V12Ga(GeS12)2 crystallizes in the orthorhombic Imm2 space group. There are five inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(10), one S(3), one S(5), one S(7), and one S(9) atom to form distorted VS6 octahedra that share  a cornercorner with one Ga(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra,  an edgeedge with one V(4)S6 octahedra,  an edgeedge with one V(5)S6 octahedra, edges with two equivalent V(1)S6 octahedra, and edges with two equivalent V(3)S6 octahedra. In the second V site, V(2) is bonded to one S(2), one S(6), two equivalent S(4), and two equivalent S(8) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ga(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, edges with two equivalent V(2)S6 octahedra, edges with two equivalent V(4)S6 octahedra, and edges with two equivalent V(5)S6 octahedra. In the third V site, V(3) is bonded to one S(3), one S(9), two equivalent S(1), and two equivalent S(7) atoms to form distorted VS6 octahedra that share corners with three equivalent Ge(1)S4 tetrahedra,  an edgeedge with one V(4)S6 octahedra,  an edgeedge with one V(5)S6 octahedra, and edges with four equivalent V(1)S6 octahedra. In the fourth V site, V(4) is bonded to one S(5), one S(8), two equivalent S(1), and two equivalent S(6) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ga(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra,  an edgeedge with one V(3)S6 octahedra,  an edgeedge with one V(4)S6 octahedra, edges with two equivalent V(1)S6 octahedra, and edges with two equivalent V(2)S6 octahedra. In the fifth V site, V(5) is bonded to one S(10), one S(4), two equivalent S(2), and two equivalent S(7) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ge(1)S4 tetrahedra, corners with two equivalent Ga(1)S4 tetrahedra,  an edgeedge with one V(3)S6 octahedra,  an edgeedge with one V(5)S6 octahedra, edges with two equivalent V(1)S6 octahedra, and edges with two equivalent V(2)S6 octahedra. Ga(1) is bonded to two equivalent S(2) and two equivalent S(5) atoms to form GaS4 tetrahedra that share corners with two equivalent V(2)S6 octahedra, corners with two equivalent V(4)S6 octahedra, corners with four equivalent V(1)S6 octahedra, and corners with four equivalent V(5)S6 octahedra. The corner-sharing octahedral tilt angles are 65°. Ge(1) is bonded to one S(3), one S(4), and two equivalent S(1) atoms to form GeS4 tetrahedra that share  a cornercorner with one V(5)S6 octahedra, corners with two equivalent V(2)S6 octahedra, corners with two equivalent V(4)S6 octahedra, corners with three equivalent V(3)S6 octahedra, and corners with four equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 64-65°. There are ten inequivalent S sites. In the first S site, S(3) is bonded to one V(3), two equivalent V(1), and one Ge(1) atom to form SV3Ge tetrahedra that share  a cornercorner with one S(4)V3Ge tetrahedra, corners with two equivalent S(1)V3Ge tetrahedra,  an edgeedge with one S(5)V3Ga tetrahedra, and edges with two equivalent S(1)V3Ge tetrahedra. In the second S site, S(4) is bonded to one V(5), two equivalent V(2), and one Ge(1) atom to form SV3Ge tetrahedra that share  a cornercorner with one S(3)V3Ge tetrahedra, corners with two equivalent S(1)V3Ge tetrahedra,  an edgeedge with one S(4)V3Ge tetrahedra, and edges with two equivalent S(2)V3Ga tetrahedra. In the third S site, S(5) is bonded to one V(4), two equivalent V(1), and one Ga(1) atom to form SV3Ga tetrahedra that share  a cornercorner with one S(5)V3Ga tetrahedra, corners with two equivalent S(2)V3Ga tetrahedra,  an edgeedge with one S(3)V3Ge tetrahedra, and edges with two equivalent S(1)V3Ge tetrahedra. In the fourth S site, S(6) is bonded in a 3-coordinate geometry to one V(2) and two equivalent V(4) atoms. In the fifth S site, S(7) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one V(5) atom. In the sixth S site, S(8) is bonded in a 3-coordinate geometry to one V(4) and two equivalent V(2) atoms. In the seventh S site, S(9) is bonded in a 3-coordinate geometry to one V(3) and two equivalent V(1) atoms. In the eighth S site, S(10) is bonded in a 3-coordinate geometry to one V(5) and two equivalent V(1) atoms. In the ninth S site, S(1) is bonded to one V(1), one V(3), one V(4), and one Ge(1) atom to form SV3Ge tetrahedra that share  a cornercorner with one S(1)V3Ge tetrahedra,  a cornercorner with one S(3)V3Ge tetrahedra,  a cornercorner with one S(4)V3Ge tetrahedra,  an edgeedge with one S(5)V3Ga tetrahedra,  an edgeedge with one S(1)V3Ge tetrahedra, and  an edgeedge with one S(3)V3Ge tetrahedra. In the tenth S site, S(2) is bonded to one V(2), two equivalent V(5), and one Ga(1) atom to form SV3Ga tetrahedra that share  a cornercorner with one S(2)V3Ga tetrahedra, corners with two equivalent S(5)V3Ga tetrahedra,  an edgeedge with one S(2)V3Ga tetrahedra, and edges with two equivalent S(4)V3Ge tetrahedra.
V12Ga(GeS12)2 crystallizes in the orthorhombic Imm2 space group. There are five inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(10), one S(3), one S(5), one S(7), and one S(9) atom to form distorted VS6 octahedra that share  a cornercorner with one Ga(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra,  an edgeedge with one V(4)S6 octahedra,  an edgeedge with one V(5)S6 octahedra, edges with two equivalent V(1)S6 octahedra, and edges with two equivalent V(3)S6 octahedra. The V(1)-S(1) bond length is 2.56 Å. The V(1)-S(10) bond length is 2.29 Å. The V(1)-S(3) bond length is 2.56 Å. The V(1)-S(5) bond length is 2.55 Å. The V(1)-S(7) bond length is 2.29 Å. The V(1)-S(9) bond length is 2.29 Å. In the second V site, V(2) is bonded to one S(2), one S(6), two equivalent S(4), and two equivalent S(8) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ga(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, edges with two equivalent V(2)S6 octahedra, edges with two equivalent V(4)S6 octahedra, and edges with two equivalent V(5)S6 octahedra. The V(2)-S(2) bond length is 2.54 Å. The V(2)-S(6) bond length is 2.29 Å. Both V(2)-S(4) bond lengths are 2.56 Å. Both V(2)-S(8) bond lengths are 2.29 Å. In the third V site, V(3) is bonded to one S(3), one S(9), two equivalent S(1), and two equivalent S(7) atoms to form distorted VS6 octahedra that share corners with three equivalent Ge(1)S4 tetrahedra,  an edgeedge with one V(4)S6 octahedra,  an edgeedge with one V(5)S6 octahedra, and edges with four equivalent V(1)S6 octahedra. The V(3)-S(3) bond length is 2.56 Å. The V(3)-S(9) bond length is 2.29 Å. Both V(3)-S(1) bond lengths are 2.56 Å. Both V(3)-S(7) bond lengths are 2.29 Å. In the fourth V site, V(4) is bonded to one S(5), one S(8), two equivalent S(1), and two equivalent S(6) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ga(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra,  an edgeedge with one V(3)S6 octahedra,  an edgeedge with one V(4)S6 octahedra, edges with two equivalent V(1)S6 octahedra, and edges with two equivalent V(2)S6 octahedra. The V(4)-S(5) bond length is 2.54 Å. The V(4)-S(8) bond length is 2.29 Å. Both V(4)-S(1) bond lengths are 2.56 Å. Both V(4)-S(6) bond lengths are 2.29 Å. In the fifth V site, V(5) is bonded to one S(10), one S(4), two equivalent S(2), and two equivalent S(7) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ge(1)S4 tetrahedra, corners with two equivalent Ga(1)S4 tetrahedra,  an edgeedge with one V(3)S6 octahedra,  an edgeedge with one V(5)S6 octahedra, edges with two equivalent V(1)S6 octahedra, and edges with two equivalent V(2)S6 octahedra. The V(5)-S(10) bond length is 2.29 Å. The V(5)-S(4) bond length is 2.56 Å. Both V(5)-S(2) bond lengths are 2.54 Å. Both V(5)-S(7) bond lengths are 2.30 Å. Ga(1) is bonded to two equivalent S(2) and two equivalent S(5) atoms to form GaS4 tetrahedra that share corners with two equivalent V(2)S6 octahedra, corners with two equivalent V(4)S6 octahedra, corners with four equivalent V(1)S6 octahedra, and corners with four equivalent V(5)S6 octahedra. The corner-sharing octahedral tilt angles are 65°. Both Ga(1)-S(2) bond lengths are 2.31 Å. Both Ga(1)-S(5) bond lengths are 2.32 Å. Ge(1) is bonded to one S(3), one S(4), and two equivalent S(1) atoms to form GeS4 tetrahedra that share  a cornercorner with one V(5)S6 octahedra, corners with two equivalent V(2)S6 octahedra, corners with two equivalent V(4)S6 octahedra, corners with three equivalent V(3)S6 octahedra, and corners with four equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 64-65°. The Ge(1)-S(3) bond length is 2.29 Å. The Ge(1)-S(4) bond length is 2.29 Å. Both Ge(1)-S(1) bond lengths are 2.29 Å. There are ten inequivalent S sites. In the first S site, S(3) is bonded to one V(3), two equivalent V(1), and one Ge(1) atom to form SV3Ge tetrahedra that share  a cornercorner with one S(4)V3Ge tetrahedra, corners with two equivalent S(1)V3Ge tetrahedra,  an edgeedge with one S(5)V3Ga tetrahedra, and edges with two equivalent S(1)V3Ge tetrahedra. In the second S site, S(4) is bonded to one V(5), two equivalent V(2), and one Ge(1) atom to form SV3Ge tetrahedra that share  a cornercorner with one S(3)V3Ge tetrahedra, corners with two equivalent S(1)V3Ge tetrahedra,  an edgeedge with one S(4)V3Ge tetrahedra, and edges with two equivalent S(2)V3Ga tetrahedra. In the third S site, S(5) is bonded to one V(4), two equivalent V(1), and one Ga(1) atom to form SV3Ga tetrahedra that share  a cornercorner with one S(5)V3Ga tetrahedra, corners with two equivalent S(2)V3Ga tetrahedra,  an edgeedge with one S(3)V3Ge tetrahedra, and edges with two equivalent S(1)V3Ge tetrahedra. In the fourth S site, S(6) is bonded in a 3-coordinate geometry to one V(2) and two equivalent V(4) atoms. In the fifth S site, S(7) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one V(5) atom. In the sixth S site, S(8) is bonded in a 3-coordinate geometry to one V(4) and two equivalent V(2) atoms. In the seventh S site, S(9) is bonded in a 3-coordinate geometry to one V(3) and two equivalent V(1) atoms. In the eighth S site, S(10) is bonded in a 3-coordinate geometry to one V(5) and two equivalent V(1) atoms. In the ninth S site, S(1) is bonded to one V(1), one V(3), one V(4), and one Ge(1) atom to form SV3Ge tetrahedra that share  a cornercorner with one S(1)V3Ge tetrahedra,  a cornercorner with one S(3)V3Ge tetrahedra,  a cornercorner with one S(4)V3Ge tetrahedra,  an edgeedge with one S(5)V3Ga tetrahedra,  an edgeedge with one S(1)V3Ge tetrahedra, and  an edgeedge with one S(3)V3Ge tetrahedra. In the tenth S site, S(2) is bonded to one V(2), two equivalent V(5), and one Ga(1) atom to form SV3Ga tetrahedra that share  a cornercorner with one S(2)V3Ga tetrahedra, corners with two equivalent S(5)V3Ga tetrahedra,  an edgeedge with one S(2)V3Ga tetrahedra, and edges with two equivalent S(4)V3Ge tetrahedra.