LiMnO2 is Caswellsilverite-like structured and crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and three equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Mn(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with six equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), and three equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second Mn site, Mn(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and edges with six equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with four equivalent O(4)Li4Mn2 octahedra, edges with two equivalent O(3)Li2Mn4 octahedra, edges with four equivalent O(4)Li4Mn2 octahedra, and edges with six equivalent O(2)Li2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Mn(2), and three equivalent Mn(1) atoms to form OLi2Mn4 octahedra that share corners with two equivalent O(2)Li2Mn4 octahedra, corners with two equivalent O(3)Li2Mn4 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent O(3)Li2Mn4 octahedra, edges with three equivalent O(2)Li2Mn4 octahedra, edges with three equivalent O(1)Li4Mn2 octahedra, and edges with four equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the third O site, O(3) is bonded to two equivalent Li(1), two equivalent Mn(1), and two equivalent Mn(2) atoms to form OLi2Mn4 octahedra that share corners with two equivalent O(3)Li2Mn4 octahedra, corners with four equivalent O(2)Li2Mn4 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with four equivalent O(2)Li2Mn4 octahedra, and edges with six equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. In the fourth O site, O(4) is bonded to one Li(2), three equivalent Li(1), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share corners with two equivalent O(2)Li2Mn4 octahedra, corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with three equivalent O(3)Li2Mn4 octahedra, edges with three equivalent O(4)Li4Mn2 octahedra, and edges with four equivalent O(2)Li2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 1-5°.
LiMnO2 is Caswellsilverite-like structured and crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and three equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Mn(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. The Li(1)-O(1) bond length is 2.25 Å. The Li(1)-O(2) bond length is 2.02 Å. The Li(1)-O(3) bond length is 2.13 Å. There is one shorter (2.13 Å) and two longer (2.15 Å) Li(1)-O(4) bond lengths. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with six equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. Both Li(2)-O(1) bond lengths are 2.16 Å. Both Li(2)-O(2) bond lengths are 2.10 Å. Both Li(2)-O(4) bond lengths are 2.05 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), and three equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. The Mn(1)-O(1) bond length is 1.95 Å. The Mn(1)-O(3) bond length is 2.04 Å. The Mn(1)-O(4) bond length is 1.93 Å. There is one shorter (2.03 Å) and two longer (2.15 Å) Mn(1)-O(2) bond lengths. In the second Mn site, Mn(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and edges with six equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. Both Mn(2)-O(2) bond lengths are 2.26 Å. Both Mn(2)-O(3) bond lengths are 2.16 Å. Both Mn(2)-O(4) bond lengths are 2.03 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with four equivalent O(4)Li4Mn2 octahedra, edges with two equivalent O(3)Li2Mn4 octahedra, edges with four equivalent O(4)Li4Mn2 octahedra, and edges with six equivalent O(2)Li2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Mn(2), and three equivalent Mn(1) atoms to form OLi2Mn4 octahedra that share corners with two equivalent O(2)Li2Mn4 octahedra, corners with two equivalent O(3)Li2Mn4 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent O(3)Li2Mn4 octahedra, edges with three equivalent O(2)Li2Mn4 octahedra, edges with three equivalent O(1)Li4Mn2 octahedra, and edges with four equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the third O site, O(3) is bonded to two equivalent Li(1), two equivalent Mn(1), and two equivalent Mn(2) atoms to form OLi2Mn4 octahedra that share corners with two equivalent O(3)Li2Mn4 octahedra, corners with four equivalent O(2)Li2Mn4 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with four equivalent O(2)Li2Mn4 octahedra, and edges with six equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. In the fourth O site, O(4) is bonded to one Li(2), three equivalent Li(1), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share corners with two equivalent O(2)Li2Mn4 octahedra, corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with three equivalent O(3)Li2Mn4 octahedra, edges with three equivalent O(4)Li4Mn2 octahedra, and edges with four equivalent O(2)Li2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 1-5°.