Na3Ni2SbO6 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with four equivalent Ni(1)O6 octahedra, and edges with six equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. In the second Na site, Na(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. Ni(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with three equivalent Ni(1)O6 octahedra, edges with three equivalent Sb(1)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-12°. Sb(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form SbO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with six equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), two equivalent Na(2), two equivalent Ni(1), and one Sb(1) atom to form a mixture of corner and edge-sharing ONa3Ni2Sb octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), two equivalent Ni(1), and one Sb(1) atom to form a mixture of corner and edge-sharing ONa3Ni2Sb octahedra. The corner-sharing octahedral tilt angles range from 0-7°.
Na3Ni2SbO6 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with four equivalent Ni(1)O6 octahedra, and edges with six equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. Both Na(1)-O(1) bond lengths are 2.46 Å. All Na(1)-O(2) bond lengths are 2.37 Å. In the second Na site, Na(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. Both Na(2)-O(1) bond lengths are 2.42 Å. There are two shorter (2.37 Å) and two longer (2.41 Å) Na(2)-O(2) bond lengths. Ni(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with three equivalent Ni(1)O6 octahedra, edges with three equivalent Sb(1)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-12°. Both Ni(1)-O(1) bond lengths are 2.13 Å. All Ni(1)-O(2) bond lengths are 2.14 Å. Sb(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form SbO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with six equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. Both Sb(1)-O(1) bond lengths are 2.03 Å. All Sb(1)-O(2) bond lengths are 2.03 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), two equivalent Na(2), two equivalent Ni(1), and one Sb(1) atom to form a mixture of corner and edge-sharing ONa3Ni2Sb octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), two equivalent Ni(1), and one Sb(1) atom to form a mixture of corner and edge-sharing ONa3Ni2Sb octahedra. The corner-sharing octahedral tilt angles range from 0-7°.