Li3NbOF6 crystallizes in the orthorhombic P2_12_12_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 7-coordinate geometry to one O(1), one F(2), one F(4), two equivalent F(1), and two equivalent F(6) atoms. In the second Li site, Li(2) is bonded in a 7-coordinate geometry to one O(1), one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom. In the third Li site, Li(3) is bonded in a 7-coordinate geometry to one O(1), one F(2), one F(4), two equivalent F(3), and two equivalent F(5) atoms. Nb(1) is bonded in a pentagonal bipyramidal geometry to one O(1), one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom. O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Nb(1) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and one Nb(1) atom to form a mixture of corner and edge-sharing FLi3Nb tetrahedra. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Nb(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Li(3), and one Nb(1) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), and one Nb(1) atom to form a mixture of distorted corner and edge-sharing FLi3Nb trigonal pyramids. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(3), and one Nb(1) atom to form a mixture of distorted corner and edge-sharing FLi3Nb tetrahedra. In the sixth F site, F(6) is bonded to one Li(2), two equivalent Li(1), and one Nb(1) atom to form a mixture of distorted corner and edge-sharing FLi3Nb tetrahedra.
Li3NbOF6 crystallizes in the orthorhombic P2_12_12_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 7-coordinate geometry to one O(1), one F(2), one F(4), two equivalent F(1), and two equivalent F(6) atoms. The Li(1)-O(1) bond length is 2.37 Å. The Li(1)-F(2) bond length is 2.49 Å. The Li(1)-F(4) bond length is 2.29 Å. There is one shorter (2.05 Å) and one longer (2.19 Å) Li(1)-F(1) bond length. There is one shorter (1.99 Å) and one longer (2.42 Å) Li(1)-F(6) bond length. In the second Li site, Li(2) is bonded in a 7-coordinate geometry to one O(1), one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom. The Li(2)-O(1) bond length is 2.07 Å. The Li(2)-F(1) bond length is 2.24 Å. The Li(2)-F(2) bond length is 1.94 Å. The Li(2)-F(3) bond length is 2.53 Å. The Li(2)-F(4) bond length is 2.16 Å. The Li(2)-F(5) bond length is 2.39 Å. The Li(2)-F(6) bond length is 2.27 Å. In the third Li site, Li(3) is bonded in a 7-coordinate geometry to one O(1), one F(2), one F(4), two equivalent F(3), and two equivalent F(5) atoms. The Li(3)-O(1) bond length is 2.54 Å. The Li(3)-F(2) bond length is 2.24 Å. The Li(3)-F(4) bond length is 2.41 Å. There is one shorter (2.02 Å) and one longer (2.28 Å) Li(3)-F(3) bond length. There is one shorter (2.06 Å) and one longer (2.11 Å) Li(3)-F(5) bond length. Nb(1) is bonded in a pentagonal bipyramidal geometry to one O(1), one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom. The Nb(1)-O(1) bond length is 1.77 Å. The Nb(1)-F(1) bond length is 2.09 Å. The Nb(1)-F(2) bond length is 2.14 Å. The Nb(1)-F(3) bond length is 2.05 Å. The Nb(1)-F(4) bond length is 2.03 Å. The Nb(1)-F(5) bond length is 2.10 Å. The Nb(1)-F(6) bond length is 2.08 Å. O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Nb(1) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and one Nb(1) atom to form a mixture of corner and edge-sharing FLi3Nb tetrahedra. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Nb(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Li(3), and one Nb(1) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), and one Nb(1) atom to form a mixture of distorted corner and edge-sharing FLi3Nb trigonal pyramids. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(3), and one Nb(1) atom to form a mixture of distorted corner and edge-sharing FLi3Nb tetrahedra. In the sixth F site, F(6) is bonded to one Li(2), two equivalent Li(1), and one Nb(1) atom to form a mixture of distorted corner and edge-sharing FLi3Nb tetrahedra.