Li4VMn(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 in a 6-coordinate geometry to one O(10), one O(2), one O(5), one O(6), one O(8), and one O(9) atom. In the fourth Li site, Li(4) is bonded to one O(1), one O(11), one O(12), one O(3), one O(4), and one O(7) atom to form distorted LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra,  an edgeedge with one W(2)O6 octahedra, edges with two equivalent W(1)O6 octahedra, and  a faceface with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 62°. V(1) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(8) atom. 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 distorted WO6 octahedra that share corners with four equivalent Mn(1)O6 octahedra and edges with two equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-42°. 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 Mn(1)O6 octahedra and  an edgeedge with one Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-42°. Mn(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 MnO6 octahedra that share  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent W(2)O6 octahedra, corners with four equivalent W(1)O6 octahedra, and  a faceface with one Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-62°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one W(1), and one Mn(1) atom to form distorted corner-sharing OLi2MnW trigonal pyramids. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(1), and one W(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one V(1), and one W(2) atom. In the fourth O site, O(4) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(4), one W(1), and one Mn(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one W(2) atom. In the sixth O site, O(6) is bonded to one Li(2), one Li(3), one W(2), and one Mn(1) atom to form distorted corner-sharing OLi2MnW trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(4), one W(2), and one Mn(1) 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 V(1), and one W(2) atom. In the ninth O site, O(9) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one W(1), and one Mn(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 V(1), and one W(2) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(1), one Li(4), one V(1), and one W(1) atom. In the twelfth O site, O(12) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(4), one W(1), and one Mn(1) atom.
Li4VMn(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 2.29 Å. The Li(1)-O(11) bond length is 2.33 Å. The Li(1)-O(4) bond length is 2.00 Å. The Li(1)-O(7) bond length is 2.03 Å. The Li(1)-O(8) bond length is 2.12 Å. The Li(1)-O(9) bond length is 2.26 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 2.07 Å. The Li(2)-O(12) bond length is 2.05 Å. The Li(2)-O(2) bond length is 2.05 Å. The Li(2)-O(3) bond length is 2.49 Å. The Li(2)-O(5) bond length is 2.21 Å. The Li(2)-O(6) bond length is 2.09 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(10), one O(2), one O(5), one O(6), one O(8), and one O(9) atom. The Li(3)-O(10) bond length is 2.41 Å. The Li(3)-O(2) bond length is 2.39 Å. The Li(3)-O(5) bond length is 2.06 Å. The Li(3)-O(6) bond length is 2.00 Å. The Li(3)-O(8) bond length is 2.49 Å. The Li(3)-O(9) bond length is 2.05 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(11), one O(12), one O(3), one O(4), and one O(7) atom to form distorted LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra,  an edgeedge with one W(2)O6 octahedra, edges with two equivalent W(1)O6 octahedra, and  a faceface with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 62°. The Li(4)-O(1) bond length is 2.04 Å. The Li(4)-O(11) bond length is 2.08 Å. The Li(4)-O(12) bond length is 2.23 Å. The Li(4)-O(3) bond length is 2.09 Å. The Li(4)-O(4) bond length is 2.18 Å. The Li(4)-O(7) bond length is 2.17 Å. V(1) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(8) atom. The V(1)-O(10) bond length is 2.10 Å. The V(1)-O(11) bond length is 1.73 Å. The V(1)-O(2) bond length is 2.30 Å. The V(1)-O(3) bond length is 1.76 Å. The V(1)-O(5) bond length is 1.78 Å. The V(1)-O(8) bond length is 2.03 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 distorted WO6 octahedra that share corners with four equivalent Mn(1)O6 octahedra and edges with two equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-42°. The W(1)-O(1) bond length is 1.96 Å. The W(1)-O(11) bond length is 2.27 Å. The W(1)-O(12) bond length is 1.92 Å. The W(1)-O(2) bond length is 1.83 Å. The W(1)-O(4) bond length is 1.92 Å. The W(1)-O(9) bond length is 1.94 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 Mn(1)O6 octahedra and  an edgeedge with one Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-42°. The W(2)-O(10) bond length is 1.86 Å. The W(2)-O(3) bond length is 2.16 Å. The W(2)-O(5) bond length is 2.16 Å. The W(2)-O(6) bond length is 1.91 Å. The W(2)-O(7) bond length is 1.87 Å. The W(2)-O(8) bond length is 1.87 Å. Mn(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 MnO6 octahedra that share  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent W(2)O6 octahedra, corners with four equivalent W(1)O6 octahedra, and  a faceface with one Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-62°. The Mn(1)-O(1) bond length is 1.94 Å. The Mn(1)-O(12) bond length is 1.99 Å. The Mn(1)-O(4) bond length is 2.00 Å. The Mn(1)-O(6) bond length is 2.17 Å. The Mn(1)-O(7) bond length is 2.23 Å. The Mn(1)-O(9) bond length is 1.95 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one W(1), and one Mn(1) atom to form distorted corner-sharing OLi2MnW trigonal pyramids. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(1), and one W(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one V(1), and one W(2) atom. In the fourth O site, O(4) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(4), one W(1), and one Mn(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one W(2) atom. In the sixth O site, O(6) is bonded to one Li(2), one Li(3), one W(2), and one Mn(1) atom to form distorted corner-sharing OLi2MnW trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(4), one W(2), and one Mn(1) 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 V(1), and one W(2) atom. In the ninth O site, O(9) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one W(1), and one Mn(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 V(1), and one W(2) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(1), one Li(4), one V(1), and one W(1) atom. In the twelfth O site, O(12) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(4), one W(1), and one Mn(1) atom.