Li4NbMn3O8 is Caswellsilverite-derived structured and crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(6), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)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 2-4°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. In the third Li site, Li(3) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(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 6-8°. Nb(1) is bonded to one O(4), one O(6), two equivalent O(2), and two equivalent O(5) atoms to form NbO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)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 2-4°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. In the second Mn site, Mn(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(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 6-8°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(2), one Mn(2), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with six equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn2Nb octahedra, edges with two equivalent O(6)Li3Mn2Nb octahedra, edges with four equivalent O(2)Li3Mn2Nb octahedra, and edges with four equivalent O(5)Li3Mn2Nb octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Nb(1), one Mn(1), and one Mn(2) atom to form OLi3Mn2Nb octahedra that share corners with six equivalent O(5)Li3Mn2Nb octahedra, edges with two equivalent O(2)Li3Mn2Nb octahedra, edges with two equivalent O(4)Li3Mn2Nb octahedra, edges with two equivalent O(5)Li3Mn2Nb octahedra, edges with two equivalent O(6)Li3Mn2Nb octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, and edges with two equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(2), one Mn(2), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with six equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn2Nb octahedra, edges with two equivalent O(6)Li3Mn2Nb octahedra, edges with four equivalent O(2)Li3Mn2Nb octahedra, and edges with four equivalent O(5)Li3Mn2Nb octahedra. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(2), one Nb(1), and two equivalent Mn(1) atoms to form OLi3Mn2Nb octahedra that share corners with six equivalent O(6)Li3Mn2Nb octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with four equivalent O(2)Li3Mn2Nb octahedra, and edges with four equivalent O(5)Li3Mn2Nb octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Li(3), one Nb(1), one Mn(1), and one Mn(2) atom to form OLi3Mn2Nb octahedra that share corners with six equivalent O(2)Li3Mn2Nb octahedra, edges with two equivalent O(2)Li3Mn2Nb octahedra, edges with two equivalent O(4)Li3Mn2Nb octahedra, edges with two equivalent O(5)Li3Mn2Nb octahedra, edges with two equivalent O(6)Li3Mn2Nb octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, and edges with two equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the sixth O site, O(6) is bonded to one Li(1), two equivalent Li(2), one Nb(1), and two equivalent Mn(1) atoms to form OLi3Mn2Nb octahedra that share corners with six equivalent O(4)Li3Mn2Nb octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with four equivalent O(2)Li3Mn2Nb octahedra, and edges with four equivalent O(5)Li3Mn2Nb octahedra. The corner-sharing octahedral tilt angles range from 0-3°.
Li4NbMn3O8 is Caswellsilverite-derived structured and crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(6), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)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 2-4°. The Li(1)-O(4) bond length is 2.33 Å. The Li(1)-O(6) bond length is 2.27 Å. Both Li(1)-O(2) bond lengths are 2.33 Å. Both Li(1)-O(5) bond lengths are 2.27 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. The Li(2)-O(1) bond length is 2.34 Å. The Li(2)-O(2) bond length is 2.14 Å. The Li(2)-O(3) bond length is 2.23 Å. The Li(2)-O(4) bond length is 2.14 Å. The Li(2)-O(5) bond length is 2.14 Å. The Li(2)-O(6) bond length is 2.14 Å. In the third Li site, Li(3) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(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 6-8°. The Li(3)-O(1) bond length is 2.23 Å. The Li(3)-O(3) bond length is 2.34 Å. Both Li(3)-O(2) bond lengths are 2.14 Å. Both Li(3)-O(5) bond lengths are 2.14 Å. Nb(1) is bonded to one O(4), one O(6), two equivalent O(2), and two equivalent O(5) atoms to form NbO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)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 2-4°. The Nb(1)-O(4) bond length is 2.06 Å. The Nb(1)-O(6) bond length is 2.06 Å. Both Nb(1)-O(2) bond lengths are 2.06 Å. Both Nb(1)-O(5) bond lengths are 2.06 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. The Mn(1)-O(1) bond length is 2.08 Å. The Mn(1)-O(2) bond length is 2.22 Å. The Mn(1)-O(3) bond length is 2.08 Å. The Mn(1)-O(4) bond length is 2.22 Å. The Mn(1)-O(5) bond length is 2.22 Å. The Mn(1)-O(6) bond length is 2.22 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(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 6-8°. The Mn(2)-O(1) bond length is 2.08 Å. The Mn(2)-O(3) bond length is 2.08 Å. Both Mn(2)-O(2) bond lengths are 2.22 Å. Both Mn(2)-O(5) bond lengths are 2.22 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(2), one Mn(2), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with six equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn2Nb octahedra, edges with two equivalent O(6)Li3Mn2Nb octahedra, edges with four equivalent O(2)Li3Mn2Nb octahedra, and edges with four equivalent O(5)Li3Mn2Nb octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Nb(1), one Mn(1), and one Mn(2) atom to form OLi3Mn2Nb octahedra that share corners with six equivalent O(5)Li3Mn2Nb octahedra, edges with two equivalent O(2)Li3Mn2Nb octahedra, edges with two equivalent O(4)Li3Mn2Nb octahedra, edges with two equivalent O(5)Li3Mn2Nb octahedra, edges with two equivalent O(6)Li3Mn2Nb octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, and edges with two equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(2), one Mn(2), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with six equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn2Nb octahedra, edges with two equivalent O(6)Li3Mn2Nb octahedra, edges with four equivalent O(2)Li3Mn2Nb octahedra, and edges with four equivalent O(5)Li3Mn2Nb octahedra. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(2), one Nb(1), and two equivalent Mn(1) atoms to form OLi3Mn2Nb octahedra that share corners with six equivalent O(6)Li3Mn2Nb octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with four equivalent O(2)Li3Mn2Nb octahedra, and edges with four equivalent O(5)Li3Mn2Nb octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Li(3), one Nb(1), one Mn(1), and one Mn(2) atom to form OLi3Mn2Nb octahedra that share corners with six equivalent O(2)Li3Mn2Nb octahedra, edges with two equivalent O(2)Li3Mn2Nb octahedra, edges with two equivalent O(4)Li3Mn2Nb octahedra, edges with two equivalent O(5)Li3Mn2Nb octahedra, edges with two equivalent O(6)Li3Mn2Nb octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, and edges with two equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the sixth O site, O(6) is bonded to one Li(1), two equivalent Li(2), one Nb(1), and two equivalent Mn(1) atoms to form OLi3Mn2Nb octahedra that share corners with six equivalent O(4)Li3Mn2Nb octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with four equivalent O(2)Li3Mn2Nb octahedra, and edges with four equivalent O(5)Li3Mn2Nb octahedra. The corner-sharing octahedral tilt angles range from 0-3°.