K2WS4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 9-coordinate geometry to two equivalent S(3), three equivalent S(2), and four equivalent S(1) atoms. In the second K site, K(2) is bonded to one S(2), two equivalent S(3), and four equivalent S(1) atoms to form distorted KS7 hexagonal pyramids that share corners with two equivalent K(2)S7 hexagonal pyramids,  a cornercorner with one W(1)S4 tetrahedra, edges with two equivalent K(2)S7 hexagonal pyramids, and edges with three equivalent W(1)S4 tetrahedra. W(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form WS4 tetrahedra that share  a cornercorner with one K(2)S7 hexagonal pyramid and edges with three equivalent K(2)S7 hexagonal 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 W(1) atom to form a mixture of distorted edge, face, and corner-sharing SK4W trigonal bipyramids. In the second S site, S(2) is bonded to one K(2), three equivalent K(1), and one W(1) atom to form a mixture of distorted edge and corner-sharing SK4W trigonal bipyramids. In the third S site, S(3) is bonded to two equivalent K(1), two equivalent K(2), and one W(1) atom to form a mixture of distorted edge and corner-sharing SK4W square pyramids.
K2WS4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 9-coordinate geometry to two equivalent S(3), three equivalent S(2), and four equivalent S(1) atoms. There is one shorter (3.17 Å) and one longer (3.27 Å) K(1)-S(3) bond length. There is one shorter (3.37 Å) and two longer (3.59 Å) K(1)-S(2) bond lengths. There are two shorter (3.31 Å) and two longer (3.41 Å) K(1)-S(1) bond lengths. In the second K site, K(2) is bonded to one S(2), two equivalent S(3), and four equivalent S(1) atoms to form distorted KS7 hexagonal pyramids that share corners with two equivalent K(2)S7 hexagonal pyramids,  a cornercorner with one W(1)S4 tetrahedra, edges with two equivalent K(2)S7 hexagonal pyramids, and edges with three equivalent W(1)S4 tetrahedra. The K(2)-S(2) bond length is 3.36 Å. Both K(2)-S(3) bond lengths are 3.53 Å. There are two shorter (3.45 Å) and two longer (3.50 Å) K(2)-S(1) bond lengths. W(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form WS4 tetrahedra that share  a cornercorner with one K(2)S7 hexagonal pyramid and edges with three equivalent K(2)S7 hexagonal pyramids. The W(1)-S(2) bond length is 2.20 Å. The W(1)-S(3) bond length is 2.19 Å. Both W(1)-S(1) bond lengths are 2.19 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 W(1) atom to form a mixture of distorted edge, face, and corner-sharing SK4W trigonal bipyramids. In the second S site, S(2) is bonded to one K(2), three equivalent K(1), and one W(1) atom to form a mixture of distorted edge and corner-sharing SK4W trigonal bipyramids. In the third S site, S(3) is bonded to two equivalent K(1), two equivalent K(2), and one W(1) atom to form a mixture of distorted edge and corner-sharing SK4W square pyramids.