NaNi3O4 is Caswellsilverite-like structured and crystallizes in the triclinic P-1 space group. Na(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form NaO6 octahedra that share corners with three equivalent Ni(1)O6 octahedra, corners with three equivalent Ni(3)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with three equivalent Ni(3)O6 octahedra, and edges with four equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form NiO6 octahedra that share corners with six equivalent Na(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with four equivalent Ni(2)O6 octahedra, and edges with four equivalent Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the second Ni site, Ni(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with three equivalent Ni(3)O6 octahedra, corners with three equivalent Ni(4)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with three equivalent Ni(3)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. In the third Ni site, Ni(3) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form NiO6 octahedra that share corners with three equivalent Na(1)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Ni(2)O6 octahedra, and edges with six equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. In the fourth Ni site, Ni(4) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form NiO6 octahedra that share corners with six equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), two equivalent Ni(2), and three equivalent Ni(3) atoms to form ONaNi5 octahedra that share corners with three equivalent O(4)Na2Ni4 octahedra, corners with three equivalent O(3)NaNi5 octahedra,  an edgeedge with one O(3)NaNi5 octahedra, edges with two equivalent O(2)Na2Ni4 octahedra, edges with four equivalent O(1)NaNi5 octahedra, and edges with five equivalent O(4)Na2Ni4 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. In the second O site, O(2) is bonded to two equivalent Na(1), one Ni(2), one Ni(4), and two equivalent Ni(1) atoms to form ONa2Ni4 octahedra that share corners with three equivalent O(2)Na2Ni4 octahedra, corners with three equivalent O(4)Na2Ni4 octahedra,  an edgeedge with one O(4)Na2Ni4 octahedra, edges with two equivalent O(1)NaNi5 octahedra, edges with three equivalent O(2)Na2Ni4 octahedra, and edges with six equivalent O(3)NaNi5 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Na(1), one Ni(1), two equivalent Ni(2), and two equivalent Ni(4) atoms to form ONaNi5 octahedra that share corners with three equivalent O(1)NaNi5 octahedra, corners with three equivalent O(3)NaNi5 octahedra,  an edgeedge with one O(1)NaNi5 octahedra, edges with two equivalent O(4)Na2Ni4 octahedra, edges with three equivalent O(3)NaNi5 octahedra, and edges with six equivalent O(2)Na2Ni4 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fourth O site, O(4) is bonded to two equivalent Na(1), one Ni(2), and three equivalent Ni(3) atoms to form ONa2Ni4 octahedra that share corners with three equivalent O(2)Na2Ni4 octahedra, corners with three equivalent O(1)NaNi5 octahedra,  an edgeedge with one O(2)Na2Ni4 octahedra, edges with two equivalent O(3)NaNi5 octahedra, edges with four equivalent O(4)Na2Ni4 octahedra, and edges with five equivalent O(1)NaNi5 octahedra. The corner-sharing octahedral tilt angles range from 1-9°.
NaNi3O4 is Caswellsilverite-like structured and crystallizes in the triclinic P-1 space group. Na(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form NaO6 octahedra that share corners with three equivalent Ni(1)O6 octahedra, corners with three equivalent Ni(3)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with three equivalent Ni(3)O6 octahedra, and edges with four equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. The Na(1)-O(1) bond length is 2.25 Å. The Na(1)-O(3) bond length is 2.27 Å. There is one shorter (2.28 Å) and one longer (2.30 Å) Na(1)-O(2) bond length. Both Na(1)-O(4) bond lengths are 2.29 Å. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form NiO6 octahedra that share corners with six equivalent Na(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with four equivalent Ni(2)O6 octahedra, and edges with four equivalent Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. Both Ni(1)-O(3) bond lengths are 1.94 Å. There are two shorter (1.92 Å) and two longer (2.11 Å) Ni(1)-O(2) bond lengths. In the second Ni site, Ni(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with three equivalent Ni(3)O6 octahedra, corners with three equivalent Ni(4)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with three equivalent Ni(3)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. The Ni(2)-O(2) bond length is 2.12 Å. The Ni(2)-O(4) bond length is 2.13 Å. There is one shorter (2.10 Å) and one longer (2.13 Å) Ni(2)-O(1) bond length. There is one shorter (2.13 Å) and one longer (2.19 Å) Ni(2)-O(3) bond length. In the third Ni site, Ni(3) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form NiO6 octahedra that share corners with three equivalent Na(1)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Ni(2)O6 octahedra, and edges with six equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. There are a spread of Ni(3)-O(1) bond distances ranging from 2.02-2.19 Å. There are a spread of Ni(3)-O(4) bond distances ranging from 2.02-2.09 Å. In the fourth Ni site, Ni(4) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form NiO6 octahedra that share corners with six equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. Both Ni(4)-O(2) bond lengths are 2.12 Å. There are two shorter (2.12 Å) and two longer (2.17 Å) Ni(4)-O(3) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), two equivalent Ni(2), and three equivalent Ni(3) atoms to form ONaNi5 octahedra that share corners with three equivalent O(4)Na2Ni4 octahedra, corners with three equivalent O(3)NaNi5 octahedra,  an edgeedge with one O(3)NaNi5 octahedra, edges with two equivalent O(2)Na2Ni4 octahedra, edges with four equivalent O(1)NaNi5 octahedra, and edges with five equivalent O(4)Na2Ni4 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. In the second O site, O(2) is bonded to two equivalent Na(1), one Ni(2), one Ni(4), and two equivalent Ni(1) atoms to form ONa2Ni4 octahedra that share corners with three equivalent O(2)Na2Ni4 octahedra, corners with three equivalent O(4)Na2Ni4 octahedra,  an edgeedge with one O(4)Na2Ni4 octahedra, edges with two equivalent O(1)NaNi5 octahedra, edges with three equivalent O(2)Na2Ni4 octahedra, and edges with six equivalent O(3)NaNi5 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Na(1), one Ni(1), two equivalent Ni(2), and two equivalent Ni(4) atoms to form ONaNi5 octahedra that share corners with three equivalent O(1)NaNi5 octahedra, corners with three equivalent O(3)NaNi5 octahedra,  an edgeedge with one O(1)NaNi5 octahedra, edges with two equivalent O(4)Na2Ni4 octahedra, edges with three equivalent O(3)NaNi5 octahedra, and edges with six equivalent O(2)Na2Ni4 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fourth O site, O(4) is bonded to two equivalent Na(1), one Ni(2), and three equivalent Ni(3) atoms to form ONa2Ni4 octahedra that share corners with three equivalent O(2)Na2Ni4 octahedra, corners with three equivalent O(1)NaNi5 octahedra,  an edgeedge with one O(2)Na2Ni4 octahedra, edges with two equivalent O(3)NaNi5 octahedra, edges with four equivalent O(4)Na2Ni4 octahedra, and edges with five equivalent O(1)NaNi5 octahedra. The corner-sharing octahedral tilt angles range from 1-9°.