K6Zn4Sn5S17 crystallizes in the monoclinic C2 space group. There are five inequivalent K sites. In the first K site, K(1) is bonded in a body-centered cubic geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. In the second K site, K(2) is bonded in a distorted bent 150 degrees geometry to two equivalent S(7) atoms. In the third K site, K(3) is bonded in a 6-coordinate geometry to one S(7), one S(8), two equivalent S(1), and two equivalent S(2) atoms. In the fourth K site, K(4) is bonded in a 6-coordinate geometry to two equivalent S(3), two equivalent S(4), and two equivalent S(8) atoms. In the fifth K site, K(5) is bonded in a 6-coordinate geometry to two equivalent S(3), two equivalent S(4), and two equivalent S(7) atoms. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(1), one S(4), one S(8), and one S(9) atom to form ZnS4 tetrahedra that share  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Sn(2)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, and corners with two equivalent Sn(3)S4 tetrahedra. In the second Zn site, Zn(2) is bonded to one S(2), one S(3), one S(7), and one S(9) atom to form ZnS4 tetrahedra that share  a cornercorner with one Zn(2)S4 tetrahedra,  a cornercorner with one Sn(3)S4 tetrahedra, corners with two equivalent Zn(1)S4 tetrahedra, and corners with two equivalent Sn(2)S4 tetrahedra. There are three inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to two equivalent S(5) and two equivalent S(6) atoms to form corner-sharing SnS4 tetrahedra. In the second Sn site, Sn(2) is bonded to one S(1), one S(3), one S(5), and one S(7) atom to form SnS4 tetrahedra that share  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Sn(1)S4 tetrahedra, and corners with two equivalent Zn(2)S4 tetrahedra. In the third Sn site, Sn(3) is bonded to one S(2), one S(4), one S(6), and one S(8) atom to form SnS4 tetrahedra that share  a cornercorner with one Zn(2)S4 tetrahedra,  a cornercorner with one Sn(1)S4 tetrahedra, and corners with two equivalent Zn(1)S4 tetrahedra. There are nine inequivalent S sites. In the first S site, S(1) is bonded to one K(1), two equivalent K(3), one Zn(1), and one Sn(2) atom to form distorted SK3ZnSn trigonal bipyramids that share  a cornercorner with one S(9)Zn4 tetrahedra,  a cornercorner with one S(1)K3ZnSn trigonal bipyramid,  a cornercorner with one S(3)K3ZnSn trigonal bipyramid,  a cornercorner with one S(4)K3ZnSn trigonal bipyramid,  an edgeedge with one S(1)K3ZnSn trigonal bipyramid,  an edgeedge with one S(3)K3ZnSn trigonal bipyramid, and  an edgeedge with one S(4)K3ZnSn trigonal bipyramid. In the second S site, S(2) is bonded in a 5-coordinate geometry to one K(1), two equivalent K(3), one Zn(2), and one Sn(3) atom. In the third S site, S(3) is bonded to one K(1), one K(4), one K(5), one Zn(2), and one Sn(2) atom to form distorted SK3ZnSn trigonal bipyramids that share  a cornercorner with one S(9)Zn4 tetrahedra,  a cornercorner with one S(1)K3ZnSn trigonal bipyramid,  a cornercorner with one S(3)K3ZnSn trigonal bipyramid, corners with four equivalent S(4)K3ZnSn trigonal bipyramids,  an edgeedge with one S(1)K3ZnSn trigonal bipyramid,  an edgeedge with one S(3)K3ZnSn trigonal bipyramid, and  an edgeedge with one S(4)K3ZnSn trigonal bipyramid. In the fourth S site, S(4) is bonded to one K(1), one K(4), one K(5), one Zn(1), and one Sn(3) atom to form distorted SK3ZnSn trigonal bipyramids that share  a cornercorner with one S(9)Zn4 tetrahedra,  a cornercorner with one S(1)K3ZnSn trigonal bipyramid,  a cornercorner with one S(4)K3ZnSn trigonal bipyramid, corners with four equivalent S(3)K3ZnSn trigonal bipyramids,  an edgeedge with one S(1)K3ZnSn trigonal bipyramid,  an edgeedge with one S(3)K3ZnSn trigonal bipyramid, and  an edgeedge with one S(4)K3ZnSn trigonal bipyramid. In the fifth S site, S(5) is bonded in a water-like geometry to one Sn(1) and one Sn(2) atom. In the sixth S site, S(6) is bonded in a water-like geometry to one Sn(1) and one Sn(3) atom. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one K(2), one K(3), one K(5), one Zn(2), and one Sn(2) atom. In the eighth S site, S(8) is bonded in a distorted see-saw-like geometry to one K(3), one K(4), one Zn(1), and one Sn(3) atom. In the ninth S site, S(9) is bonded to two equivalent Zn(1) and two equivalent Zn(2) atoms to form corner-sharing SZn4 tetrahedra.
K6Zn4Sn5S17 crystallizes in the monoclinic C2 space group. There are five inequivalent K sites. In the first K site, K(1) is bonded in a body-centered cubic geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. Both K(1)-S(1) bond lengths are 3.50 Å. Both K(1)-S(2) bond lengths are 3.52 Å. Both K(1)-S(3) bond lengths are 3.52 Å. Both K(1)-S(4) bond lengths are 3.49 Å. In the second K site, K(2) is bonded in a distorted bent 150 degrees geometry to two equivalent S(7) atoms. Both K(2)-S(7) bond lengths are 3.27 Å. In the third K site, K(3) is bonded in a 6-coordinate geometry to one S(7), one S(8), two equivalent S(1), and two equivalent S(2) atoms. The K(3)-S(7) bond length is 3.45 Å. The K(3)-S(8) bond length is 3.37 Å. There is one shorter (3.22 Å) and one longer (3.38 Å) K(3)-S(1) bond length. There is one shorter (3.23 Å) and one longer (3.45 Å) K(3)-S(2) bond length. In the fourth K site, K(4) is bonded in a 6-coordinate geometry to two equivalent S(3), two equivalent S(4), and two equivalent S(8) atoms. Both K(4)-S(3) bond lengths are 3.24 Å. Both K(4)-S(4) bond lengths are 3.43 Å. Both K(4)-S(8) bond lengths are 3.42 Å. In the fifth K site, K(5) is bonded in a 6-coordinate geometry to two equivalent S(3), two equivalent S(4), and two equivalent S(7) atoms. Both K(5)-S(3) bond lengths are 3.42 Å. Both K(5)-S(4) bond lengths are 3.23 Å. Both K(5)-S(7) bond lengths are 3.42 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(1), one S(4), one S(8), and one S(9) atom to form ZnS4 tetrahedra that share  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Sn(2)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, and corners with two equivalent Sn(3)S4 tetrahedra. The Zn(1)-S(1) bond length is 2.37 Å. The Zn(1)-S(4) bond length is 2.35 Å. The Zn(1)-S(8) bond length is 2.35 Å. The Zn(1)-S(9) bond length is 2.36 Å. In the second Zn site, Zn(2) is bonded to one S(2), one S(3), one S(7), and one S(9) atom to form ZnS4 tetrahedra that share  a cornercorner with one Zn(2)S4 tetrahedra,  a cornercorner with one Sn(3)S4 tetrahedra, corners with two equivalent Zn(1)S4 tetrahedra, and corners with two equivalent Sn(2)S4 tetrahedra. The Zn(2)-S(2) bond length is 2.36 Å. The Zn(2)-S(3) bond length is 2.36 Å. The Zn(2)-S(7) bond length is 2.37 Å. The Zn(2)-S(9) bond length is 2.34 Å. There are three inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to two equivalent S(5) and two equivalent S(6) atoms to form corner-sharing SnS4 tetrahedra. Both Sn(1)-S(5) bond lengths are 2.45 Å. Both Sn(1)-S(6) bond lengths are 2.43 Å. In the second Sn site, Sn(2) is bonded to one S(1), one S(3), one S(5), and one S(7) atom to form SnS4 tetrahedra that share  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Sn(1)S4 tetrahedra, and corners with two equivalent Zn(2)S4 tetrahedra. The Sn(2)-S(1) bond length is 2.40 Å. The Sn(2)-S(3) bond length is 2.40 Å. The Sn(2)-S(5) bond length is 2.49 Å. The Sn(2)-S(7) bond length is 2.42 Å. In the third Sn site, Sn(3) is bonded to one S(2), one S(4), one S(6), and one S(8) atom to form SnS4 tetrahedra that share  a cornercorner with one Zn(2)S4 tetrahedra,  a cornercorner with one Sn(1)S4 tetrahedra, and corners with two equivalent Zn(1)S4 tetrahedra. The Sn(3)-S(2) bond length is 2.43 Å. The Sn(3)-S(4) bond length is 2.40 Å. The Sn(3)-S(6) bond length is 2.49 Å. The Sn(3)-S(8) bond length is 2.39 Å. There are nine inequivalent S sites. In the first S site, S(1) is bonded to one K(1), two equivalent K(3), one Zn(1), and one Sn(2) atom to form distorted SK3ZnSn trigonal bipyramids that share  a cornercorner with one S(9)Zn4 tetrahedra,  a cornercorner with one S(1)K3ZnSn trigonal bipyramid,  a cornercorner with one S(3)K3ZnSn trigonal bipyramid,  a cornercorner with one S(4)K3ZnSn trigonal bipyramid,  an edgeedge with one S(1)K3ZnSn trigonal bipyramid,  an edgeedge with one S(3)K3ZnSn trigonal bipyramid, and  an edgeedge with one S(4)K3ZnSn trigonal bipyramid. In the second S site, S(2) is bonded in a 5-coordinate geometry to one K(1), two equivalent K(3), one Zn(2), and one Sn(3) atom. In the third S site, S(3) is bonded to one K(1), one K(4), one K(5), one Zn(2), and one Sn(2) atom to form distorted SK3ZnSn trigonal bipyramids that share  a cornercorner with one S(9)Zn4 tetrahedra,  a cornercorner with one S(1)K3ZnSn trigonal bipyramid,  a cornercorner with one S(3)K3ZnSn trigonal bipyramid, corners with four equivalent S(4)K3ZnSn trigonal bipyramids,  an edgeedge with one S(1)K3ZnSn trigonal bipyramid,  an edgeedge with one S(3)K3ZnSn trigonal bipyramid, and  an edgeedge with one S(4)K3ZnSn trigonal bipyramid. In the fourth S site, S(4) is bonded to one K(1), one K(4), one K(5), one Zn(1), and one Sn(3) atom to form distorted SK3ZnSn trigonal bipyramids that share  a cornercorner with one S(9)Zn4 tetrahedra,  a cornercorner with one S(1)K3ZnSn trigonal bipyramid,  a cornercorner with one S(4)K3ZnSn trigonal bipyramid, corners with four equivalent S(3)K3ZnSn trigonal bipyramids,  an edgeedge with one S(1)K3ZnSn trigonal bipyramid,  an edgeedge with one S(3)K3ZnSn trigonal bipyramid, and  an edgeedge with one S(4)K3ZnSn trigonal bipyramid. In the fifth S site, S(5) is bonded in a water-like geometry to one Sn(1) and one Sn(2) atom. In the sixth S site, S(6) is bonded in a water-like geometry to one Sn(1) and one Sn(3) atom. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one K(2), one K(3), one K(5), one Zn(2), and one Sn(2) atom. In the eighth S site, S(8) is bonded in a distorted see-saw-like geometry to one K(3), one K(4), one Zn(1), and one Sn(3) atom. In the ninth S site, S(9) is bonded to two equivalent Zn(1) and two equivalent Zn(2) atoms to form corner-sharing SZn4 tetrahedra.