Ca2SnS4 crystallizes in the orthorhombic Pnma 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(2), two equivalent S(3), and four equivalent S(1) atoms. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to one S(2) and four equivalent S(1) atoms. Sn(1) is bonded in a distorted tetrahedral geometry to one S(2), one S(3), and two equivalent S(1) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), and one Sn(1) atom. In the second S site, S(2) is bonded in a T-shaped geometry to one Ca(1), one Ca(2), and one Sn(1) atom. In the third S site, S(3) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Sn(1) atom.
Ca2SnS4 crystallizes in the orthorhombic Pnma 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(2), two equivalent S(3), and four equivalent S(1) atoms. The Ca(1)-S(2) bond length is 2.95 Å. There is one shorter (2.83 Å) and one longer (2.85 Å) Ca(1)-S(3) bond length. There are two shorter (3.04 Å) and two longer (3.43 Å) Ca(1)-S(1) bond lengths. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to one S(2) and four equivalent S(1) atoms. The Ca(2)-S(2) bond length is 2.72 Å. There are two shorter (2.83 Å) and two longer (3.00 Å) Ca(2)-S(1) bond lengths. Sn(1) is bonded in a distorted tetrahedral geometry to one S(2), one S(3), and two equivalent S(1) atoms. The Sn(1)-S(2) bond length is 2.34 Å. The Sn(1)-S(3) bond length is 2.40 Å. Both Sn(1)-S(1) bond lengths are 2.42 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), and one Sn(1) atom. In the second S site, S(2) is bonded in a T-shaped geometry to one Ca(1), one Ca(2), and one Sn(1) atom. In the third S site, S(3) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Sn(1) atom.