Ca4SnS6 crystallizes in the trigonal R-3c space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to six equivalent S(1) atoms. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to eight equivalent S(1) atoms. Sn(1) is bonded in an octahedral geometry to six equivalent S(1) atoms. S(1) is bonded to one Ca(1), four equivalent Ca(2), and one Sn(1) atom to form a mixture of distorted corner, edge, and face-sharing SCa5Sn octahedra. The corner-sharing octahedral tilt angles range from 0-68°.
Ca4SnS6 crystallizes in the trigonal R-3c space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to six equivalent S(1) atoms. All Ca(1)-S(1) bond lengths are 2.84 Å. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to eight equivalent S(1) atoms. There are a spread of Ca(2)-S(1) bond distances ranging from 2.96-3.22 Å. Sn(1) is bonded in an octahedral geometry to six equivalent S(1) atoms. All Sn(1)-S(1) bond lengths are 2.56 Å. S(1) is bonded to one Ca(1), four equivalent Ca(2), and one Sn(1) atom to form a mixture of distorted corner, edge, and face-sharing SCa5Sn octahedra. The corner-sharing octahedral tilt angles range from 0-68°.