Ba3GeS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one S(2), one S(3), two equivalent S(4), and four equivalent S(1) atoms. Ge(1) is bonded in a tetrahedral geometry to one S(2), one S(3), and two equivalent S(1) atoms. There are four inequivalent S sites. In the first S site, S(4) is bonded to two equivalent Ba(2) and four equivalent Ba(1) atoms to form SBa6 octahedra that share corners with four equivalent S(2)Ba5Ge octahedra, corners with six equivalent S(4)Ba6 octahedra, and faces with two equivalent S(2)Ba5Ge octahedra. The corner-sharing octahedral tilt angles range from 29-53°. In the second S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and one Ge(1) atom. In the third S site, S(2) is bonded to one Ba(2), four equivalent Ba(1), and one Ge(1) atom to form distorted SBa5Ge octahedra that share corners with four equivalent S(4)Ba6 octahedra, edges with two equivalent S(2)Ba5Ge octahedra, and faces with two equivalent S(4)Ba6 octahedra. The corner-sharing octahedral tilt angles range from 36-53°. In the fourth S site, S(3) is bonded in a 6-coordinate geometry to one Ba(2), four equivalent Ba(1), and one Ge(1) atom.
Ba3GeS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. There is one shorter (3.33 Å) and one longer (3.61 Å) Ba(1)-S(1) bond length. There is one shorter (3.27 Å) and one longer (3.42 Å) Ba(1)-S(2) bond length. There is one shorter (3.29 Å) and one longer (3.46 Å) Ba(1)-S(3) bond length. There is one shorter (3.33 Å) and one longer (3.39 Å) Ba(1)-S(4) bond length. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one S(2), one S(3), two equivalent S(4), and four equivalent S(1) atoms. The Ba(2)-S(2) bond length is 3.22 Å. The Ba(2)-S(3) bond length is 3.35 Å. There is one shorter (3.15 Å) and one longer (3.48 Å) Ba(2)-S(4) bond length. There are two shorter (3.08 Å) and two longer (3.27 Å) Ba(2)-S(1) bond lengths. Ge(1) is bonded in a tetrahedral geometry to one S(2), one S(3), and two equivalent S(1) atoms. The Ge(1)-S(2) bond length is 2.19 Å. The Ge(1)-S(3) bond length is 2.22 Å. Both Ge(1)-S(1) bond lengths are 2.19 Å. There are four inequivalent S sites. In the first S site, S(4) is bonded to two equivalent Ba(2) and four equivalent Ba(1) atoms to form SBa6 octahedra that share corners with four equivalent S(2)Ba5Ge octahedra, corners with six equivalent S(4)Ba6 octahedra, and faces with two equivalent S(2)Ba5Ge octahedra. The corner-sharing octahedral tilt angles range from 29-53°. In the second S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and one Ge(1) atom. In the third S site, S(2) is bonded to one Ba(2), four equivalent Ba(1), and one Ge(1) atom to form distorted SBa5Ge octahedra that share corners with four equivalent S(4)Ba6 octahedra, edges with two equivalent S(2)Ba5Ge octahedra, and faces with two equivalent S(4)Ba6 octahedra. The corner-sharing octahedral tilt angles range from 36-53°. In the fourth S site, S(3) is bonded in a 6-coordinate geometry to one Ba(2), four equivalent Ba(1), and one Ge(1) atom.