NiAlO3 crystallizes in the hexagonal P6_3cm space group. Ni(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form corner-sharing NiO5 trigonal bipyramids. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded in a 6-coordinate geometry to three equivalent O(3) and three equivalent O(4) atoms. In the second Al site, Al(2) is bonded in a 7-coordinate geometry to one O(2), three equivalent O(3), and three equivalent O(4) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to three equivalent Ni(1) atoms. In the second O site, O(2) is bonded to three equivalent Ni(1) and one Al(2) atom to form a mixture of distorted edge and corner-sharing OAlNi3 tetrahedra. In the third O site, O(3) is bonded to one Ni(1), one Al(2), and two equivalent Al(1) atoms to form OAl3Ni tetrahedra that share corners with four equivalent O(4)Al3Ni tetrahedra, corners with six equivalent O(3)Al3Ni tetrahedra,  an edgeedge with one O(2)AlNi3 tetrahedra, and edges with three equivalent O(4)Al3Ni tetrahedra. In the fourth O site, O(4) is bonded to one Ni(1), one Al(2), and two equivalent Al(1) atoms to form OAl3Ni tetrahedra that share corners with two equivalent O(2)AlNi3 tetrahedra, corners with four equivalent O(3)Al3Ni tetrahedra, corners with six equivalent O(4)Al3Ni tetrahedra, and edges with three equivalent O(3)Al3Ni tetrahedra.
NiAlO3 crystallizes in the hexagonal P6_3cm space group. Ni(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form corner-sharing NiO5 trigonal bipyramids. The Ni(1)-O(2) bond length is 1.84 Å. The Ni(1)-O(3) bond length is 1.88 Å. The Ni(1)-O(4) bond length is 1.90 Å. Both Ni(1)-O(1) bond lengths are 1.82 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded in a 6-coordinate geometry to three equivalent O(3) and three equivalent O(4) atoms. All Al(1)-O(3) bond lengths are 1.98 Å. All Al(1)-O(4) bond lengths are 2.02 Å. In the second Al site, Al(2) is bonded in a 7-coordinate geometry to one O(2), three equivalent O(3), and three equivalent O(4) atoms. The Al(2)-O(2) bond length is 2.22 Å. All Al(2)-O(3) bond lengths are 2.08 Å. All Al(2)-O(4) bond lengths are 1.97 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to three equivalent Ni(1) atoms. In the second O site, O(2) is bonded to three equivalent Ni(1) and one Al(2) atom to form a mixture of distorted edge and corner-sharing OAlNi3 tetrahedra. In the third O site, O(3) is bonded to one Ni(1), one Al(2), and two equivalent Al(1) atoms to form OAl3Ni tetrahedra that share corners with four equivalent O(4)Al3Ni tetrahedra, corners with six equivalent O(3)Al3Ni tetrahedra,  an edgeedge with one O(2)AlNi3 tetrahedra, and edges with three equivalent O(4)Al3Ni tetrahedra. In the fourth O site, O(4) is bonded to one Ni(1), one Al(2), and two equivalent Al(1) atoms to form OAl3Ni tetrahedra that share corners with two equivalent O(2)AlNi3 tetrahedra, corners with four equivalent O(3)Al3Ni tetrahedra, corners with six equivalent O(4)Al3Ni tetrahedra, and edges with three equivalent O(3)Al3Ni tetrahedra.