Na3Mn2SbO6 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 Mn(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and edges with six equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. 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 Mn(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 Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. Mn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 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 Mn(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 13-14°. 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 Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. 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 Mn(1), and one Sb(1) atom to form a mixture of edge and corner-sharing ONa3Mn2Sb octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), two equivalent Mn(1), and one Sb(1) atom to form a mixture of edge and corner-sharing ONa3Mn2Sb octahedra. The corner-sharing octahedral tilt angles range from 0-8°.
Na3Mn2SbO6 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 Mn(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and edges with six equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. Both Na(1)-O(1) bond lengths are 2.59 Å. All Na(1)-O(2) bond lengths are 2.39 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 Mn(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 Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. Both Na(2)-O(1) bond lengths are 2.43 Å. There are two shorter (2.40 Å) and two longer (2.53 Å) Na(2)-O(2) bond lengths. Mn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 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 Mn(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 13-14°. Both Mn(1)-O(1) bond lengths are 2.24 Å. There are two shorter (2.25 Å) and two longer (2.26 Å) Mn(1)-O(2) bond lengths. 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 Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. Both Sb(1)-O(1) bond lengths are 2.04 Å. All Sb(1)-O(2) bond lengths are 2.05 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 Mn(1), and one Sb(1) atom to form a mixture of edge and corner-sharing ONa3Mn2Sb octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), two equivalent Mn(1), and one Sb(1) atom to form a mixture of edge and corner-sharing ONa3Mn2Sb octahedra. The corner-sharing octahedral tilt angles range from 0-8°.