KAg2SbS3 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(1), one S(3), one S(6), two equivalent S(2), and two equivalent S(5) atoms. In the second K site, K(2) is bonded in a 5-coordinate geometry to one S(2), one S(3), one S(4), and two equivalent S(6) atoms. There are four inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 3-coordinate geometry to one S(2), one S(3), and one S(6) atom. In the second Ag site, Ag(2) is bonded to one S(3), one S(6), and two equivalent S(4) atoms to form distorted edge-sharing AgS4 tetrahedra. In the third Ag site, Ag(3) is bonded in a 3-coordinate geometry to one S(1), one S(4), and one S(5) atom. In the fourth Ag site, Ag(4) is bonded to one S(2), one S(5), and two equivalent S(1) atoms to form distorted edge-sharing AgS4 tetrahedra. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 3-coordinate geometry to one S(1), one S(3), and one S(4) atom. In the second Sb site, Sb(2) is bonded in a 3-coordinate geometry to one S(2), one S(5), and one S(6) atom. There are six inequivalent S sites. In the first S site, S(1) is bonded to one K(1), one Ag(3), two equivalent Ag(4), and one Sb(1) atom to form distorted SKAg3Sb trigonal bipyramids that share corners with two equivalent S(2)K3Ag2Sb octahedra, corners with three equivalent S(5)K2Ag2Sb square pyramids, corners with two equivalent S(4)KAg3Sb trigonal bipyramids,  an edgeedge with one S(2)K3Ag2Sb octahedra,  an edgeedge with one S(5)K2Ag2Sb square pyramid, and  an edgeedge with one S(1)KAg3Sb trigonal bipyramid. The corner-sharing octahedral tilt angles range from 54-62°. In the second S site, S(2) is bonded to one K(2), two equivalent K(1), one Ag(1), one Ag(4), and one Sb(2) atom to form distorted SK3Ag2Sb octahedra that share corners with two equivalent S(5)K2Ag2Sb square pyramids,  a cornercorner with one S(4)KAg3Sb trigonal bipyramid, corners with two equivalent S(1)KAg3Sb trigonal bipyramids,  an edgeedge with one S(2)K3Ag2Sb octahedra, edges with two equivalent S(5)K2Ag2Sb square pyramids, and  an edgeedge with one S(1)KAg3Sb trigonal bipyramid. In the third S site, S(3) is bonded in a 5-coordinate geometry to one K(1), one K(2), one Ag(1), one Ag(2), and one Sb(1) atom. In the fourth S site, S(4) is bonded to one K(2), one Ag(3), two equivalent Ag(2), and one Sb(1) atom to form distorted SKAg3Sb trigonal bipyramids that share  a cornercorner with one S(2)K3Ag2Sb octahedra,  a cornercorner with one S(5)K2Ag2Sb square pyramid, corners with two equivalent S(1)KAg3Sb trigonal bipyramids, and  an edgeedge with one S(4)KAg3Sb trigonal bipyramid. The corner-sharing octahedral tilt angles are 49°. In the fifth S site, S(5) is bonded to two equivalent K(1), one Ag(3), one Ag(4), and one Sb(2) atom to form SK2Ag2Sb square pyramids that share corners with two equivalent S(2)K3Ag2Sb octahedra,  a cornercorner with one S(4)KAg3Sb trigonal bipyramid, corners with three equivalent S(1)KAg3Sb trigonal bipyramids, edges with two equivalent S(2)K3Ag2Sb octahedra,  an edgeedge with one S(5)K2Ag2Sb square pyramid, and  an edgeedge with one S(1)KAg3Sb trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-104°. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to one K(1), two equivalent K(2), one Ag(1), one Ag(2), and one Sb(2) atom.
KAg2SbS3 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(1), one S(3), one S(6), two equivalent S(2), and two equivalent S(5) atoms. The K(1)-S(1) bond length is 3.29 Å. The K(1)-S(3) bond length is 3.49 Å. The K(1)-S(6) bond length is 3.42 Å. There is one shorter (3.26 Å) and one longer (3.45 Å) K(1)-S(2) bond length. There is one shorter (3.21 Å) and one longer (3.27 Å) K(1)-S(5) bond length. In the second K site, K(2) is bonded in a 5-coordinate geometry to one S(2), one S(3), one S(4), and two equivalent S(6) atoms. The K(2)-S(2) bond length is 3.35 Å. The K(2)-S(3) bond length is 3.40 Å. The K(2)-S(4) bond length is 3.25 Å. There is one shorter (3.27 Å) and one longer (3.43 Å) K(2)-S(6) bond length. There are four inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 3-coordinate geometry to one S(2), one S(3), and one S(6) atom. The Ag(1)-S(2) bond length is 2.57 Å. The Ag(1)-S(3) bond length is 2.59 Å. The Ag(1)-S(6) bond length is 2.58 Å. In the second Ag site, Ag(2) is bonded to one S(3), one S(6), and two equivalent S(4) atoms to form distorted edge-sharing AgS4 tetrahedra. The Ag(2)-S(3) bond length is 2.64 Å. The Ag(2)-S(6) bond length is 2.60 Å. There is one shorter (2.61 Å) and one longer (2.78 Å) Ag(2)-S(4) bond length. In the third Ag site, Ag(3) is bonded in a 3-coordinate geometry to one S(1), one S(4), and one S(5) atom. The Ag(3)-S(1) bond length is 2.66 Å. The Ag(3)-S(4) bond length is 2.53 Å. The Ag(3)-S(5) bond length is 2.55 Å. In the fourth Ag site, Ag(4) is bonded to one S(2), one S(5), and two equivalent S(1) atoms to form distorted edge-sharing AgS4 tetrahedra. The Ag(4)-S(2) bond length is 2.65 Å. The Ag(4)-S(5) bond length is 2.58 Å. There is one shorter (2.60 Å) and one longer (2.70 Å) Ag(4)-S(1) bond length. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 3-coordinate geometry to one S(1), one S(3), and one S(4) atom. The Sb(1)-S(1) bond length is 2.47 Å. The Sb(1)-S(3) bond length is 2.50 Å. The Sb(1)-S(4) bond length is 2.49 Å. In the second Sb site, Sb(2) is bonded in a 3-coordinate geometry to one S(2), one S(5), and one S(6) atom. The Sb(2)-S(2) bond length is 2.48 Å. The Sb(2)-S(5) bond length is 2.48 Å. The Sb(2)-S(6) bond length is 2.49 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to one K(1), one Ag(3), two equivalent Ag(4), and one Sb(1) atom to form distorted SKAg3Sb trigonal bipyramids that share corners with two equivalent S(2)K3Ag2Sb octahedra, corners with three equivalent S(5)K2Ag2Sb square pyramids, corners with two equivalent S(4)KAg3Sb trigonal bipyramids,  an edgeedge with one S(2)K3Ag2Sb octahedra,  an edgeedge with one S(5)K2Ag2Sb square pyramid, and  an edgeedge with one S(1)KAg3Sb trigonal bipyramid. The corner-sharing octahedral tilt angles range from 54-62°. In the second S site, S(2) is bonded to one K(2), two equivalent K(1), one Ag(1), one Ag(4), and one Sb(2) atom to form distorted SK3Ag2Sb octahedra that share corners with two equivalent S(5)K2Ag2Sb square pyramids,  a cornercorner with one S(4)KAg3Sb trigonal bipyramid, corners with two equivalent S(1)KAg3Sb trigonal bipyramids,  an edgeedge with one S(2)K3Ag2Sb octahedra, edges with two equivalent S(5)K2Ag2Sb square pyramids, and  an edgeedge with one S(1)KAg3Sb trigonal bipyramid. In the third S site, S(3) is bonded in a 5-coordinate geometry to one K(1), one K(2), one Ag(1), one Ag(2), and one Sb(1) atom. In the fourth S site, S(4) is bonded to one K(2), one Ag(3), two equivalent Ag(2), and one Sb(1) atom to form distorted SKAg3Sb trigonal bipyramids that share  a cornercorner with one S(2)K3Ag2Sb octahedra,  a cornercorner with one S(5)K2Ag2Sb square pyramid, corners with two equivalent S(1)KAg3Sb trigonal bipyramids, and  an edgeedge with one S(4)KAg3Sb trigonal bipyramid. The corner-sharing octahedral tilt angles are 49°. In the fifth S site, S(5) is bonded to two equivalent K(1), one Ag(3), one Ag(4), and one Sb(2) atom to form SK2Ag2Sb square pyramids that share corners with two equivalent S(2)K3Ag2Sb octahedra,  a cornercorner with one S(4)KAg3Sb trigonal bipyramid, corners with three equivalent S(1)KAg3Sb trigonal bipyramids, edges with two equivalent S(2)K3Ag2Sb octahedra,  an edgeedge with one S(5)K2Ag2Sb square pyramid, and  an edgeedge with one S(1)KAg3Sb trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-104°. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to one K(1), two equivalent K(2), one Ag(1), one Ag(2), and one Sb(2) atom.