Li6Nb3V3O16 is Hausmannite-derived structured and crystallizes in the monoclinic Cm space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Nb(2)O6 octahedra, corners with three equivalent Li(6)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-58°. In the second Li site, Li(2) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-59°. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(5), one O(7), and two equivalent O(11) atoms. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms. In the sixth Li site, Li(6) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, corners with three equivalent Li(1)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-72°. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form NbO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. In the second Nb site, Nb(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form NbO6 octahedra that share corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one Li(6)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, edges with two equivalent Nb(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-58°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one Li(6)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and edges with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. In the second V site, V(2) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one Nb(2), and one V(1) atom to form OLi2NbV trigonal pyramids that share  a cornercorner with one O(2)Li2V2 tetrahedra,  a cornercorner with one O(4)LiNbV2 tetrahedra, corners with three equivalent O(9)Li2NbV tetrahedra,  a cornercorner with one O(1)Li2NbV trigonal pyramid, and  an edgeedge with one O(1)Li2NbV trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Li(6), and two equivalent V(2) atoms to form OLi2V2 tetrahedra that share corners with two equivalent O(4)LiNbV2 tetrahedra, corners with two equivalent O(1)Li2NbV trigonal pyramids, and corners with two equivalent O(7)Li2V2 trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(1), and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded to one Li(4), one Nb(1), and two equivalent V(2) atoms to form distorted OLiNbV2 tetrahedra that share corners with two equivalent O(2)Li2V2 tetrahedra, corners with two equivalent O(1)Li2NbV trigonal pyramids, and  an edgeedge with one O(7)Li2V2 trigonal pyramid. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), two equivalent Nb(2), and one V(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(6), one Nb(1), and one V(2) atom. In the seventh O site, O(7) is bonded to one Li(3), one Li(5), and two equivalent V(2) atoms to form OLi2V2 trigonal pyramids that share corners with two equivalent O(9)Li2NbV tetrahedra, corners with two equivalent O(2)Li2V2 tetrahedra, and  an edgeedge with one O(4)LiNbV2 tetrahedra. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), and two equivalent Nb(2) atoms. In the ninth O site, O(9) is bonded to one Li(2), one Li(5), one Nb(2), and one V(1) atom to form distorted OLi2NbV tetrahedra that share  a cornercorner with one O(9)Li2NbV tetrahedra,  a cornercorner with one O(7)Li2V2 trigonal pyramid, corners with three equivalent O(1)Li2NbV trigonal pyramids, and  an edgeedge with one O(9)Li2NbV tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(6), two equivalent Nb(2), and one V(1) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one Nb(1), and one V(2) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(2), one Li(5), and two equivalent Nb(2) atoms.
Li6Nb3V3O16 is Hausmannite-derived structured and crystallizes in the monoclinic Cm space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Nb(2)O6 octahedra, corners with three equivalent Li(6)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-58°. The Li(1)-O(2) bond length is 2.36 Å. The Li(1)-O(8) bond length is 2.25 Å. Both Li(1)-O(1) bond lengths are 2.13 Å. Both Li(1)-O(6) bond lengths are 2.47 Å. In the second Li site, Li(2) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-59°. The Li(2)-O(12) bond length is 2.04 Å. The Li(2)-O(3) bond length is 2.13 Å. Both Li(2)-O(9) bond lengths are 2.02 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(5), one O(7), and two equivalent O(11) atoms. The Li(3)-O(5) bond length is 1.82 Å. The Li(3)-O(7) bond length is 1.92 Å. Both Li(3)-O(11) bond lengths are 1.96 Å. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. The Li(4)-O(4) bond length is 1.83 Å. The Li(4)-O(8) bond length is 2.05 Å. Both Li(4)-O(1) bond lengths are 1.93 Å. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms. The Li(5)-O(12) bond length is 2.56 Å. The Li(5)-O(7) bond length is 2.13 Å. Both Li(5)-O(11) bond lengths are 2.18 Å. Both Li(5)-O(9) bond lengths are 2.47 Å. In the sixth Li site, Li(6) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, corners with three equivalent Li(1)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-72°. The Li(6)-O(10) bond length is 2.18 Å. The Li(6)-O(2) bond length is 2.08 Å. Both Li(6)-O(6) bond lengths are 2.00 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form NbO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The Nb(1)-O(3) bond length is 2.10 Å. The Nb(1)-O(4) bond length is 2.01 Å. Both Nb(1)-O(11) bond lengths are 2.14 Å. Both Nb(1)-O(6) bond lengths are 1.91 Å. In the second Nb site, Nb(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form NbO6 octahedra that share corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one Li(6)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, edges with two equivalent Nb(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-58°. The Nb(2)-O(1) bond length is 2.02 Å. The Nb(2)-O(10) bond length is 2.03 Å. The Nb(2)-O(12) bond length is 2.01 Å. The Nb(2)-O(5) bond length is 2.08 Å. The Nb(2)-O(8) bond length is 2.03 Å. The Nb(2)-O(9) bond length is 1.96 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one Li(6)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and edges with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. The V(1)-O(10) bond length is 2.15 Å. The V(1)-O(5) bond length is 2.10 Å. Both V(1)-O(1) bond lengths are 2.01 Å. Both V(1)-O(9) bond lengths are 2.04 Å. In the second V site, V(2) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The V(2)-O(11) bond length is 1.87 Å. The V(2)-O(2) bond length is 1.92 Å. The V(2)-O(3) bond length is 2.03 Å. The V(2)-O(4) bond length is 2.09 Å. The V(2)-O(6) bond length is 2.08 Å. The V(2)-O(7) bond length is 1.99 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(2), and one V(1) atom to form OLi2NbV trigonal pyramids that share  a cornercorner with one O(2)Li2V2 tetrahedra,  a cornercorner with one O(4)LiNbV2 tetrahedra, corners with three equivalent O(9)Li2NbV tetrahedra,  a cornercorner with one O(1)Li2NbV trigonal pyramid, and  an edgeedge with one O(1)Li2NbV trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Li(6), and two equivalent V(2) atoms to form OLi2V2 tetrahedra that share corners with two equivalent O(4)LiNbV2 tetrahedra, corners with two equivalent O(1)Li2NbV trigonal pyramids, and corners with two equivalent O(7)Li2V2 trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(1), and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded to one Li(4), one Nb(1), and two equivalent V(2) atoms to form distorted OLiNbV2 tetrahedra that share corners with two equivalent O(2)Li2V2 tetrahedra, corners with two equivalent O(1)Li2NbV trigonal pyramids, and  an edgeedge with one O(7)Li2V2 trigonal pyramid. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), two equivalent Nb(2), and one V(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(6), one Nb(1), and one V(2) atom. In the seventh O site, O(7) is bonded to one Li(3), one Li(5), and two equivalent V(2) atoms to form OLi2V2 trigonal pyramids that share corners with two equivalent O(9)Li2NbV tetrahedra, corners with two equivalent O(2)Li2V2 tetrahedra, and  an edgeedge with one O(4)LiNbV2 tetrahedra. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), and two equivalent Nb(2) atoms. In the ninth O site, O(9) is bonded to one Li(2), one Li(5), one Nb(2), and one V(1) atom to form distorted OLi2NbV tetrahedra that share  a cornercorner with one O(9)Li2NbV tetrahedra,  a cornercorner with one O(7)Li2V2 trigonal pyramid, corners with three equivalent O(1)Li2NbV trigonal pyramids, and  an edgeedge with one O(9)Li2NbV tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(6), two equivalent Nb(2), and one V(1) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one Nb(1), and one V(2) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(2), one Li(5), and two equivalent Nb(2) atoms.