NaNi5O6 is Caswellsilverite-like structured and crystallizes in the monoclinic C2 space group. Na(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form NaO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Ni(5)O6 octahedra,  a cornercorner with one Ni(6)O6 octahedra,  a cornercorner with one Ni(7)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one Ni(5)O6 octahedra,  an edgeedge with one Ni(6)O6 octahedra,  an edgeedge with one Ni(7)O6 octahedra, edges with three equivalent Ni(4)O6 octahedra, and edges with three equivalent Ni(8)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. There are eight inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with two equivalent Ni(8)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Ni(8)O6 octahedra, edges with three equivalent Ni(2)O6 octahedra, and edges with three equivalent Ni(7)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the second Ni site, Ni(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with two equivalent Ni(8)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Ni(8)O6 octahedra, edges with three equivalent Ni(1)O6 octahedra, and edges with three equivalent Ni(7)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. In the third Ni site, Ni(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with two equivalent Ni(8)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Ni(8)O6 octahedra, edges with three equivalent Ni(5)O6 octahedra, and edges with three equivalent Ni(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. In the fourth Ni site, Ni(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form NiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Ni(5)O6 octahedra,  a cornercorner with one Ni(6)O6 octahedra,  a cornercorner with one Ni(7)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one Ni(5)O6 octahedra,  an edgeedge with one Ni(6)O6 octahedra,  an edgeedge with one Ni(7)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Ni(8)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-11°. In the fifth Ni site, Ni(5) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with two equivalent Ni(8)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Ni(8)O6 octahedra, edges with three equivalent Ni(3)O6 octahedra, and edges with three equivalent Ni(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the sixth Ni site, Ni(6) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with two equivalent Ni(8)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Ni(8)O6 octahedra, edges with three equivalent Ni(3)O6 octahedra, and edges with three equivalent Ni(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. In the seventh Ni site, Ni(7) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with two equivalent Ni(8)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Ni(8)O6 octahedra, edges with three equivalent Ni(1)O6 octahedra, and edges with three equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. In the eighth Ni site, Ni(8) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form NiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Ni(5)O6 octahedra,  a cornercorner with one Ni(6)O6 octahedra,  a cornercorner with one Ni(7)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one Ni(5)O6 octahedra,  an edgeedge with one Ni(6)O6 octahedra,  an edgeedge with one Ni(7)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Ni(1), one Ni(2), one Ni(4), one Ni(7), and one Ni(8) atom to form a mixture of corner and edge-sharing ONaNi5 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 Ni(3), one Ni(4), one Ni(5), one Ni(6), and one Ni(8) atom to form a mixture of corner and edge-sharing ONaNi5 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. In the third O site, O(3) is bonded to one Na(1), one Ni(3), one Ni(4), one Ni(5), one Ni(6), and one Ni(8) atom to form a mixture of corner and edge-sharing ONaNi5 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the fourth O site, O(4) is bonded to one Na(1), one Ni(1), one Ni(2), one Ni(4), one Ni(7), and one Ni(8) atom to form a mixture of corner and edge-sharing ONaNi5 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the fifth O site, O(5) is bonded to one Na(1), one Ni(1), one Ni(2), one Ni(4), one Ni(7), and one Ni(8) atom to form a mixture of corner and edge-sharing ONaNi5 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the sixth O site, O(6) is bonded to one Na(1), one Ni(3), one Ni(4), one Ni(5), one Ni(6), and one Ni(8) atom to form a mixture of corner and edge-sharing ONaNi5 octahedra. The corner-sharing octahedral tilt angles range from 1-8°.
NaNi5O6 is Caswellsilverite-like structured and crystallizes in the monoclinic C2 space group. Na(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form NaO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Ni(5)O6 octahedra,  a cornercorner with one Ni(6)O6 octahedra,  a cornercorner with one Ni(7)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one Ni(5)O6 octahedra,  an edgeedge with one Ni(6)O6 octahedra,  an edgeedge with one Ni(7)O6 octahedra, edges with three equivalent Ni(4)O6 octahedra, and edges with three equivalent Ni(8)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. The Na(1)-O(1) bond length is 2.27 Å. The Na(1)-O(2) bond length is 2.27 Å. The Na(1)-O(3) bond length is 2.25 Å. The Na(1)-O(4) bond length is 2.24 Å. The Na(1)-O(5) bond length is 2.24 Å. The Na(1)-O(6) bond length is 2.30 Å. There are eight inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with two equivalent Ni(8)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Ni(8)O6 octahedra, edges with three equivalent Ni(2)O6 octahedra, and edges with three equivalent Ni(7)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. Both Ni(1)-O(1) bond lengths are 1.98 Å. Both Ni(1)-O(4) bond lengths are 2.14 Å. Both Ni(1)-O(5) bond lengths are 2.15 Å. In the second Ni site, Ni(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with two equivalent Ni(8)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Ni(8)O6 octahedra, edges with three equivalent Ni(1)O6 octahedra, and edges with three equivalent Ni(7)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. Both Ni(2)-O(1) bond lengths are 2.14 Å. Both Ni(2)-O(4) bond lengths are 2.15 Å. Both Ni(2)-O(5) bond lengths are 2.03 Å. In the third Ni site, Ni(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with two equivalent Ni(8)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Ni(8)O6 octahedra, edges with three equivalent Ni(5)O6 octahedra, and edges with three equivalent Ni(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. Both Ni(3)-O(2) bond lengths are 2.11 Å. Both Ni(3)-O(3) bond lengths are 2.00 Å. Both Ni(3)-O(6) bond lengths are 2.19 Å. In the fourth Ni site, Ni(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form NiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Ni(5)O6 octahedra,  a cornercorner with one Ni(6)O6 octahedra,  a cornercorner with one Ni(7)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one Ni(5)O6 octahedra,  an edgeedge with one Ni(6)O6 octahedra,  an edgeedge with one Ni(7)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Ni(8)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-11°. The Ni(4)-O(1) bond length is 2.12 Å. The Ni(4)-O(2) bond length is 2.14 Å. The Ni(4)-O(3) bond length is 2.09 Å. The Ni(4)-O(4) bond length is 2.11 Å. The Ni(4)-O(5) bond length is 2.09 Å. The Ni(4)-O(6) bond length is 2.13 Å. In the fifth Ni site, Ni(5) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with two equivalent Ni(8)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Ni(8)O6 octahedra, edges with three equivalent Ni(3)O6 octahedra, and edges with three equivalent Ni(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. Both Ni(5)-O(2) bond lengths are 2.03 Å. Both Ni(5)-O(3) bond lengths are 2.14 Å. Both Ni(5)-O(6) bond lengths are 2.15 Å. In the sixth Ni site, Ni(6) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with two equivalent Ni(8)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Ni(8)O6 octahedra, edges with three equivalent Ni(3)O6 octahedra, and edges with three equivalent Ni(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. Both Ni(6)-O(2) bond lengths are 2.01 Å. Both Ni(6)-O(3) bond lengths are 2.20 Å. Both Ni(6)-O(6) bond lengths are 1.94 Å. In the seventh Ni site, Ni(7) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ni(4)O6 octahedra, corners with two equivalent Ni(8)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ni(4)O6 octahedra, edges with two equivalent Ni(8)O6 octahedra, edges with three equivalent Ni(1)O6 octahedra, and edges with three equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. Both Ni(7)-O(1) bond lengths are 2.13 Å. Both Ni(7)-O(4) bond lengths are 2.03 Å. Both Ni(7)-O(5) bond lengths are 2.16 Å. In the eighth Ni site, Ni(8) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form NiO6 octahedra that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one Ni(5)O6 octahedra,  a cornercorner with one Ni(6)O6 octahedra,  a cornercorner with one Ni(7)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one Ni(5)O6 octahedra,  an edgeedge with one Ni(6)O6 octahedra,  an edgeedge with one Ni(7)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. The Ni(8)-O(1) bond length is 2.12 Å. The Ni(8)-O(2) bond length is 2.25 Å. The Ni(8)-O(3) bond length is 2.09 Å. The Ni(8)-O(4) bond length is 2.09 Å. The Ni(8)-O(5) bond length is 2.10 Å. The Ni(8)-O(6) bond length is 2.11 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Ni(1), one Ni(2), one Ni(4), one Ni(7), and one Ni(8) atom to form a mixture of corner and edge-sharing ONaNi5 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 Ni(3), one Ni(4), one Ni(5), one Ni(6), and one Ni(8) atom to form a mixture of corner and edge-sharing ONaNi5 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. In the third O site, O(3) is bonded to one Na(1), one Ni(3), one Ni(4), one Ni(5), one Ni(6), and one Ni(8) atom to form a mixture of corner and edge-sharing ONaNi5 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the fourth O site, O(4) is bonded to one Na(1), one Ni(1), one Ni(2), one Ni(4), one Ni(7), and one Ni(8) atom to form a mixture of corner and edge-sharing ONaNi5 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the fifth O site, O(5) is bonded to one Na(1), one Ni(1), one Ni(2), one Ni(4), one Ni(7), and one Ni(8) atom to form a mixture of corner and edge-sharing ONaNi5 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the sixth O site, O(6) is bonded to one Na(1), one Ni(3), one Ni(4), one Ni(5), one Ni(6), and one Ni(8) atom to form a mixture of corner and edge-sharing ONaNi5 octahedra. The corner-sharing octahedral tilt angles range from 1-8°.