TlAg3Tl4(PS3)4 crystallizes in the monoclinic C2/c space group. The structure consists of four 7440-28-0 atoms inside a Ag3Tl4(PS3)4 framework. In the Ag3Tl4(PS3)4 framework, there are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent S(2) and two equivalent S(5) atoms to form AgS4 tetrahedra that share corners with four equivalent P(2)PS3 tetrahedra. In the second Ag site, Ag(2) is bonded in a distorted see-saw-like geometry to one S(3), one S(4), one S(5), and one S(6) atom. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 5-coordinate geometry to one S(2), one S(3), one S(4), and two equivalent S(1) atoms. In the second Tl site, Tl(2) is bonded in a 3-coordinate geometry to one S(3) and two equivalent S(1) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded in a distorted tetrahedral geometry to one P(1), one S(1), one S(3), and one S(4) atom. In the second P site, P(2) is bonded to one P(2), one S(2), one S(5), and one S(6) atom to form distorted PPS3 tetrahedra that share corners with two equivalent Ag(1)S4 tetrahedra. There are six inequivalent S sites. In the first S site, S(5) is bonded in a 3-coordinate geometry to one Ag(1), one Ag(2), and one P(2) atom. In the second S site, S(6) is bonded in a water-like geometry to one Ag(2) and one P(2) atom. In the third S site, S(1) is bonded in a distorted single-bond geometry to two equivalent Tl(1), two equivalent Tl(2), and one P(1) atom. In the fourth S site, S(2) is bonded in a distorted water-like geometry to one Ag(1), one Tl(1), and one P(2) atom. In the fifth S site, S(3) is bonded in a distorted water-like geometry to one Ag(2), one Tl(1), one Tl(2), and one P(1) atom. In the sixth S site, S(4) is bonded in a distorted water-like geometry to one Ag(2), one Tl(1), and one P(1) atom.
TlAg3Tl4(PS3)4 crystallizes in the monoclinic C2/c space group. The structure consists of four 7440-28-0 atoms inside a Ag3Tl4(PS3)4 framework. In the Ag3Tl4(PS3)4 framework, there are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent S(2) and two equivalent S(5) atoms to form AgS4 tetrahedra that share corners with four equivalent P(2)PS3 tetrahedra. Both Ag(1)-S(2) bond lengths are 2.56 Å. Both Ag(1)-S(5) bond lengths are 2.60 Å. In the second Ag site, Ag(2) is bonded in a distorted see-saw-like geometry to one S(3), one S(4), one S(5), and one S(6) atom. The Ag(2)-S(3) bond length is 2.59 Å. The Ag(2)-S(4) bond length is 2.69 Å. The Ag(2)-S(5) bond length is 2.82 Å. The Ag(2)-S(6) bond length is 2.55 Å. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 5-coordinate geometry to one S(2), one S(3), one S(4), and two equivalent S(1) atoms. The Tl(1)-S(2) bond length is 3.23 Å. The Tl(1)-S(3) bond length is 3.29 Å. The Tl(1)-S(4) bond length is 3.31 Å. There is one shorter (3.19 Å) and one longer (3.23 Å) Tl(1)-S(1) bond length. In the second Tl site, Tl(2) is bonded in a 3-coordinate geometry to one S(3) and two equivalent S(1) atoms. The Tl(2)-S(3) bond length is 3.30 Å. There is one shorter (3.16 Å) and one longer (3.24 Å) Tl(2)-S(1) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded in a distorted tetrahedral geometry to one P(1), one S(1), one S(3), and one S(4) atom. The P(1)-P(1) bond length is 2.30 Å. The P(1)-S(1) bond length is 2.05 Å. The P(1)-S(3) bond length is 2.04 Å. The P(1)-S(4) bond length is 2.04 Å. In the second P site, P(2) is bonded to one P(2), one S(2), one S(5), and one S(6) atom to form distorted PPS3 tetrahedra that share corners with two equivalent Ag(1)S4 tetrahedra. The P(2)-P(2) bond length is 2.31 Å. The P(2)-S(2) bond length is 2.05 Å. The P(2)-S(5) bond length is 2.06 Å. The P(2)-S(6) bond length is 2.04 Å. There are six inequivalent S sites. In the first S site, S(5) is bonded in a 3-coordinate geometry to one Ag(1), one Ag(2), and one P(2) atom. In the second S site, S(6) is bonded in a water-like geometry to one Ag(2) and one P(2) atom. In the third S site, S(1) is bonded in a distorted single-bond geometry to two equivalent Tl(1), two equivalent Tl(2), and one P(1) atom. In the fourth S site, S(2) is bonded in a distorted water-like geometry to one Ag(1), one Tl(1), and one P(2) atom. In the fifth S site, S(3) is bonded in a distorted water-like geometry to one Ag(2), one Tl(1), one Tl(2), and one P(1) atom. In the sixth S site, S(4) is bonded in a distorted water-like geometry to one Ag(2), one Tl(1), and one P(1) atom.