Al5(NiO4)3 is beta indium sulfide-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form NiO6 octahedra that share  a cornercorner with one Al(3)O4 tetrahedra, corners with two equivalent Al(1)O4 tetrahedra, corners with three equivalent Al(2)O4 tetrahedra,  an edgeedge with one Al(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Al(5)O6 octahedra. In the second Ni site, Ni(2) is bonded to two equivalent O(3), two equivalent O(6), and two equivalent O(9) atoms to form NiO6 octahedra that share corners with two equivalent Al(1)O4 tetrahedra, corners with four equivalent Al(3)O4 tetrahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Al(4)O6 octahedra. There are five inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1), one O(9), and two equivalent O(4) atoms to form AlO4 tetrahedra that share corners with two equivalent Ni(2)O6 octahedra, corners with two equivalent Al(5)O6 octahedra, corners with three equivalent Al(4)O6 octahedra, and corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-62°. In the second Al site, Al(2) is bonded to one O(2), one O(7), and two equivalent O(5) atoms to form AlO4 tetrahedra that share corners with three equivalent Al(5)O6 octahedra and corners with six equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-58°. In the third Al site, Al(3) is bonded to one O(3), one O(8), and two equivalent O(6) atoms to form AlO4 tetrahedra that share  a cornercorner with one Al(5)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra, corners with three equivalent Al(4)O6 octahedra, and corners with four equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-58°. In the fourth Al site, Al(4) is bonded to one O(1), one O(3), two equivalent O(4), and two equivalent O(6) atoms to form AlO6 octahedra that share corners with three equivalent Al(1)O4 tetrahedra, corners with three equivalent Al(3)O4 tetrahedra,  an edgeedge with one Al(5)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. In the fifth Al site, Al(5) is bonded to one O(7), one O(8), two equivalent O(4), and two equivalent O(5) atoms to form AlO6 octahedra that share  a cornercorner with one Al(3)O4 tetrahedra, corners with two equivalent Al(1)O4 tetrahedra, corners with three equivalent Al(2)O4 tetrahedra,  an edgeedge with one Al(4)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Ni(1), one Al(1), and one Al(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Ni(1) and one Al(2) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to two equivalent Ni(2), one Al(3), and one Al(4) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Ni(1), one Al(1), one Al(4), and one Al(5) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Ni(1), one Al(2), and one Al(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ni(2), one Al(3), and one Al(4) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to two equivalent Ni(1), one Al(2), and one Al(5) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to two equivalent Ni(1), one Al(3), and one Al(5) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to two equivalent Ni(2) and one Al(1) atom.
Al5(NiO4)3 is beta indium sulfide-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form NiO6 octahedra that share  a cornercorner with one Al(3)O4 tetrahedra, corners with two equivalent Al(1)O4 tetrahedra, corners with three equivalent Al(2)O4 tetrahedra,  an edgeedge with one Al(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Al(5)O6 octahedra. The Ni(1)-O(1) bond length is 2.05 Å. The Ni(1)-O(2) bond length is 1.93 Å. The Ni(1)-O(4) bond length is 1.94 Å. The Ni(1)-O(5) bond length is 1.89 Å. The Ni(1)-O(7) bond length is 2.06 Å. The Ni(1)-O(8) bond length is 2.05 Å. In the second Ni site, Ni(2) is bonded to two equivalent O(3), two equivalent O(6), and two equivalent O(9) atoms to form NiO6 octahedra that share corners with two equivalent Al(1)O4 tetrahedra, corners with four equivalent Al(3)O4 tetrahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Al(4)O6 octahedra. Both Ni(2)-O(3) bond lengths are 2.06 Å. Both Ni(2)-O(6) bond lengths are 1.92 Å. Both Ni(2)-O(9) bond lengths are 1.96 Å. There are five inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1), one O(9), and two equivalent O(4) atoms to form AlO4 tetrahedra that share corners with two equivalent Ni(2)O6 octahedra, corners with two equivalent Al(5)O6 octahedra, corners with three equivalent Al(4)O6 octahedra, and corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-62°. The Al(1)-O(1) bond length is 1.85 Å. The Al(1)-O(9) bond length is 1.79 Å. Both Al(1)-O(4) bond lengths are 1.86 Å. In the second Al site, Al(2) is bonded to one O(2), one O(7), and two equivalent O(5) atoms to form AlO4 tetrahedra that share corners with three equivalent Al(5)O6 octahedra and corners with six equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-58°. The Al(2)-O(2) bond length is 1.79 Å. The Al(2)-O(7) bond length is 1.81 Å. Both Al(2)-O(5) bond lengths are 1.78 Å. In the third Al site, Al(3) is bonded to one O(3), one O(8), and two equivalent O(6) atoms to form AlO4 tetrahedra that share  a cornercorner with one Al(5)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra, corners with three equivalent Al(4)O6 octahedra, and corners with four equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-58°. The Al(3)-O(3) bond length is 1.80 Å. The Al(3)-O(8) bond length is 1.81 Å. Both Al(3)-O(6) bond lengths are 1.78 Å. In the fourth Al site, Al(4) is bonded to one O(1), one O(3), two equivalent O(4), and two equivalent O(6) atoms to form AlO6 octahedra that share corners with three equivalent Al(1)O4 tetrahedra, corners with three equivalent Al(3)O4 tetrahedra,  an edgeedge with one Al(5)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The Al(4)-O(1) bond length is 1.92 Å. The Al(4)-O(3) bond length is 1.90 Å. Both Al(4)-O(4) bond lengths are 2.03 Å. Both Al(4)-O(6) bond lengths are 1.85 Å. In the fifth Al site, Al(5) is bonded to one O(7), one O(8), two equivalent O(4), and two equivalent O(5) atoms to form AlO6 octahedra that share  a cornercorner with one Al(3)O4 tetrahedra, corners with two equivalent Al(1)O4 tetrahedra, corners with three equivalent Al(2)O4 tetrahedra,  an edgeedge with one Al(4)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The Al(5)-O(7) bond length is 1.89 Å. The Al(5)-O(8) bond length is 1.89 Å. Both Al(5)-O(4) bond lengths are 2.03 Å. Both Al(5)-O(5) bond lengths are 1.85 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Ni(1), one Al(1), and one Al(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Ni(1) and one Al(2) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to two equivalent Ni(2), one Al(3), and one Al(4) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Ni(1), one Al(1), one Al(4), and one Al(5) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Ni(1), one Al(2), and one Al(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ni(2), one Al(3), and one Al(4) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to two equivalent Ni(1), one Al(2), and one Al(5) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to two equivalent Ni(1), one Al(3), and one Al(5) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to two equivalent Ni(2) and one Al(1) atom.