Ca2SnS4 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 7-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. In the second Ca site, Ca(2) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(2), and three equivalent S(4) atoms. Sn(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(1), two equivalent Ca(2), and one Sn(1) atom to form a mixture of distorted corner and edge-sharing SCa4Sn trigonal bipyramids. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Ca(1), 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 two equivalent Ca(1) and one Sn(1) atom. In the fourth S site, S(4) is bonded to one Ca(1), three equivalent Ca(2), and one Sn(1) atom to form a mixture of distorted corner and edge-sharing SCa4Sn trigonal bipyramids.
Ca2SnS4 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 7-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. The Ca(1)-S(4) bond length is 2.98 Å. There is one shorter (2.95 Å) and one longer (3.02 Å) Ca(1)-S(1) bond length. There is one shorter (2.83 Å) and one longer (3.42 Å) Ca(1)-S(2) bond length. There is one shorter (2.93 Å) and one longer (3.23 Å) Ca(1)-S(3) bond length. In the second Ca site, Ca(2) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(2), and three equivalent S(4) atoms. There is one shorter (3.05 Å) and one longer (3.22 Å) Ca(2)-S(1) bond length. There is one shorter (2.77 Å) and one longer (3.10 Å) Ca(2)-S(2) bond length. There are a spread of Ca(2)-S(4) bond distances ranging from 2.92-3.14 Å. Sn(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. The Sn(1)-S(1) bond length is 2.40 Å. The Sn(1)-S(2) bond length is 2.41 Å. The Sn(1)-S(3) bond length is 2.37 Å. The Sn(1)-S(4) bond length is 2.43 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(1), two equivalent Ca(2), and one Sn(1) atom to form a mixture of distorted corner and edge-sharing SCa4Sn trigonal bipyramids. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Ca(1), 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 two equivalent Ca(1) and one Sn(1) atom. In the fourth S site, S(4) is bonded to one Ca(1), three equivalent Ca(2), and one Sn(1) atom to form a mixture of distorted corner and edge-sharing SCa4Sn trigonal bipyramids.