometry to one Ca(1), one Sn(4), one Sn(5), and one Sn(6) atom.
CaSn6S13 crystallizes in the triclinic P-1 space group. Ca(1) is bonded in a 5-coordinate geometry to one S(10), one S(13), one S(3), one S(4), and one S(8) atom. The Ca(1)-S(10) bond length is 3.06 Å. The Ca(1)-S(13) bond length is 3.26 Å. The Ca(1)-S(3) bond length is 3.21 Å. The Ca(1)-S(4) bond length is 3.12 Å. The Ca(1)-S(8) bond length is 2.99 Å. There are six inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to one S(10), one S(2), one S(5), one S(6), one S(7), and one S(9) atom to form SnS6 octahedra that share corners with two equivalent Sn(3)S6 octahedra, corners with two equivalent Sn(5)S6 octahedra, corners with two equivalent Sn(6)S6 octahedra,  an edgeedge with one Sn(4)S6 octahedra, and  an edgeedge with one Sn(2)S5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 49-64°. The Sn(1)-S(10) bond length is 2.50 Å. The Sn(1)-S(2) bond length is 2.59 Å. The Sn(1)-S(5) bond length is 2.73 Å. The Sn(1)-S(6) bond length is 2.52 Å. The Sn(1)-S(7) bond length is 2.59 Å. The Sn(1)-S(9) bond length is 2.67 Å. In the second Sn site, Sn(2) is bonded to one S(1), one S(11), one S(4), one S(6), and one S(9) atom to form a mixture of corner and edge-sharing SnS5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 54-73°. The Sn(2)-S(1) bond length is 2.60 Å. The Sn(2)-S(11) bond length is 2.62 Å. The Sn(2)-S(4) bond length is 2.47 Å. The Sn(2)-S(6) bond length is 2.54 Å. The Sn(2)-S(9) bond length is 2.52 Å. In the third Sn site, Sn(3) is bonded to one S(1), one S(10), one S(2), one S(4), and two equivalent S(12) atoms to form distorted SnS6 octahedra that share  a cornercorner with one Sn(4)S6 octahedra, corners with two equivalent Sn(1)S6 octahedra, corners with two equivalent Sn(2)S5 trigonal bipyramids,  an edgeedge with one Sn(3)S6 octahedra, and  a faceface with one Sn(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 51-64°. The Sn(3)-S(1) bond length is 2.78 Å. The Sn(3)-S(10) bond length is 2.49 Å. The Sn(3)-S(2) bond length is 2.66 Å. The Sn(3)-S(4) bond length is 2.56 Å. There is one shorter (2.55 Å) and one longer (2.64 Å) Sn(3)-S(12) bond length. In the fourth Sn site, Sn(4) is bonded to one S(1), one S(11), one S(12), one S(13), one S(2), and one S(7) atom to form SnS6 octahedra that share  a cornercorner with one Sn(3)S6 octahedra, corners with two equivalent Sn(5)S6 octahedra, corners with two equivalent Sn(6)S6 octahedra,  an edgeedge with one Sn(1)S6 octahedra,  an edgeedge with one Sn(2)S5 trigonal bipyramid, and  a faceface with one Sn(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. The Sn(4)-S(1) bond length is 2.60 Å. The Sn(4)-S(11) bond length is 2.49 Å. The Sn(4)-S(12) bond length is 2.67 Å. The Sn(4)-S(13) bond length is 2.62 Å. The Sn(4)-S(2) bond length is 2.56 Å. The Sn(4)-S(7) bond length is 2.56 Å. In the fifth Sn site, Sn(5) is bonded to one S(13), one S(7), one S(8), one S(9), and two equivalent S(3) atoms to form SnS6 octahedra that share corners with two equivalent Sn(1)S6 octahedra, corners with two equivalent Sn(4)S6 octahedra,  a cornercorner with one Sn(2)S5 trigonal bipyramid,  an edgeedge with one Sn(5)S6 octahedra, and edges with two equivalent Sn(6)S6 octahedra. The corner-sharing octahedral tilt angles range from 49-60°. The Sn(5)-S(13) bond length is 2.60 Å. The Sn(5)-S(7) bond length is 2.56 Å. The Sn(5)-S(8) bond length is 2.54 Å. The Sn(5)-S(9) bond length is 2.67 Å. There is one shorter (2.58 Å) and one longer (2.69 Å) Sn(5)-S(3) bond length. In the sixth Sn site, Sn(6) is bonded to one S(11), one S(13), one S(3), one S(8), and two equivalent S(5) atoms to form SnS6 octahedra that share corners with two equivalent Sn(1)S6 octahedra, corners with two equivalent Sn(4)S6 octahedra,  a cornercorner with one Sn(2)S5 trigonal bipyramid,  an edgeedge with one Sn(6)S6 octahedra, and edges with two equivalent Sn(5)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-59°. The Sn(6)-S(11) bond length is 2.62 Å. The Sn(6)-S(13) bond length is 2.60 Å. The Sn(6)-S(3) bond length is 2.58 Å. The Sn(6)-S(8) bond length is 2.58 Å. There is one shorter (2.51 Å) and one longer (2.62 Å) Sn(6)-S(5) bond length. There are thirteen inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Sn(2), one Sn(3), and one Sn(4) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Sn(1), one Sn(3), and one Sn(4) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Sn(6), and two equivalent Sn(5) atoms. In the fourth S site, S(4) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Sn(2), and one Sn(3) atom. In the fifth S site, S(5) is bonded in a distorted trigonal planar geometry to one Sn(1) and two equivalent Sn(6) atoms. In the sixth S site, S(6) is bonded in an L-shaped geometry to one Sn(1) and one Sn(2) atom. In the seventh S site, S(7) is bonded in a trigonal planar geometry to one Sn(1), one Sn(4), and one Sn(5) atom. In the eighth S site, S(8) is bonded in a trigonal non-coplanar geometry to one Ca(1), one Sn(5), and one Sn(6) atom. In the ninth S site, S(9) is bonded in a distorted trigonal planar geometry to one Sn(1), one Sn(2), and one Sn(5) atom. In the tenth S site, S(10) is bonded in a distorted trigonal planar geometry to one Ca(1), one Sn(1), and one Sn(3) atom. In the eleventh S site, S(11) is bonded in a distorted trigonal planar geometry to one Sn(2), one Sn(4), and one Sn(6) atom. In the twelfth S site, S(12) is bonded in a distorted T-shaped geometry to one Sn(4) and two equivalent Sn(3) atoms. In the thirteenth S site, S(13) is bonded in a tetrahedral geometry to one Ca(1), one Sn(4), one Sn(5), and one Sn(6) atom.