KCu2AsS3 crystallizes in the triclinic P-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), one S(3), one S(4), two equivalent S(1), and two equivalent S(5) atoms. In the second K site, K(2) is bonded in a 6-coordinate geometry to one S(1), one S(6), two equivalent S(2), and two equivalent S(4) atoms. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one S(2), one S(4), and two equivalent S(6) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one As(1)CuS3 tetrahedra, corners with three equivalent As(2)CuS3 tetrahedra, and  an edgeedge with one Cu(1)S4 tetrahedra. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one As(2), one S(1), one S(2), and one S(4) atom. In the third Cu site, Cu(3) is bonded to one S(1), one S(5), and two equivalent S(3) atoms to form CuS4 tetrahedra that share corners with two equivalent As(1)CuS3 tetrahedra, corners with two equivalent As(2)CuS3 tetrahedra, and  an edgeedge with one Cu(3)S4 tetrahedra. In the fourth Cu site, Cu(4) is bonded in a 4-coordinate geometry to one As(1), one S(3), one S(5), and one S(6) atom. There are two inequivalent As sites. In the first As site, As(1) is bonded to one Cu(4), one S(1), one S(2), and one S(5) atom to form distorted AsCuS3 tetrahedra that share  a cornercorner with one S(5)K2Cu2As square pyramid,  a cornercorner with one Cu(1)S4 tetrahedra, corners with two equivalent Cu(3)S4 tetrahedra, and  a cornercorner with one S(6)KCu3As trigonal bipyramid. In the second As site, As(2) is bonded to one Cu(2), one S(3), one S(4), and one S(6) atom to form distorted AsCuS3 tetrahedra that share corners with two equivalent Cu(3)S4 tetrahedra and corners with three equivalent Cu(1)S4 tetrahedra. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one K(2), two equivalent K(1), one Cu(2), one Cu(3), and one As(1) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one K(1), two equivalent K(2), one Cu(1), one Cu(2), and one As(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one K(1), one Cu(4), two equivalent Cu(3), and one As(2) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one K(1), two equivalent K(2), one Cu(1), one Cu(2), and one As(2) atom. In the fifth S site, S(5) is bonded to two equivalent K(1), one Cu(3), one Cu(4), and one As(1) atom to form distorted SK2Cu2As square pyramids that share  a cornercorner with one As(1)CuS3 tetrahedra,  a cornercorner with one S(6)KCu3As trigonal bipyramid, and  an edgeedge with one S(5)K2Cu2As square pyramid. In the sixth S site, S(6) is bonded to one K(2), one Cu(4), two equivalent Cu(1), and one As(2) atom to form distorted SKCu3As trigonal bipyramids that share  a cornercorner with one S(5)K2Cu2As square pyramid,  a cornercorner with one As(1)CuS3 tetrahedra, and  an edgeedge with one S(6)KCu3As trigonal bipyramid.
KCu2AsS3 crystallizes in the triclinic P-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), one S(3), one S(4), two equivalent S(1), and two equivalent S(5) atoms. The K(1)-S(2) bond length is 3.30 Å. The K(1)-S(3) bond length is 3.17 Å. The K(1)-S(4) bond length is 3.54 Å. There is one shorter (3.27 Å) and one longer (3.32 Å) K(1)-S(1) bond length. There is one shorter (3.21 Å) and one longer (3.26 Å) K(1)-S(5) bond length. In the second K site, K(2) is bonded in a 6-coordinate geometry to one S(1), one S(6), two equivalent S(2), and two equivalent S(4) atoms. The K(2)-S(1) bond length is 3.29 Å. The K(2)-S(6) bond length is 3.15 Å. There is one shorter (3.25 Å) and one longer (3.31 Å) K(2)-S(2) bond length. There is one shorter (3.30 Å) and one longer (3.45 Å) K(2)-S(4) bond length. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one S(2), one S(4), and two equivalent S(6) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one As(1)CuS3 tetrahedra, corners with three equivalent As(2)CuS3 tetrahedra, and  an edgeedge with one Cu(1)S4 tetrahedra. The Cu(1)-S(2) bond length is 2.32 Å. The Cu(1)-S(4) bond length is 2.32 Å. There is one shorter (2.35 Å) and one longer (2.46 Å) Cu(1)-S(6) bond length. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one As(2), one S(1), one S(2), and one S(4) atom. The Cu(2)-As(2) bond length is 2.66 Å. The Cu(2)-S(1) bond length is 2.30 Å. The Cu(2)-S(2) bond length is 2.29 Å. The Cu(2)-S(4) bond length is 2.31 Å. In the third Cu site, Cu(3) is bonded to one S(1), one S(5), and two equivalent S(3) atoms to form CuS4 tetrahedra that share corners with two equivalent As(1)CuS3 tetrahedra, corners with two equivalent As(2)CuS3 tetrahedra, and  an edgeedge with one Cu(3)S4 tetrahedra. The Cu(3)-S(1) bond length is 2.34 Å. The Cu(3)-S(5) bond length is 2.32 Å. There is one shorter (2.35 Å) and one longer (2.38 Å) Cu(3)-S(3) bond length. In the fourth Cu site, Cu(4) is bonded in a 4-coordinate geometry to one As(1), one S(3), one S(5), and one S(6) atom. The Cu(4)-As(1) bond length is 2.55 Å. The Cu(4)-S(3) bond length is 2.31 Å. The Cu(4)-S(5) bond length is 2.28 Å. The Cu(4)-S(6) bond length is 2.27 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded to one Cu(4), one S(1), one S(2), and one S(5) atom to form distorted AsCuS3 tetrahedra that share  a cornercorner with one S(5)K2Cu2As square pyramid,  a cornercorner with one Cu(1)S4 tetrahedra, corners with two equivalent Cu(3)S4 tetrahedra, and  a cornercorner with one S(6)KCu3As trigonal bipyramid. The As(1)-S(1) bond length is 2.33 Å. The As(1)-S(2) bond length is 2.33 Å. The As(1)-S(5) bond length is 2.31 Å. In the second As site, As(2) is bonded to one Cu(2), one S(3), one S(4), and one S(6) atom to form distorted AsCuS3 tetrahedra that share corners with two equivalent Cu(3)S4 tetrahedra and corners with three equivalent Cu(1)S4 tetrahedra. The As(2)-S(3) bond length is 2.32 Å. The As(2)-S(4) bond length is 2.36 Å. The As(2)-S(6) bond length is 2.33 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one K(2), two equivalent K(1), one Cu(2), one Cu(3), and one As(1) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one K(1), two equivalent K(2), one Cu(1), one Cu(2), and one As(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one K(1), one Cu(4), two equivalent Cu(3), and one As(2) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one K(1), two equivalent K(2), one Cu(1), one Cu(2), and one As(2) atom. In the fifth S site, S(5) is bonded to two equivalent K(1), one Cu(3), one Cu(4), and one As(1) atom to form distorted SK2Cu2As square pyramids that share  a cornercorner with one As(1)CuS3 tetrahedra,  a cornercorner with one S(6)KCu3As trigonal bipyramid, and  an edgeedge with one S(5)K2Cu2As square pyramid. In the sixth S site, S(6) is bonded to one K(2), one Cu(4), two equivalent Cu(1), and one As(2) atom to form distorted SKCu3As trigonal bipyramids that share  a cornercorner with one S(5)K2Cu2As square pyramid,  a cornercorner with one As(1)CuS3 tetrahedra, and  an edgeedge with one S(6)KCu3As trigonal bipyramid.