K3SbS4 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(1), and four equivalent S(3) atoms. In the second K site, K(2) is bonded to one S(1), two equivalent S(2), and three equivalent S(3) atoms to form distorted KS6 pentagonal pyramids that share corners with seven equivalent K(2)S6 pentagonal pyramids, corners with two equivalent Sb(1)S4 tetrahedra, edges with three equivalent K(2)S6 pentagonal pyramids, and edges with two equivalent Sb(1)S4 tetrahedra. Sb(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form SbS4 tetrahedra that share corners with four equivalent K(2)S6 pentagonal pyramids and edges with four equivalent K(2)S6 pentagonal pyramids. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent K(1), two equivalent K(2), and one Sb(1) atom to form distorted corner-sharing SK4Sb trigonal bipyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to one K(1), four equivalent K(2), and one Sb(1) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to two equivalent K(1), three equivalent K(2), and one Sb(1) atom.
K3SbS4 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(1), and four equivalent S(3) atoms. The K(1)-S(2) bond length is 3.30 Å. There is one shorter (3.14 Å) and one longer (3.27 Å) K(1)-S(1) bond length. There are two shorter (3.28 Å) and two longer (3.70 Å) K(1)-S(3) bond lengths. In the second K site, K(2) is bonded to one S(1), two equivalent S(2), and three equivalent S(3) atoms to form distorted KS6 pentagonal pyramids that share corners with seven equivalent K(2)S6 pentagonal pyramids, corners with two equivalent Sb(1)S4 tetrahedra, edges with three equivalent K(2)S6 pentagonal pyramids, and edges with two equivalent Sb(1)S4 tetrahedra. The K(2)-S(1) bond length is 3.22 Å. There is one shorter (3.23 Å) and one longer (3.30 Å) K(2)-S(2) bond length. There are a spread of K(2)-S(3) bond distances ranging from 3.21-3.39 Å. Sb(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form SbS4 tetrahedra that share corners with four equivalent K(2)S6 pentagonal pyramids and edges with four equivalent K(2)S6 pentagonal pyramids. The Sb(1)-S(1) bond length is 2.36 Å. The Sb(1)-S(2) bond length is 2.36 Å. Both Sb(1)-S(3) bond lengths are 2.35 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent K(1), two equivalent K(2), and one Sb(1) atom to form distorted corner-sharing SK4Sb trigonal bipyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to one K(1), four equivalent K(2), and one Sb(1) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to two equivalent K(1), three equivalent K(2), and one Sb(1) atom.