Mo12NiAl3 crystallizes in the orthorhombic Pmmm space group. There are five inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 6-coordinate geometry to one Mo(1), one Mo(2), two equivalent Ni(1), and two equivalent Al(1) atoms. In the second Mo site, Mo(2) is bonded in a 6-coordinate geometry to one Mo(1), one Mo(2), two equivalent Al(1), and two equivalent Al(2) atoms. In the third Mo site, Mo(3) is bonded in a 6-coordinate geometry to two equivalent Mo(3), two equivalent Al(1), and two equivalent Al(2) atoms. In the fourth Mo site, Mo(4) is bonded in a 6-coordinate geometry to two equivalent Mo(4), two equivalent Ni(1), and two equivalent Al(1) atoms. In the fifth Mo site, Mo(5) is bonded in a 6-coordinate geometry to two equivalent Mo(5), one Ni(1), one Al(2), and two equivalent Al(1) atoms. Ni(1) is bonded to four equivalent Mo(1), four equivalent Mo(4), and four equivalent Mo(5) atoms to form NiMo12 cuboctahedra that share edges with two equivalent Al(2)Mo12 cuboctahedra, edges with four equivalent Ni(1)Mo12 cuboctahedra, and faces with eight equivalent Al(1)Mo12 cuboctahedra. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to two equivalent Mo(1), two equivalent Mo(2), two equivalent Mo(3), two equivalent Mo(4), and four equivalent Mo(5) atoms to form AlMo12 cuboctahedra that share edges with six equivalent Al(1)Mo12 cuboctahedra, faces with four equivalent Ni(1)Mo12 cuboctahedra, and faces with four equivalent Al(2)Mo12 cuboctahedra. In the second Al site, Al(2) is bonded to four equivalent Mo(2), four equivalent Mo(3), and four equivalent Mo(5) atoms to form AlMo12 cuboctahedra that share edges with two equivalent Ni(1)Mo12 cuboctahedra, edges with four equivalent Al(2)Mo12 cuboctahedra, and faces with eight equivalent Al(1)Mo12 cuboctahedra.
Mo12NiAl3 crystallizes in the orthorhombic Pmmm space group. There are five inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 6-coordinate geometry to one Mo(1), one Mo(2), two equivalent Ni(1), and two equivalent Al(1) atoms. The Mo(1)-Mo(1) bond length is 2.46 Å. The Mo(1)-Mo(2) bond length is 2.51 Å. Both Mo(1)-Ni(1) bond lengths are 2.77 Å. Both Mo(1)-Al(1) bond lengths are 2.78 Å. In the second Mo site, Mo(2) is bonded in a 6-coordinate geometry to one Mo(1), one Mo(2), two equivalent Al(1), and two equivalent Al(2) atoms. The Mo(2)-Mo(2) bond length is 2.48 Å. Both Mo(2)-Al(1) bond lengths are 2.78 Å. Both Mo(2)-Al(2) bond lengths are 2.77 Å. In the third Mo site, Mo(3) is bonded in a 6-coordinate geometry to two equivalent Mo(3), two equivalent Al(1), and two equivalent Al(2) atoms. There is one shorter (2.46 Å) and one longer (2.51 Å) Mo(3)-Mo(3) bond length. Both Mo(3)-Al(1) bond lengths are 2.79 Å. Both Mo(3)-Al(2) bond lengths are 2.77 Å. In the fourth Mo site, Mo(4) is bonded in a 6-coordinate geometry to two equivalent Mo(4), two equivalent Ni(1), and two equivalent Al(1) atoms. Both Mo(4)-Mo(4) bond lengths are 2.48 Å. Both Mo(4)-Ni(1) bond lengths are 2.78 Å. Both Mo(4)-Al(1) bond lengths are 2.78 Å. In the fifth Mo site, Mo(5) is bonded in a 6-coordinate geometry to two equivalent Mo(5), one Ni(1), one Al(2), and two equivalent Al(1) atoms. There is one shorter (2.48 Å) and one longer (2.49 Å) Mo(5)-Mo(5) bond length. The Mo(5)-Ni(1) bond length is 2.76 Å. The Mo(5)-Al(2) bond length is 2.80 Å. Both Mo(5)-Al(1) bond lengths are 2.78 Å. Ni(1) is bonded to four equivalent Mo(1), four equivalent Mo(4), and four equivalent Mo(5) atoms to form NiMo12 cuboctahedra that share edges with two equivalent Al(2)Mo12 cuboctahedra, edges with four equivalent Ni(1)Mo12 cuboctahedra, and faces with eight equivalent Al(1)Mo12 cuboctahedra. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to two equivalent Mo(1), two equivalent Mo(2), two equivalent Mo(3), two equivalent Mo(4), and four equivalent Mo(5) atoms to form AlMo12 cuboctahedra that share edges with six equivalent Al(1)Mo12 cuboctahedra, faces with four equivalent Ni(1)Mo12 cuboctahedra, and faces with four equivalent Al(2)Mo12 cuboctahedra. In the second Al site, Al(2) is bonded to four equivalent Mo(2), four equivalent Mo(3), and four equivalent Mo(5) atoms to form AlMo12 cuboctahedra that share edges with two equivalent Ni(1)Mo12 cuboctahedra, edges with four equivalent Al(2)Mo12 cuboctahedra, and faces with eight equivalent Al(1)Mo12 cuboctahedra.