Al(V4Ge)3 crystallizes in the orthorhombic Pmmm space group. There are five inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one V(1), one V(2), four equivalent V(3), two equivalent Al(1), and two equivalent Ge(2) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one V(1), one V(2), four equivalent V(3), two equivalent Ge(1), and two equivalent Ge(2) atoms. In the third V site, V(3) is bonded in a 14-coordinate geometry to two equivalent V(1), two equivalent V(2), two equivalent V(3), two equivalent V(4), two equivalent V(5), one Al(1), one Ge(1), and two equivalent Ge(2) atoms. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to two equivalent V(4), four equivalent V(3), two equivalent Al(1), and two equivalent Ge(2) atoms. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to two equivalent V(5), four equivalent V(3), two equivalent Ge(1), and two equivalent Ge(2) atoms. Al(1) is bonded to four equivalent V(1), four equivalent V(3), and four equivalent V(4) atoms to form AlV12 cuboctahedra that share edges with two equivalent Ge(1)V12 cuboctahedra, edges with four equivalent Al(1)V12 cuboctahedra, and faces with eight equivalent Ge(2)V12 cuboctahedra. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to four equivalent V(2), four equivalent V(3), and four equivalent V(5) atoms to form GeV12 cuboctahedra that share edges with two equivalent Al(1)V12 cuboctahedra, edges with four equivalent Ge(1)V12 cuboctahedra, and faces with eight equivalent Ge(2)V12 cuboctahedra. In the second Ge site, Ge(2) is bonded to two equivalent V(1), two equivalent V(2), two equivalent V(4), two equivalent V(5), and four equivalent V(3) atoms to form GeV12 cuboctahedra that share edges with six equivalent Ge(2)V12 cuboctahedra, faces with four equivalent Al(1)V12 cuboctahedra, and faces with four equivalent Ge(1)V12 cuboctahedra.
Al(V4Ge)3 crystallizes in the orthorhombic Pmmm space group. There are five inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one V(1), one V(2), four equivalent V(3), two equivalent Al(1), and two equivalent Ge(2) atoms. The V(1)-V(1) bond length is 2.37 Å. The V(1)-V(2) bond length is 2.37 Å. All V(1)-V(3) bond lengths are 2.92 Å. Both V(1)-Al(1) bond lengths are 2.66 Å. Both V(1)-Ge(2) bond lengths are 2.66 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one V(1), one V(2), four equivalent V(3), two equivalent Ge(1), and two equivalent Ge(2) atoms. The V(2)-V(2) bond length is 2.38 Å. All V(2)-V(3) bond lengths are 2.91 Å. Both V(2)-Ge(1) bond lengths are 2.66 Å. Both V(2)-Ge(2) bond lengths are 2.65 Å. In the third V site, V(3) is bonded in a 14-coordinate geometry to two equivalent V(1), two equivalent V(2), two equivalent V(3), two equivalent V(4), two equivalent V(5), one Al(1), one Ge(1), and two equivalent Ge(2) atoms. There is one shorter (2.37 Å) and one longer (2.38 Å) V(3)-V(3) bond length. Both V(3)-V(4) bond lengths are 2.92 Å. Both V(3)-V(5) bond lengths are 2.90 Å. The V(3)-Al(1) bond length is 2.67 Å. The V(3)-Ge(1) bond length is 2.64 Å. Both V(3)-Ge(2) bond lengths are 2.66 Å. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to two equivalent V(4), four equivalent V(3), two equivalent Al(1), and two equivalent Ge(2) atoms. There is one shorter (2.37 Å) and one longer (2.38 Å) V(4)-V(4) bond length. Both V(4)-Al(1) bond lengths are 2.66 Å. Both V(4)-Ge(2) bond lengths are 2.66 Å. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to two equivalent V(5), four equivalent V(3), two equivalent Ge(1), and two equivalent Ge(2) atoms. There is one shorter (2.37 Å) and one longer (2.38 Å) V(5)-V(5) bond length. Both V(5)-Ge(1) bond lengths are 2.66 Å. Both V(5)-Ge(2) bond lengths are 2.65 Å. Al(1) is bonded to four equivalent V(1), four equivalent V(3), and four equivalent V(4) atoms to form AlV12 cuboctahedra that share edges with two equivalent Ge(1)V12 cuboctahedra, edges with four equivalent Al(1)V12 cuboctahedra, and faces with eight equivalent Ge(2)V12 cuboctahedra. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to four equivalent V(2), four equivalent V(3), and four equivalent V(5) atoms to form GeV12 cuboctahedra that share edges with two equivalent Al(1)V12 cuboctahedra, edges with four equivalent Ge(1)V12 cuboctahedra, and faces with eight equivalent Ge(2)V12 cuboctahedra. In the second Ge site, Ge(2) is bonded to two equivalent V(1), two equivalent V(2), two equivalent V(4), two equivalent V(5), and four equivalent V(3) atoms to form GeV12 cuboctahedra that share edges with six equivalent Ge(2)V12 cuboctahedra, faces with four equivalent Al(1)V12 cuboctahedra, and faces with four equivalent Ge(1)V12 cuboctahedra.