CsTb2Ag3Te5 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded in a 8-coordinate geometry to two equivalent Te(2), two equivalent Te(3), and four equivalent Te(1) atoms. Tb(1) is bonded to one Te(3), two equivalent Te(1), and three equivalent Te(2) atoms to form TbTe6 octahedra that share  a cornercorner with one Tb(1)Te6 octahedra, corners with four equivalent Ag(2)Te4 tetrahedra, edges with four equivalent Tb(1)Te6 octahedra, edges with two equivalent Ag(1)Te4 tetrahedra, and edges with three equivalent Ag(2)Te4 tetrahedra. The corner-sharing octahedral tilt angles are 39°. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent Te(1) and two equivalent Te(3) atoms to form distorted AgTe4 tetrahedra that share corners with two equivalent Ag(1)Te4 tetrahedra, corners with four equivalent Ag(2)Te4 tetrahedra, and edges with four equivalent Tb(1)Te6 octahedra. In the second Ag site, Ag(2) is bonded to two equivalent Te(1) and two equivalent Te(2) atoms to form distorted AgTe4 tetrahedra that share corners with four equivalent Tb(1)Te6 octahedra, corners with two equivalent Ag(1)Te4 tetrahedra, corners with two equivalent Ag(2)Te4 tetrahedra, edges with three equivalent Tb(1)Te6 octahedra, and  an edgeedge with one Ag(2)Te4 tetrahedra. The corner-sharing octahedral tilt angles range from 11-61°. There are three inequivalent Te sites. In the first Te site, Te(3) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Tb(1), and two equivalent Ag(1) atoms. In the second Te site, Te(1) is bonded in a 7-coordinate geometry to two equivalent Cs(1), two equivalent Tb(1), one Ag(1), and two equivalent Ag(2) atoms. In the third Te site, Te(2) is bonded to one Cs(1), three equivalent Tb(1), and two equivalent Ag(2) atoms to form a mixture of distorted corner and edge-sharing TeCsTb3Ag2 octahedra. The corner-sharing octahedral tilt angles are 61°.
CsTb2Ag3Te5 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded in a 8-coordinate geometry to two equivalent Te(2), two equivalent Te(3), and four equivalent Te(1) atoms. Both Cs(1)-Te(2) bond lengths are 3.87 Å. Both Cs(1)-Te(3) bond lengths are 3.86 Å. All Cs(1)-Te(1) bond lengths are 3.93 Å. Tb(1) is bonded to one Te(3), two equivalent Te(1), and three equivalent Te(2) atoms to form TbTe6 octahedra that share  a cornercorner with one Tb(1)Te6 octahedra, corners with four equivalent Ag(2)Te4 tetrahedra, edges with four equivalent Tb(1)Te6 octahedra, edges with two equivalent Ag(1)Te4 tetrahedra, and edges with three equivalent Ag(2)Te4 tetrahedra. The corner-sharing octahedral tilt angles are 39°. The Tb(1)-Te(3) bond length is 3.09 Å. Both Tb(1)-Te(1) bond lengths are 3.15 Å. There is one shorter (3.11 Å) and two longer (3.18 Å) Tb(1)-Te(2) bond lengths. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent Te(1) and two equivalent Te(3) atoms to form distorted AgTe4 tetrahedra that share corners with two equivalent Ag(1)Te4 tetrahedra, corners with four equivalent Ag(2)Te4 tetrahedra, and edges with four equivalent Tb(1)Te6 octahedra. Both Ag(1)-Te(1) bond lengths are 2.91 Å. Both Ag(1)-Te(3) bond lengths are 2.79 Å. In the second Ag site, Ag(2) is bonded to two equivalent Te(1) and two equivalent Te(2) atoms to form distorted AgTe4 tetrahedra that share corners with four equivalent Tb(1)Te6 octahedra, corners with two equivalent Ag(1)Te4 tetrahedra, corners with two equivalent Ag(2)Te4 tetrahedra, edges with three equivalent Tb(1)Te6 octahedra, and  an edgeedge with one Ag(2)Te4 tetrahedra. The corner-sharing octahedral tilt angles range from 11-61°. There is one shorter (2.87 Å) and one longer (2.90 Å) Ag(2)-Te(1) bond length. Both Ag(2)-Te(2) bond lengths are 2.86 Å. There are three inequivalent Te sites. In the first Te site, Te(3) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Tb(1), and two equivalent Ag(1) atoms. In the second Te site, Te(1) is bonded in a 7-coordinate geometry to two equivalent Cs(1), two equivalent Tb(1), one Ag(1), and two equivalent Ag(2) atoms. In the third Te site, Te(2) is bonded to one Cs(1), three equivalent Tb(1), and two equivalent Ag(2) atoms to form a mixture of distorted corner and edge-sharing TeCsTb3Ag2 octahedra. The corner-sharing octahedral tilt angles are 61°.