KAuS5 crystallizes in the orthorhombic Ibam space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to two equivalent Au(1), four equivalent S(1), and four equivalent S(2) atoms. In the second K site, K(2) is bonded in a 10-coordinate geometry to two equivalent S(3), four equivalent S(1), and four equivalent S(2) atoms. Au(1) is bonded in a distorted linear geometry to one K(1) and two equivalent S(2) atoms. There are three inequivalent S sites. In the first S site, S(3) is bonded in a distorted water-like geometry to one K(2) and two equivalent S(1) atoms. In the second S site, S(1) is bonded to one K(1), one K(2), one S(2), and one S(3) atom to form distorted SK2S2 tetrahedra that share corners with five equivalent S(1)K2S2 tetrahedra, corners with six equivalent S(2)K2AuS tetrahedra,  an edgeedge with one S(2)K2AuS tetrahedra, and  an edgeedge with one S(1)K2S2 tetrahedra. In the third S site, S(2) is bonded to one K(1), one K(2), one Au(1), and one S(1) atom to form SK2AuS tetrahedra that share corners with six equivalent S(1)K2S2 tetrahedra, corners with seven equivalent S(2)K2AuS tetrahedra, and  an edgeedge with one S(1)K2S2 tetrahedra.
KAuS5 crystallizes in the orthorhombic Ibam space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to two equivalent Au(1), four equivalent S(1), and four equivalent S(2) atoms. Both K(1)-Au(1) bond lengths are 3.92 Å. All K(1)-S(1) bond lengths are 3.45 Å. All K(1)-S(2) bond lengths are 3.35 Å. In the second K site, K(2) is bonded in a 10-coordinate geometry to two equivalent S(3), four equivalent S(1), and four equivalent S(2) atoms. Both K(2)-S(3) bond lengths are 3.74 Å. All K(2)-S(1) bond lengths are 3.55 Å. All K(2)-S(2) bond lengths are 3.25 Å. Au(1) is bonded in a distorted linear geometry to one K(1) and two equivalent S(2) atoms. Both Au(1)-S(2) bond lengths are 2.31 Å. There are three inequivalent S sites. In the first S site, S(3) is bonded in a distorted water-like geometry to one K(2) and two equivalent S(1) atoms. Both S(3)-S(1) bond lengths are 2.06 Å. In the second S site, S(1) is bonded to one K(1), one K(2), one S(2), and one S(3) atom to form distorted SK2S2 tetrahedra that share corners with five equivalent S(1)K2S2 tetrahedra, corners with six equivalent S(2)K2AuS tetrahedra,  an edgeedge with one S(2)K2AuS tetrahedra, and  an edgeedge with one S(1)K2S2 tetrahedra. The S(1)-S(2) bond length is 2.07 Å. In the third S site, S(2) is bonded to one K(1), one K(2), one Au(1), and one S(1) atom to form SK2AuS tetrahedra that share corners with six equivalent S(1)K2S2 tetrahedra, corners with seven equivalent S(2)K2AuS tetrahedra, and  an edgeedge with one S(1)K2S2 tetrahedra.