Al(V4Si)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 14-coordinate geometry to one V(1), one V(2), four equivalent V(3), four equivalent V(4), two equivalent Al(1), and two equivalent Si(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 Si(1), and two equivalent Si(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 Si(1), and two equivalent Si(2) atoms. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to two equivalent V(4), four equivalent V(1), four equivalent V(3), two equivalent Al(1), and two equivalent Si(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 Si(1), and two equivalent Si(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 Si(1)V12 cuboctahedra, edges with four equivalent Al(1)V12 cuboctahedra, and faces with eight equivalent Si(2)V12 cuboctahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to four equivalent V(2), four equivalent V(3), and four equivalent V(5) atoms to form SiV12 cuboctahedra that share edges with two equivalent Al(1)V12 cuboctahedra, edges with four equivalent Si(1)V12 cuboctahedra, and faces with eight equivalent Si(2)V12 cuboctahedra. In the second Si site, Si(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 SiV12 cuboctahedra that share edges with six equivalent Si(2)V12 cuboctahedra, faces with four equivalent Al(1)V12 cuboctahedra, and faces with four equivalent Si(1)V12 cuboctahedra.
Al(V4Si)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 14-coordinate geometry to one V(1), one V(2), four equivalent V(3), four equivalent V(4), two equivalent Al(1), and two equivalent Si(2) atoms. The V(1)-V(1) bond length is 2.41 Å. The V(1)-V(2) bond length is 2.32 Å. All V(1)-V(3) bond lengths are 2.89 Å. All V(1)-V(4) bond lengths are 2.88 Å. Both V(1)-Al(1) bond lengths are 2.64 Å. Both V(1)-Si(2) bond lengths are 2.63 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 Si(1), and two equivalent Si(2) atoms. The V(2)-V(2) bond length is 2.37 Å. All V(2)-V(3) bond lengths are 2.87 Å. Both V(2)-Si(1) bond lengths are 2.63 Å. Both V(2)-Si(2) bond lengths are 2.62 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 Si(1), and two equivalent Si(2) atoms. There is one shorter (2.33 Å) and one longer (2.39 Å) V(3)-V(3) bond length. Both V(3)-V(4) bond lengths are 2.93 Å. Both V(3)-V(5) bond lengths are 2.84 Å. The V(3)-Al(1) bond length is 2.68 Å. The V(3)-Si(1) bond length is 2.60 Å. Both V(3)-Si(2) bond lengths are 2.62 Å. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to two equivalent V(4), four equivalent V(1), four equivalent V(3), two equivalent Al(1), and two equivalent Si(2) atoms. There is one shorter (2.28 Å) and one longer (2.42 Å) V(4)-V(4) bond length. Both V(4)-Al(1) bond lengths are 2.65 Å. Both V(4)-Si(2) bond lengths are 2.63 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 Si(1), and two equivalent Si(2) atoms. There is one shorter (2.34 Å) and one longer (2.36 Å) V(5)-V(5) bond length. Both V(5)-Si(1) bond lengths are 2.63 Å. Both V(5)-Si(2) bond lengths are 2.62 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 Si(1)V12 cuboctahedra, edges with four equivalent Al(1)V12 cuboctahedra, and faces with eight equivalent Si(2)V12 cuboctahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to four equivalent V(2), four equivalent V(3), and four equivalent V(5) atoms to form SiV12 cuboctahedra that share edges with two equivalent Al(1)V12 cuboctahedra, edges with four equivalent Si(1)V12 cuboctahedra, and faces with eight equivalent Si(2)V12 cuboctahedra. In the second Si site, Si(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 SiV12 cuboctahedra that share edges with six equivalent Si(2)V12 cuboctahedra, faces with four equivalent Al(1)V12 cuboctahedra, and faces with four equivalent Si(1)V12 cuboctahedra.