K3AsS4 crystallizes in the orthorhombic Pna2_1 space group. There are three 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), two equivalent S(3), and two equivalent S(4) atoms. In the second K site, K(2) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. In the third K site, K(3) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. As(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. There are four inequivalent S sites. In the first S site, S(1) is bonded to one K(3), two equivalent K(1), two equivalent K(2), and one As(1) atom to form edge-sharing SK5As octahedra. In the second S site, S(2) is bonded in a 6-coordinate geometry to one K(1), two equivalent K(2), two equivalent K(3), and one As(1) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to two equivalent K(1), two equivalent K(2), two equivalent K(3), and one As(1) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one K(2), two equivalent K(1), two equivalent K(3), and one As(1) atom.
K3AsS4 crystallizes in the orthorhombic Pna2_1 space group. There are three 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), two equivalent S(3), and two equivalent S(4) atoms. The K(1)-S(2) bond length is 3.30 Å. There is one shorter (3.17 Å) and one longer (3.22 Å) K(1)-S(1) bond length. There is one shorter (3.34 Å) and one longer (3.52 Å) K(1)-S(3) bond length. There is one shorter (3.28 Å) and one longer (3.44 Å) K(1)-S(4) bond length. In the second K site, K(2) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. The K(2)-S(4) bond length is 3.30 Å. There is one shorter (3.17 Å) and one longer (3.22 Å) K(2)-S(1) bond length. There is one shorter (3.29 Å) and one longer (3.43 Å) K(2)-S(2) bond length. There is one shorter (3.33 Å) and one longer (3.55 Å) K(2)-S(3) bond length. In the third K site, K(3) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. The K(3)-S(1) bond length is 3.12 Å. There is one shorter (3.30 Å) and one longer (3.67 Å) K(3)-S(2) bond length. There is one shorter (3.34 Å) and one longer (3.38 Å) K(3)-S(3) bond length. There is one shorter (3.29 Å) and one longer (3.70 Å) K(3)-S(4) bond length. As(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. The As(1)-S(1) bond length is 2.17 Å. The As(1)-S(2) bond length is 2.17 Å. The As(1)-S(3) bond length is 2.18 Å. The As(1)-S(4) bond length is 2.17 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one K(3), two equivalent K(1), two equivalent K(2), and one As(1) atom to form edge-sharing SK5As octahedra. In the second S site, S(2) is bonded in a 6-coordinate geometry to one K(1), two equivalent K(2), two equivalent K(3), and one As(1) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to two equivalent K(1), two equivalent K(2), two equivalent K(3), and one As(1) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one K(2), two equivalent K(1), two equivalent K(3), and one As(1) atom.