Cs2AgSbS4 crystallizes in the triclinic P-1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 7-coordinate geometry to one S(1), one S(4), two equivalent S(2), and three equivalent S(3) atoms. In the second Cs site, Cs(2) is bonded in a 11-coordinate geometry to two equivalent Ag(1), two equivalent S(2), two equivalent S(3), two equivalent S(4), and three equivalent S(1) atoms. Ag(1) is bonded to two equivalent Cs(2), one S(1), one S(2), and two equivalent S(4) atoms to form distorted AgCs2S4 tetrahedra that share corners with two equivalent Ag(1)Cs2S4 tetrahedra, corners with two equivalent Sb(1)S4 tetrahedra,  an edgeedge with one Ag(1)Cs2S4 tetrahedra, and  an edgeedge with one Sb(1)S4 tetrahedra. Sb(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form SbS4 tetrahedra that share corners with two equivalent Ag(1)Cs2S4 tetrahedra and  an edgeedge with one Ag(1)Cs2S4 tetrahedra. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Cs(1), three equivalent Cs(2), one Ag(1), and one Sb(1) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one Ag(1), and one Sb(1) atom. In the third S site, S(3) is bonded in a 1-coordinate geometry to two equivalent Cs(2), three equivalent Cs(1), and one Sb(1) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Cs(1), two equivalent Cs(2), two equivalent Ag(1), and one Sb(1) atom.
Cs2AgSbS4 crystallizes in the triclinic P-1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 7-coordinate geometry to one S(1), one S(4), two equivalent S(2), and three equivalent S(3) atoms. The Cs(1)-S(1) bond length is 3.77 Å. The Cs(1)-S(4) bond length is 3.62 Å. There is one shorter (3.51 Å) and one longer (3.73 Å) Cs(1)-S(2) bond length. There are a spread of Cs(1)-S(3) bond distances ranging from 3.73-3.83 Å. In the second Cs site, Cs(2) is bonded in a 11-coordinate geometry to two equivalent Ag(1), two equivalent S(2), two equivalent S(3), two equivalent S(4), and three equivalent S(1) atoms. There is one shorter (4.07 Å) and one longer (4.22 Å) Cs(2)-Ag(1) bond length. There is one shorter (3.69 Å) and one longer (4.06 Å) Cs(2)-S(2) bond length. There is one shorter (4.18 Å) and one longer (4.20 Å) Cs(2)-S(3) bond length. There is one shorter (3.67 Å) and one longer (3.70 Å) Cs(2)-S(4) bond length. There are a spread of Cs(2)-S(1) bond distances ranging from 3.64-3.92 Å. Ag(1) is bonded to two equivalent Cs(2), one S(1), one S(2), and two equivalent S(4) atoms to form distorted AgCs2S4 tetrahedra that share corners with two equivalent Ag(1)Cs2S4 tetrahedra, corners with two equivalent Sb(1)S4 tetrahedra,  an edgeedge with one Ag(1)Cs2S4 tetrahedra, and  an edgeedge with one Sb(1)S4 tetrahedra. The Ag(1)-S(1) bond length is 2.61 Å. The Ag(1)-S(2) bond length is 2.52 Å. There is one shorter (2.56 Å) and one longer (2.99 Å) Ag(1)-S(4) bond length. Sb(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form SbS4 tetrahedra that share corners with two equivalent Ag(1)Cs2S4 tetrahedra and  an edgeedge with one Ag(1)Cs2S4 tetrahedra. The Sb(1)-S(1) bond length is 2.37 Å. The Sb(1)-S(2) bond length is 2.39 Å. The Sb(1)-S(3) bond length is 2.35 Å. The Sb(1)-S(4) bond length is 2.39 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Cs(1), three equivalent Cs(2), one Ag(1), and one Sb(1) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one Ag(1), and one Sb(1) atom. In the third S site, S(3) is bonded in a 1-coordinate geometry to two equivalent Cs(2), three equivalent Cs(1), and one Sb(1) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Cs(1), two equivalent Cs(2), two equivalent Ag(1), and one Sb(1) atom.