Li3MnO4 is Caswellsilverite-like structured and crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)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 7-10°. In the second Li site, Li(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the third Li site, Li(3) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)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 7-10°. Mn(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with six equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with four equivalent O(2)Li5Mn octahedra, and edges with four equivalent O(4)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Mn(1) atom to form OLi5Mn octahedra that share corners with six equivalent O(4)Li5Mn octahedra, edges with two equivalent O(2)Li5Mn octahedra, edges with two equivalent O(4)Li5Mn octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, and edges with four equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Li(1), one Li(3), two equivalent Li(2), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with six equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with four equivalent O(2)Li5Mn octahedra, and edges with four equivalent O(4)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Mn(1) atom to form OLi5Mn octahedra that share corners with six equivalent O(2)Li5Mn octahedra, edges with two equivalent O(2)Li5Mn octahedra, edges with two equivalent O(4)Li5Mn octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, and edges with four equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.
Li3MnO4 is Caswellsilverite-like structured and crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)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 7-10°. The Li(1)-O(1) bond length is 2.05 Å. The Li(1)-O(3) bond length is 2.08 Å. There is one shorter (2.06 Å) and one longer (2.09 Å) Li(1)-O(2) bond length. There is one shorter (2.03 Å) and one longer (2.07 Å) Li(1)-O(4) bond length. In the second Li site, Li(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. The Li(2)-O(2) bond length is 2.24 Å. The Li(2)-O(4) bond length is 2.24 Å. There is one shorter (2.14 Å) and one longer (2.20 Å) Li(2)-O(1) bond length. There is one shorter (2.15 Å) and one longer (2.17 Å) Li(2)-O(3) bond length. In the third Li site, Li(3) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)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 7-10°. The Li(3)-O(1) bond length is 2.08 Å. The Li(3)-O(3) bond length is 2.10 Å. There is one shorter (2.05 Å) and one longer (2.06 Å) Li(3)-O(2) bond length. There is one shorter (2.04 Å) and one longer (2.08 Å) Li(3)-O(4) bond length. Mn(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. The Mn(1)-O(2) bond length is 1.90 Å. The Mn(1)-O(4) bond length is 1.90 Å. Both Mn(1)-O(1) bond lengths are 1.94 Å. Both Mn(1)-O(3) bond lengths are 1.95 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with six equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with four equivalent O(2)Li5Mn octahedra, and edges with four equivalent O(4)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Mn(1) atom to form OLi5Mn octahedra that share corners with six equivalent O(4)Li5Mn octahedra, edges with two equivalent O(2)Li5Mn octahedra, edges with two equivalent O(4)Li5Mn octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, and edges with four equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Li(1), one Li(3), two equivalent Li(2), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with six equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with four equivalent O(2)Li5Mn octahedra, and edges with four equivalent O(4)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Mn(1) atom to form OLi5Mn octahedra that share corners with six equivalent O(2)Li5Mn octahedra, edges with two equivalent O(2)Li5Mn octahedra, edges with two equivalent O(4)Li5Mn octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, and edges with four equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.