Li2MnNiO4 is Caswellsilverite-derived structured and crystallizes in the orthorhombic C222 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second Li site, Li(2) 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 Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second Mn site, Mn(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one Mn(2), and two equivalent Ni(1) atoms to form OLi3MnNi2 octahedra that share corners with two equivalent O(1)Li3MnNi2 octahedra, corners with four equivalent O(2)Li3MnNi2 octahedra, edges with two equivalent O(1)Li3MnNi2 octahedra, edges with two equivalent O(2)Li3MnNi2 octahedra, and edges with eight equivalent O(3)Li3Mn2Ni octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), one Mn(1), and two equivalent Ni(1) atoms to form OLi3MnNi2 octahedra that share corners with two equivalent O(2)Li3MnNi2 octahedra, corners with four equivalent O(1)Li3MnNi2 octahedra, edges with two equivalent O(1)Li3MnNi2 octahedra, edges with two equivalent O(2)Li3MnNi2 octahedra, and edges with eight equivalent O(3)Li3Mn2Ni octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(2), and one Ni(1) atom to form OLi3Mn2Ni octahedra that share corners with six equivalent O(3)Li3Mn2Ni octahedra, edges with four equivalent O(3)Li3Mn2Ni octahedra, edges with four equivalent O(1)Li3MnNi2 octahedra, and edges with four equivalent O(2)Li3MnNi2 octahedra. The corner-sharing octahedral tilt angles range from 2-5°.
Li2MnNiO4 is Caswellsilverite-derived structured and crystallizes in the orthorhombic C222 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. Both Li(1)-O(1) bond lengths are 2.39 Å. All Li(1)-O(3) bond lengths are 2.03 Å. In the second Li site, Li(2) 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 Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. Both Li(2)-O(2) bond lengths are 2.38 Å. All Li(2)-O(3) bond lengths are 2.03 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. Both Li(3)-O(1) bond lengths are 2.04 Å. Both Li(3)-O(2) bond lengths are 2.04 Å. Both Li(3)-O(3) bond lengths are 2.25 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Both Mn(1)-O(2) bond lengths are 1.93 Å. All Mn(1)-O(3) bond lengths are 1.95 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Both Mn(2)-O(1) bond lengths are 1.91 Å. All Mn(2)-O(3) bond lengths are 2.11 Å. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. Both Ni(1)-O(1) bond lengths are 2.05 Å. Both Ni(1)-O(2) bond lengths are 2.03 Å. Both Ni(1)-O(3) bond lengths are 2.06 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one Mn(2), and two equivalent Ni(1) atoms to form OLi3MnNi2 octahedra that share corners with two equivalent O(1)Li3MnNi2 octahedra, corners with four equivalent O(2)Li3MnNi2 octahedra, edges with two equivalent O(1)Li3MnNi2 octahedra, edges with two equivalent O(2)Li3MnNi2 octahedra, and edges with eight equivalent O(3)Li3Mn2Ni octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), one Mn(1), and two equivalent Ni(1) atoms to form OLi3MnNi2 octahedra that share corners with two equivalent O(2)Li3MnNi2 octahedra, corners with four equivalent O(1)Li3MnNi2 octahedra, edges with two equivalent O(1)Li3MnNi2 octahedra, edges with two equivalent O(2)Li3MnNi2 octahedra, and edges with eight equivalent O(3)Li3Mn2Ni octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(2), and one Ni(1) atom to form OLi3Mn2Ni octahedra that share corners with six equivalent O(3)Li3Mn2Ni octahedra, edges with four equivalent O(3)Li3Mn2Ni octahedra, edges with four equivalent O(1)Li3MnNi2 octahedra, and edges with four equivalent O(2)Li3MnNi2 octahedra. The corner-sharing octahedral tilt angles range from 2-5°.