K5Zn4Sn5S17NH4 crystallizes in the tetragonal I-4m2 space group. The structure consists of two ammonium molecules inside a K5Zn4Sn5S17 framework. In the K5Zn4Sn5S17 framework, there are two inequivalent K sites. In the first K site, K(1) is bonded in a 6-coordinate geometry to two equivalent S(2) and four equivalent S(4) atoms. In the second K site, K(2) is bonded in a body-centered cubic geometry to eight equivalent S(4) atoms. Zn(1) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form ZnS4 tetrahedra that share corners with three equivalent Zn(1)S4 tetrahedra and corners with three equivalent Sn(2)S4 tetrahedra. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to four equivalent S(1) atoms to form corner-sharing SnS4 tetrahedra. In the second Sn site, Sn(2) is bonded to one S(1), one S(2), and two equivalent S(4) atoms to form SnS4 tetrahedra that share  a cornercorner with one Sn(1)S4 tetrahedra and corners with three equivalent Zn(1)S4 tetrahedra. There are four inequivalent S sites. In the first S site, S(1) is bonded in a water-like geometry to one Sn(1) and one Sn(2) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to two equivalent K(1), one Zn(1), and one Sn(2) atom. In the third S site, S(3) is bonded to four equivalent Zn(1) atoms to form corner-sharing SZn4 tetrahedra. In the fourth S site, S(4) is bonded to one K(2), two equivalent K(1), one Zn(1), and one Sn(2) atom to form distorted SK3ZnSn trigonal bipyramids that share  a cornercorner with one S(3)Zn4 tetrahedra, corners with seven equivalent S(4)K3ZnSn trigonal bipyramids, and edges with four equivalent S(4)K3ZnSn trigonal bipyramids.
K5Zn4Sn5S17NH4 crystallizes in the tetragonal I-4m2 space group. The structure consists of two ammonium molecules inside a K5Zn4Sn5S17 framework. In the K5Zn4Sn5S17 framework, there are two inequivalent K sites. In the first K site, K(1) is bonded in a 6-coordinate geometry to two equivalent S(2) and four equivalent S(4) atoms. Both K(1)-S(2) bond lengths are 3.42 Å. There are two shorter (3.25 Å) and two longer (3.40 Å) K(1)-S(4) bond lengths. In the second K site, K(2) is bonded in a body-centered cubic geometry to eight equivalent S(4) atoms. All K(2)-S(4) bond lengths are 3.50 Å. Zn(1) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form ZnS4 tetrahedra that share corners with three equivalent Zn(1)S4 tetrahedra and corners with three equivalent Sn(2)S4 tetrahedra. The Zn(1)-S(2) bond length is 2.36 Å. The Zn(1)-S(3) bond length is 2.34 Å. Both Zn(1)-S(4) bond lengths are 2.36 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to four equivalent S(1) atoms to form corner-sharing SnS4 tetrahedra. All Sn(1)-S(1) bond lengths are 2.44 Å. In the second Sn site, Sn(2) is bonded to one S(1), one S(2), and two equivalent S(4) atoms to form SnS4 tetrahedra that share  a cornercorner with one Sn(1)S4 tetrahedra and corners with three equivalent Zn(1)S4 tetrahedra. The Sn(2)-S(1) bond length is 2.50 Å. The Sn(2)-S(2) bond length is 2.40 Å. Both Sn(2)-S(4) bond lengths are 2.40 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a water-like geometry to one Sn(1) and one Sn(2) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to two equivalent K(1), one Zn(1), and one Sn(2) atom. In the third S site, S(3) is bonded to four equivalent Zn(1) atoms to form corner-sharing SZn4 tetrahedra. In the fourth S site, S(4) is bonded to one K(2), two equivalent K(1), one Zn(1), and one Sn(2) atom to form distorted SK3ZnSn trigonal bipyramids that share  a cornercorner with one S(3)Zn4 tetrahedra, corners with seven equivalent S(4)K3ZnSn trigonal bipyramids, and edges with four equivalent S(4)K3ZnSn trigonal bipyramids.