Li6Bi2O7 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Li(3)O4 tetrahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, corners with four equivalent Li(2)O5 trigonal bipyramids, edges with four equivalent Bi(1)O6 octahedra, edges with two equivalent Li(3)O4 tetrahedra, and edges with two equivalent Li(2)O5 trigonal bipyramids. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form LiO5 trigonal bipyramids that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(2)O5 trigonal bipyramids, corners with four equivalent Li(1)O5 trigonal bipyramids, edges with four equivalent Bi(1)O6 octahedra,  an edgeedge with one Li(3)O4 tetrahedra, and edges with two equivalent Li(1)O5 trigonal bipyramids. In the third Li site, Li(3) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with five equivalent Bi(1)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, corners with three equivalent Li(2)O5 trigonal bipyramids,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(3)O4 tetrahedra,  an edgeedge with one Li(2)O5 trigonal bipyramid, and edges with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 10-78°. Bi(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form BiO6 octahedra that share corners with three equivalent Bi(1)O6 octahedra, corners with five equivalent Li(3)O4 tetrahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(3)O4 tetrahedra, edges with four equivalent Li(1)O5 trigonal bipyramids, and edges with four equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-26°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Bi(1) atoms to form OLi4Bi2 octahedra that share corners with six equivalent O(3)Li5Bi octahedra, edges with two equivalent O(3)Li5Bi octahedra, edges with four equivalent O(2)Li4Bi2 octahedra, and edges with four equivalent O(4)Li3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-22°. In the second O site, O(2) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Bi(1) atoms to form distorted OLi4Bi2 octahedra that share corners with six equivalent O(4)Li3Bi2 trigonal bipyramids, edges with two equivalent O(1)Li4Bi2 octahedra, edges with two equivalent O(2)Li4Bi2 octahedra, edges with four equivalent O(3)Li5Bi octahedra, and  an edgeedge with one O(4)Li3Bi2 trigonal bipyramid. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Bi(1) atom to form OLi5Bi octahedra that share corners with three equivalent O(1)Li4Bi2 octahedra,  a cornercorner with one O(4)Li3Bi2 trigonal bipyramid,  an edgeedge with one O(1)Li4Bi2 octahedra, edges with two equivalent O(3)Li5Bi octahedra, edges with four equivalent O(2)Li4Bi2 octahedra, and edges with three equivalent O(4)Li3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-22°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Bi(1) atoms to form distorted OLi3Bi2 trigonal bipyramids that share  a cornercorner with one O(3)Li5Bi octahedra, corners with six equivalent O(2)Li4Bi2 octahedra, corners with two equivalent O(4)Li3Bi2 trigonal bipyramids,  an edgeedge with one O(2)Li4Bi2 octahedra, edges with two equivalent O(1)Li4Bi2 octahedra, and edges with three equivalent O(3)Li5Bi octahedra. The corner-sharing octahedral tilt angles range from 6-80°.
Li6Bi2O7 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Li(3)O4 tetrahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, corners with four equivalent Li(2)O5 trigonal bipyramids, edges with four equivalent Bi(1)O6 octahedra, edges with two equivalent Li(3)O4 tetrahedra, and edges with two equivalent Li(2)O5 trigonal bipyramids. The Li(1)-O(1) bond length is 2.33 Å. The Li(1)-O(2) bond length is 2.23 Å. The Li(1)-O(4) bond length is 2.42 Å. There is one shorter (1.97 Å) and one longer (2.00 Å) Li(1)-O(3) bond length. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form LiO5 trigonal bipyramids that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(2)O5 trigonal bipyramids, corners with four equivalent Li(1)O5 trigonal bipyramids, edges with four equivalent Bi(1)O6 octahedra,  an edgeedge with one Li(3)O4 tetrahedra, and edges with two equivalent Li(1)O5 trigonal bipyramids. The Li(2)-O(1) bond length is 2.29 Å. The Li(2)-O(2) bond length is 2.17 Å. The Li(2)-O(4) bond length is 2.23 Å. There is one shorter (2.07 Å) and one longer (2.17 Å) Li(2)-O(3) bond length. In the third Li site, Li(3) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with five equivalent Bi(1)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, corners with three equivalent Li(2)O5 trigonal bipyramids,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(3)O4 tetrahedra,  an edgeedge with one Li(2)O5 trigonal bipyramid, and edges with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 10-78°. The Li(3)-O(3) bond length is 1.94 Å. The Li(3)-O(4) bond length is 2.01 Å. There is one shorter (1.99 Å) and one longer (2.04 Å) Li(3)-O(2) bond length. Bi(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form BiO6 octahedra that share corners with three equivalent Bi(1)O6 octahedra, corners with five equivalent Li(3)O4 tetrahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(3)O4 tetrahedra, edges with four equivalent Li(1)O5 trigonal bipyramids, and edges with four equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-26°. The Bi(1)-O(1) bond length is 2.20 Å. The Bi(1)-O(3) bond length is 2.16 Å. There is one shorter (2.26 Å) and one longer (2.33 Å) Bi(1)-O(2) bond length. There is one shorter (2.17 Å) and one longer (2.19 Å) Bi(1)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Bi(1) atoms to form OLi4Bi2 octahedra that share corners with six equivalent O(3)Li5Bi octahedra, edges with two equivalent O(3)Li5Bi octahedra, edges with four equivalent O(2)Li4Bi2 octahedra, and edges with four equivalent O(4)Li3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-22°. In the second O site, O(2) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Bi(1) atoms to form distorted OLi4Bi2 octahedra that share corners with six equivalent O(4)Li3Bi2 trigonal bipyramids, edges with two equivalent O(1)Li4Bi2 octahedra, edges with two equivalent O(2)Li4Bi2 octahedra, edges with four equivalent O(3)Li5Bi octahedra, and  an edgeedge with one O(4)Li3Bi2 trigonal bipyramid. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Bi(1) atom to form OLi5Bi octahedra that share corners with three equivalent O(1)Li4Bi2 octahedra,  a cornercorner with one O(4)Li3Bi2 trigonal bipyramid,  an edgeedge with one O(1)Li4Bi2 octahedra, edges with two equivalent O(3)Li5Bi octahedra, edges with four equivalent O(2)Li4Bi2 octahedra, and edges with three equivalent O(4)Li3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-22°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Bi(1) atoms to form distorted OLi3Bi2 trigonal bipyramids that share  a cornercorner with one O(3)Li5Bi octahedra, corners with six equivalent O(2)Li4Bi2 octahedra, corners with two equivalent O(4)Li3Bi2 trigonal bipyramids,  an edgeedge with one O(2)Li4Bi2 octahedra, edges with two equivalent O(1)Li4Bi2 octahedra, and edges with three equivalent O(3)Li5Bi octahedra. The corner-sharing octahedral tilt angles range from 6-80°.