LiNi3AlO5 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, corners with two equivalent Al(1)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with three equivalent Ni(3)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Ni(3)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, and edges with three equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. In the second Ni site, Ni(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NiO6 octahedra that share corners with two equivalent Ni(4)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Al(1)O6 octahedra, edges with four equivalent Ni(1)O6 octahedra, and edges with four equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the third Ni site, Ni(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Al(1)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Al(1)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. In the fourth Ni site, Ni(4) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NiO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra, corners with four equivalent Al(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with four equivalent Ni(1)O6 octahedra, and edges with four equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. Al(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form AlO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, edges with two equivalent Al(1)O6 octahedra, edges with three equivalent Ni(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ni(2), one Ni(4), two equivalent Ni(1), and two equivalent Ni(3) atoms to form ONi6 octahedra that share corners with two equivalent O(1)Ni6 octahedra, corners with four equivalent O(3)Li2Al2Ni2 octahedra, edges with two equivalent O(3)Li2Al2Ni2 octahedra, edges with two equivalent O(1)Ni6 octahedra, and edges with eight equivalent O(2)LiAlNi4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(2) is bonded to one Li(1), one Ni(1), one Ni(2), one Ni(3), one Ni(4), and one Al(1) atom to form OLiAlNi4 octahedra that share corners with two equivalent O(3)Li2Al2Ni2 octahedra, corners with four equivalent O(2)LiAlNi4 octahedra, edges with three equivalent O(2)LiAlNi4 octahedra, edges with four equivalent O(1)Ni6 octahedra, and edges with five equivalent O(3)Li2Al2Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to two equivalent Li(1), one Ni(1), one Ni(3), and two equivalent Al(1) atoms to form OLi2Al2Ni2 octahedra that share corners with two equivalent O(3)Li2Al2Ni2 octahedra, corners with two equivalent O(2)LiAlNi4 octahedra, corners with two equivalent O(1)Ni6 octahedra,  an edgeedge with one O(1)Ni6 octahedra, edges with five equivalent O(2)LiAlNi4 octahedra, and edges with six equivalent O(3)Li2Al2Ni2 octahedra. The corner-sharing octahedral tilt angles range from 3-7°.
LiNi3AlO5 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, corners with two equivalent Al(1)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with three equivalent Ni(3)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. Both Li(1)-O(2) bond lengths are 2.08 Å. There are two shorter (2.07 Å) and two longer (2.28 Å) Li(1)-O(3) bond lengths. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Ni(3)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, and edges with three equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. Both Ni(1)-O(1) bond lengths are 2.09 Å. Both Ni(1)-O(2) bond lengths are 2.12 Å. Both Ni(1)-O(3) bond lengths are 2.06 Å. In the second Ni site, Ni(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NiO6 octahedra that share corners with two equivalent Ni(4)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Al(1)O6 octahedra, edges with four equivalent Ni(1)O6 octahedra, and edges with four equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. Both Ni(2)-O(1) bond lengths are 2.14 Å. All Ni(2)-O(2) bond lengths are 2.07 Å. In the third Ni site, Ni(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Al(1)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Al(1)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. Both Ni(3)-O(1) bond lengths are 2.12 Å. Both Ni(3)-O(2) bond lengths are 2.09 Å. Both Ni(3)-O(3) bond lengths are 2.12 Å. In the fourth Ni site, Ni(4) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NiO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra, corners with four equivalent Al(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with four equivalent Ni(1)O6 octahedra, and edges with four equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. Both Ni(4)-O(1) bond lengths are 2.06 Å. All Ni(4)-O(2) bond lengths are 2.18 Å. Al(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form AlO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, edges with two equivalent Al(1)O6 octahedra, edges with three equivalent Ni(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. Both Al(1)-O(2) bond lengths are 1.97 Å. There are two shorter (1.92 Å) and two longer (1.96 Å) Al(1)-O(3) bond lengths. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ni(2), one Ni(4), two equivalent Ni(1), and two equivalent Ni(3) atoms to form ONi6 octahedra that share corners with two equivalent O(1)Ni6 octahedra, corners with four equivalent O(3)Li2Al2Ni2 octahedra, edges with two equivalent O(3)Li2Al2Ni2 octahedra, edges with two equivalent O(1)Ni6 octahedra, and edges with eight equivalent O(2)LiAlNi4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(2) is bonded to one Li(1), one Ni(1), one Ni(2), one Ni(3), one Ni(4), and one Al(1) atom to form OLiAlNi4 octahedra that share corners with two equivalent O(3)Li2Al2Ni2 octahedra, corners with four equivalent O(2)LiAlNi4 octahedra, edges with three equivalent O(2)LiAlNi4 octahedra, edges with four equivalent O(1)Ni6 octahedra, and edges with five equivalent O(3)Li2Al2Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to two equivalent Li(1), one Ni(1), one Ni(3), and two equivalent Al(1) atoms to form OLi2Al2Ni2 octahedra that share corners with two equivalent O(3)Li2Al2Ni2 octahedra, corners with two equivalent O(2)LiAlNi4 octahedra, corners with two equivalent O(1)Ni6 octahedra,  an edgeedge with one O(1)Ni6 octahedra, edges with five equivalent O(2)LiAlNi4 octahedra, and edges with six equivalent O(3)Li2Al2Ni2 octahedra. The corner-sharing octahedral tilt angles range from 3-7°.