Li3Mn2SbO6 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Sb(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Sb(1)O6 octahedra, corners with five equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-18°. Mn(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-18°. Sb(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form SbO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-8°. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), two equivalent Mn(1), and one Sb(1) atom to form OLi3Mn2Sb octahedra that share  a cornercorner with one O(1)Li3Mn2Sb octahedra,  a cornercorner with one O(3)Li3MnSb2 octahedra, corners with four equivalent O(2)Li3Mn3 octahedra, edges with four equivalent O(1)Li3Mn2Sb octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, and edges with four equivalent O(3)Li3MnSb2 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and three equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(3)Li3MnSb2 octahedra, corners with four equivalent O(1)Li3Mn2Sb octahedra, edges with four equivalent O(1)Li3Mn2Sb octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, and edges with four equivalent O(3)Li3MnSb2 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and two equivalent Sb(1) atoms to form OLi3MnSb2 octahedra that share  a cornercorner with one O(1)Li3Mn2Sb octahedra,  a cornercorner with one O(2)Li3Mn3 octahedra, corners with four equivalent O(3)Li3MnSb2 octahedra, edges with four equivalent O(1)Li3Mn2Sb octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, and edges with four equivalent O(3)Li3MnSb2 octahedra. The corner-sharing octahedral tilt angles range from 0-15°.
Li3Mn2SbO6 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Sb(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. Both Li(1)-O(2) bond lengths are 2.08 Å. All Li(1)-O(3) bond lengths are 2.39 Å. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Sb(1)O6 octahedra, corners with five equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-18°. The Li(2)-O(3) bond length is 2.11 Å. Both Li(2)-O(2) bond lengths are 2.11 Å. There are two shorter (2.40 Å) and one longer (2.41 Å) Li(2)-O(1) bond length. Mn(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-18°. The Mn(1)-O(3) bond length is 2.34 Å. Both Mn(1)-O(1) bond lengths are 2.29 Å. There is one shorter (2.15 Å) and two longer (2.18 Å) Mn(1)-O(2) bond lengths. Sb(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form SbO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-8°. Both Sb(1)-O(1) bond lengths are 1.96 Å. All Sb(1)-O(3) bond lengths are 2.09 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), two equivalent Mn(1), and one Sb(1) atom to form OLi3Mn2Sb octahedra that share  a cornercorner with one O(1)Li3Mn2Sb octahedra,  a cornercorner with one O(3)Li3MnSb2 octahedra, corners with four equivalent O(2)Li3Mn3 octahedra, edges with four equivalent O(1)Li3Mn2Sb octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, and edges with four equivalent O(3)Li3MnSb2 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and three equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(3)Li3MnSb2 octahedra, corners with four equivalent O(1)Li3Mn2Sb octahedra, edges with four equivalent O(1)Li3Mn2Sb octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, and edges with four equivalent O(3)Li3MnSb2 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and two equivalent Sb(1) atoms to form OLi3MnSb2 octahedra that share  a cornercorner with one O(1)Li3Mn2Sb octahedra,  a cornercorner with one O(2)Li3Mn3 octahedra, corners with four equivalent O(3)Li3MnSb2 octahedra, edges with four equivalent O(1)Li3Mn2Sb octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, and edges with four equivalent O(3)Li3MnSb2 octahedra. The corner-sharing octahedral tilt angles range from 0-15°.