Ca3SnS5 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to eight equivalent S(2) atoms. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to two equivalent S(1) and six equivalent S(2) atoms. Sn(1) is bonded in a tetrahedral geometry to four equivalent S(2) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a square co-planar geometry to four equivalent Ca(2) atoms. In the second S site, S(2) is bonded to two equivalent Ca(1), three equivalent Ca(2), and one Sn(1) atom to form a mixture of distorted edge, face, and corner-sharing SCa5Sn octahedra. The corner-sharing octahedral tilt angles range from 33-56°.
Ca3SnS5 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to eight equivalent S(2) atoms. All Ca(1)-S(2) bond lengths are 3.26 Å. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to two equivalent S(1) and six equivalent S(2) atoms. Both Ca(2)-S(1) bond lengths are 2.88 Å. There are two shorter (2.77 Å) and four longer (3.23 Å) Ca(2)-S(2) bond lengths. Sn(1) is bonded in a tetrahedral geometry to four equivalent S(2) atoms. All Sn(1)-S(2) bond lengths are 2.36 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a square co-planar geometry to four equivalent Ca(2) atoms. In the second S site, S(2) is bonded to two equivalent Ca(1), three equivalent Ca(2), and one Sn(1) atom to form a mixture of distorted edge, face, and corner-sharing SCa5Sn octahedra. The corner-sharing octahedral tilt angles range from 33-56°.