Li4NbMn(WO6)2 is Ilmenite-derived structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(4), one O(7), one O(8), and one O(9) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(2), one O(3), one O(5), and one O(6) atom. In the third Li site, Li(3) is bonded to one O(10), one O(2), one O(5), one O(6), one O(8), and one O(9) atom to form distorted LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Nb(1)O6 octahedra,  an edgeedge with one W(1)O6 octahedra, edges with two equivalent W(2)O6 octahedra, and  a faceface with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-64°. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one O(1), one O(11), one O(3), and one O(7) atom. Nb(1) is bonded to one O(1), one O(12), one O(4), one O(6), one O(7), and one O(9) atom to form NbO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent W(2)O6 octahedra, and corners with four equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-64°. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(1), one O(11), one O(12), one O(2), one O(4), and one O(9) atom to form WO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Nb(1)O6 octahedra, and  an edgeedge with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-42°. In the second W site, W(2) is bonded to one O(10), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form WO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, and edges with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-38°. Mn(1) is bonded to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent W(1)O6 octahedra, corners with four equivalent W(2)O6 octahedra, and  a faceface with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-64°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one Nb(1), and one W(1) atom to form a mixture of distorted corner and edge-sharing OLi2NbW tetrahedra. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one W(1), and one Mn(1) atom. In the third O site, O(3) is bonded to one Li(2), one Li(4), one W(2), and one Mn(1) atom to form distorted OLi2MnW tetrahedra that share  a cornercorner with one O(1)Li2NbW tetrahedra and corners with two equivalent O(11)Li2MnW tetrahedra. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Nb(1), and one W(1) atom. In the fifth O site, O(5) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one W(2), and one Mn(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Nb(1), and one W(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(4), one Nb(1), and one W(2) atom. In the eighth O site, O(8) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one W(2), and one Mn(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Nb(1), and one W(1) atom. In the tenth O site, O(10) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one W(2), and one Mn(1) atom. In the eleventh O site, O(11) is bonded to one Li(1), one Li(4), one W(1), and one Mn(1) atom to form distorted OLi2MnW tetrahedra that share  a cornercorner with one O(1)Li2NbW tetrahedra, corners with two equivalent O(3)Li2MnW tetrahedra, and  an edgeedge with one O(1)Li2NbW tetrahedra. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(2), one Nb(1), and one W(1) atom.
Li4NbMn(WO6)2 is Ilmenite-derived structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(4), one O(7), one O(8), and one O(9) atom. The Li(1)-O(1) bond length is 2.30 Å. The Li(1)-O(11) bond length is 2.12 Å. The Li(1)-O(4) bond length is 2.10 Å. The Li(1)-O(7) bond length is 2.07 Å. The Li(1)-O(8) bond length is 2.04 Å. The Li(1)-O(9) bond length is 2.47 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(2), one O(3), one O(5), and one O(6) atom. The Li(2)-O(10) bond length is 2.01 Å. The Li(2)-O(12) bond length is 2.14 Å. The Li(2)-O(2) bond length is 2.03 Å. The Li(2)-O(3) bond length is 2.26 Å. The Li(2)-O(5) bond length is 2.32 Å. The Li(2)-O(6) bond length is 2.40 Å. In the third Li site, Li(3) is bonded to one O(10), one O(2), one O(5), one O(6), one O(8), and one O(9) atom to form distorted LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Nb(1)O6 octahedra,  an edgeedge with one W(1)O6 octahedra, edges with two equivalent W(2)O6 octahedra, and  a faceface with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-64°. The Li(3)-O(10) bond length is 2.20 Å. The Li(3)-O(2) bond length is 2.25 Å. The Li(3)-O(5) bond length is 2.08 Å. The Li(3)-O(6) bond length is 2.07 Å. The Li(3)-O(8) bond length is 2.24 Å. The Li(3)-O(9) bond length is 2.09 Å. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one O(1), one O(11), one O(3), and one O(7) atom. The Li(4)-O(1) bond length is 2.01 Å. The Li(4)-O(11) bond length is 1.97 Å. The Li(4)-O(3) bond length is 2.00 Å. The Li(4)-O(7) bond length is 2.52 Å. Nb(1) is bonded to one O(1), one O(12), one O(4), one O(6), one O(7), and one O(9) atom to form NbO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent W(2)O6 octahedra, and corners with four equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-64°. The Nb(1)-O(1) bond length is 1.93 Å. The Nb(1)-O(12) bond length is 2.08 Å. The Nb(1)-O(4) bond length is 2.13 Å. The Nb(1)-O(6) bond length is 1.89 Å. The Nb(1)-O(7) bond length is 2.23 Å. The Nb(1)-O(9) bond length is 1.91 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(1), one O(11), one O(12), one O(2), one O(4), and one O(9) atom to form WO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Nb(1)O6 octahedra, and  an edgeedge with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-42°. The W(1)-O(1) bond length is 2.08 Å. The W(1)-O(11) bond length is 1.91 Å. The W(1)-O(12) bond length is 1.90 Å. The W(1)-O(2) bond length is 1.88 Å. The W(1)-O(4) bond length is 1.89 Å. The W(1)-O(9) bond length is 2.09 Å. In the second W site, W(2) is bonded to one O(10), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form WO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, and edges with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-38°. The W(2)-O(10) bond length is 1.93 Å. The W(2)-O(3) bond length is 1.95 Å. The W(2)-O(5) bond length is 1.96 Å. The W(2)-O(6) bond length is 2.14 Å. The W(2)-O(7) bond length is 1.87 Å. The W(2)-O(8) bond length is 1.92 Å. Mn(1) is bonded to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent W(1)O6 octahedra, corners with four equivalent W(2)O6 octahedra, and  a faceface with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-64°. The Mn(1)-O(10) bond length is 2.02 Å. The Mn(1)-O(11) bond length is 2.16 Å. The Mn(1)-O(2) bond length is 2.23 Å. The Mn(1)-O(3) bond length is 1.96 Å. The Mn(1)-O(5) bond length is 1.95 Å. The Mn(1)-O(8) bond length is 2.02 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one Nb(1), and one W(1) atom to form a mixture of distorted corner and edge-sharing OLi2NbW tetrahedra. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one W(1), and one Mn(1) atom. In the third O site, O(3) is bonded to one Li(2), one Li(4), one W(2), and one Mn(1) atom to form distorted OLi2MnW tetrahedra that share  a cornercorner with one O(1)Li2NbW tetrahedra and corners with two equivalent O(11)Li2MnW tetrahedra. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Nb(1), and one W(1) atom. In the fifth O site, O(5) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one W(2), and one Mn(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Nb(1), and one W(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(4), one Nb(1), and one W(2) atom. In the eighth O site, O(8) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one W(2), and one Mn(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Nb(1), and one W(1) atom. In the tenth O site, O(10) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one W(2), and one Mn(1) atom. In the eleventh O site, O(11) is bonded to one Li(1), one Li(4), one W(1), and one Mn(1) atom to form distorted OLi2MnW tetrahedra that share  a cornercorner with one O(1)Li2NbW tetrahedra, corners with two equivalent O(3)Li2MnW tetrahedra, and  an edgeedge with one O(1)Li2NbW tetrahedra. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(2), one Nb(1), and one W(1) atom.