CsTaGeS5 crystallizes in the triclinic P-1 space group. Cs(1) is bonded in a 9-coordinate geometry to one S(1), one S(4), two equivalent S(2), two equivalent S(5), and three equivalent S(3) atoms. Ta(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form TaS6 octahedra that share corners with two equivalent Ge(1)S4 tetrahedra and edges with two equivalent Ta(1)S6 octahedra. Ge(1) is bonded to one S(3), one S(4), and two equivalent S(5) atoms to form GeS4 tetrahedra that share corners with two equivalent Ta(1)S6 octahedra and  an edgeedge with one Ge(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 71-74°. There are five inequivalent S sites. In the first S site, S(1) is bonded in a distorted L-shaped geometry to one Cs(1) and two equivalent Ta(1) atoms. In the second S site, S(2) is bonded in a 4-coordinate geometry to two equivalent Cs(1) and two equivalent Ta(1) atoms. In the third S site, S(3) is bonded in a distorted water-like geometry to three equivalent Cs(1), one Ta(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a distorted water-like geometry to one Cs(1), one Ta(1), and one Ge(1) atom. In the fifth S site, S(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Cs(1) and two equivalent Ge(1) atoms.
CsTaGeS5 crystallizes in the triclinic P-1 space group. Cs(1) is bonded in a 9-coordinate geometry to one S(1), one S(4), two equivalent S(2), two equivalent S(5), and three equivalent S(3) atoms. The Cs(1)-S(1) bond length is 3.68 Å. The Cs(1)-S(4) bond length is 3.88 Å. There is one shorter (3.61 Å) and one longer (3.70 Å) Cs(1)-S(2) bond length. There is one shorter (3.58 Å) and one longer (3.60 Å) Cs(1)-S(5) bond length. There are a spread of Cs(1)-S(3) bond distances ranging from 3.65-3.93 Å. Ta(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form TaS6 octahedra that share corners with two equivalent Ge(1)S4 tetrahedra and edges with two equivalent Ta(1)S6 octahedra. The Ta(1)-S(3) bond length is 2.54 Å. The Ta(1)-S(4) bond length is 2.49 Å. There is one shorter (2.34 Å) and one longer (2.55 Å) Ta(1)-S(1) bond length. There is one shorter (2.34 Å) and one longer (2.57 Å) Ta(1)-S(2) bond length. Ge(1) is bonded to one S(3), one S(4), and two equivalent S(5) atoms to form GeS4 tetrahedra that share corners with two equivalent Ta(1)S6 octahedra and  an edgeedge with one Ge(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 71-74°. The Ge(1)-S(3) bond length is 2.21 Å. The Ge(1)-S(4) bond length is 2.21 Å. There is one shorter (2.27 Å) and one longer (2.29 Å) Ge(1)-S(5) bond length. There are five inequivalent S sites. In the first S site, S(1) is bonded in a distorted L-shaped geometry to one Cs(1) and two equivalent Ta(1) atoms. In the second S site, S(2) is bonded in a 4-coordinate geometry to two equivalent Cs(1) and two equivalent Ta(1) atoms. In the third S site, S(3) is bonded in a distorted water-like geometry to three equivalent Cs(1), one Ta(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a distorted water-like geometry to one Cs(1), one Ta(1), and one Ge(1) atom. In the fifth S site, S(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Cs(1) and two equivalent Ge(1) atoms.