Na2Ni3O5 is Caswellsilverite-like structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form NaO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. In the second Na site, Na(2) is bonded to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share  a cornercorner with one Ni(3)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-16°. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form NiO6 octahedra that share  a cornercorner with one Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with three equivalent Na(2)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-16°. In the second Ni site, Ni(2) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form NiO6 octahedra that share  a cornercorner with one Ni(4)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with three equivalent Na(1)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-15°. In the third Ni site, Ni(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form NiO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-12°. In the fourth Ni site, Ni(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-12°. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one Ni(1), one Ni(2), one Ni(3), and one Ni(4) atom to form ONa2Ni4 octahedra that share  a cornercorner with one O(5)Na2Ni4 octahedra,  a cornercorner with one O(3)Na3Ni3 octahedra, corners with two equivalent O(1)Na2Ni4 octahedra, corners with two equivalent O(4)Na3Ni3 octahedra,  an edgeedge with one O(1)Na2Ni4 octahedra, edges with two equivalent O(3)Na3Ni3 octahedra, edges with two equivalent O(4)Na3Ni3 octahedra, edges with three equivalent O(5)Na2Ni4 octahedra, and edges with four equivalent O(2)Na2Ni4 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Ni(3), one Ni(4), and two equivalent Ni(1) atoms to form ONa2Ni4 octahedra that share  a cornercorner with one O(3)Na3Ni3 octahedra,  a cornercorner with one O(4)Na3Ni3 octahedra, corners with two equivalent O(2)Na2Ni4 octahedra, corners with two equivalent O(5)Na2Ni4 octahedra,  an edgeedge with one O(2)Na2Ni4 octahedra, edges with two equivalent O(5)Na2Ni4 octahedra, edges with two equivalent O(3)Na3Ni3 octahedra, edges with three equivalent O(4)Na3Ni3 octahedra, and edges with four equivalent O(1)Na2Ni4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(2), one Ni(1), and two equivalent Ni(2) atoms to form ONa3Ni3 octahedra that share  a cornercorner with one O(1)Na2Ni4 octahedra,  a cornercorner with one O(2)Na2Ni4 octahedra, corners with two equivalent O(5)Na2Ni4 octahedra, corners with two equivalent O(4)Na3Ni3 octahedra, edges with two equivalent O(1)Na2Ni4 octahedra, edges with two equivalent O(2)Na2Ni4 octahedra, edges with two equivalent O(3)Na3Ni3 octahedra, edges with three equivalent O(5)Na2Ni4 octahedra, and edges with three equivalent O(4)Na3Ni3 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. In the fourth O site, O(4) is bonded to one Na(1), two equivalent Na(2), one Ni(1), one Ni(2), and one Ni(3) atom to form ONa3Ni3 octahedra that share  a cornercorner with one O(2)Na2Ni4 octahedra,  a cornercorner with one O(4)Na3Ni3 octahedra, corners with two equivalent O(1)Na2Ni4 octahedra, corners with two equivalent O(3)Na3Ni3 octahedra,  an edgeedge with one O(4)Na3Ni3 octahedra, edges with two equivalent O(1)Na2Ni4 octahedra, edges with three equivalent O(2)Na2Ni4 octahedra, edges with three equivalent O(5)Na2Ni4 octahedra, and edges with three equivalent O(3)Na3Ni3 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one Ni(1), one Ni(4), and two equivalent Ni(2) atoms to form ONa2Ni4 octahedra that share  a cornercorner with one O(1)Na2Ni4 octahedra,  a cornercorner with one O(5)Na2Ni4 octahedra, corners with two equivalent O(2)Na2Ni4 octahedra, corners with two equivalent O(3)Na3Ni3 octahedra,  an edgeedge with one O(5)Na2Ni4 octahedra, edges with two equivalent O(2)Na2Ni4 octahedra, edges with three equivalent O(1)Na2Ni4 octahedra, edges with three equivalent O(3)Na3Ni3 octahedra, and edges with three equivalent O(4)Na3Ni3 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.
Na2Ni3O5 is Caswellsilverite-like structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form NaO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. The Na(1)-O(2) bond length is 2.36 Å. The Na(1)-O(3) bond length is 2.31 Å. The Na(1)-O(4) bond length is 2.36 Å. The Na(1)-O(5) bond length is 2.32 Å. There is one shorter (2.25 Å) and one longer (2.35 Å) Na(1)-O(1) bond length. In the second Na site, Na(2) is bonded to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share  a cornercorner with one Ni(3)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-16°. The Na(2)-O(2) bond length is 2.30 Å. The Na(2)-O(5) bond length is 2.23 Å. There is one shorter (2.31 Å) and one longer (2.32 Å) Na(2)-O(3) bond length. There is one shorter (2.26 Å) and one longer (2.42 Å) Na(2)-O(4) bond length. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form NiO6 octahedra that share  a cornercorner with one Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with three equivalent Na(2)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-16°. The Ni(1)-O(1) bond length is 2.13 Å. The Ni(1)-O(3) bond length is 2.09 Å. The Ni(1)-O(4) bond length is 2.09 Å. The Ni(1)-O(5) bond length is 2.07 Å. There is one shorter (2.07 Å) and one longer (2.12 Å) Ni(1)-O(2) bond length. In the second Ni site, Ni(2) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form NiO6 octahedra that share  a cornercorner with one Ni(4)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with three equivalent Na(1)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one Ni(4)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-15°. The Ni(2)-O(1) bond length is 2.12 Å. The Ni(2)-O(4) bond length is 1.94 Å. Both Ni(2)-O(3) bond lengths are 1.94 Å. There is one shorter (1.92 Å) and one longer (2.29 Å) Ni(2)-O(5) bond length. In the third Ni site, Ni(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form NiO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-12°. Both Ni(3)-O(1) bond lengths are 1.91 Å. Both Ni(3)-O(2) bond lengths are 1.92 Å. Both Ni(3)-O(4) bond lengths are 1.94 Å. In the fourth Ni site, Ni(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(3)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-12°. Both Ni(4)-O(1) bond lengths are 2.13 Å. Both Ni(4)-O(2) bond lengths are 2.17 Å. Both Ni(4)-O(5) bond lengths are 2.14 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one Ni(1), one Ni(2), one Ni(3), and one Ni(4) atom to form ONa2Ni4 octahedra that share  a cornercorner with one O(5)Na2Ni4 octahedra,  a cornercorner with one O(3)Na3Ni3 octahedra, corners with two equivalent O(1)Na2Ni4 octahedra, corners with two equivalent O(4)Na3Ni3 octahedra,  an edgeedge with one O(1)Na2Ni4 octahedra, edges with two equivalent O(3)Na3Ni3 octahedra, edges with two equivalent O(4)Na3Ni3 octahedra, edges with three equivalent O(5)Na2Ni4 octahedra, and edges with four equivalent O(2)Na2Ni4 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Ni(3), one Ni(4), and two equivalent Ni(1) atoms to form ONa2Ni4 octahedra that share  a cornercorner with one O(3)Na3Ni3 octahedra,  a cornercorner with one O(4)Na3Ni3 octahedra, corners with two equivalent O(2)Na2Ni4 octahedra, corners with two equivalent O(5)Na2Ni4 octahedra,  an edgeedge with one O(2)Na2Ni4 octahedra, edges with two equivalent O(5)Na2Ni4 octahedra, edges with two equivalent O(3)Na3Ni3 octahedra, edges with three equivalent O(4)Na3Ni3 octahedra, and edges with four equivalent O(1)Na2Ni4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(2), one Ni(1), and two equivalent Ni(2) atoms to form ONa3Ni3 octahedra that share  a cornercorner with one O(1)Na2Ni4 octahedra,  a cornercorner with one O(2)Na2Ni4 octahedra, corners with two equivalent O(5)Na2Ni4 octahedra, corners with two equivalent O(4)Na3Ni3 octahedra, edges with two equivalent O(1)Na2Ni4 octahedra, edges with two equivalent O(2)Na2Ni4 octahedra, edges with two equivalent O(3)Na3Ni3 octahedra, edges with three equivalent O(5)Na2Ni4 octahedra, and edges with three equivalent O(4)Na3Ni3 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. In the fourth O site, O(4) is bonded to one Na(1), two equivalent Na(2), one Ni(1), one Ni(2), and one Ni(3) atom to form ONa3Ni3 octahedra that share  a cornercorner with one O(2)Na2Ni4 octahedra,  a cornercorner with one O(4)Na3Ni3 octahedra, corners with two equivalent O(1)Na2Ni4 octahedra, corners with two equivalent O(3)Na3Ni3 octahedra,  an edgeedge with one O(4)Na3Ni3 octahedra, edges with two equivalent O(1)Na2Ni4 octahedra, edges with three equivalent O(2)Na2Ni4 octahedra, edges with three equivalent O(5)Na2Ni4 octahedra, and edges with three equivalent O(3)Na3Ni3 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one Ni(1), one Ni(4), and two equivalent Ni(2) atoms to form ONa2Ni4 octahedra that share  a cornercorner with one O(1)Na2Ni4 octahedra,  a cornercorner with one O(5)Na2Ni4 octahedra, corners with two equivalent O(2)Na2Ni4 octahedra, corners with two equivalent O(3)Na3Ni3 octahedra,  an edgeedge with one O(5)Na2Ni4 octahedra, edges with two equivalent O(2)Na2Ni4 octahedra, edges with three equivalent O(1)Na2Ni4 octahedra, edges with three equivalent O(3)Na3Ni3 octahedra, and edges with three equivalent O(4)Na3Ni3 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.