Li7Bi(BO4)2 crystallizes in the monoclinic C2/m space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent B(1)O4 tetrahedra,  an edgeedge with one Li(3)O4 tetrahedra, and  an edgeedge with one B(2)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(2), one O(5), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent B(1)O4 tetrahedra, corners with two equivalent B(2)O4 tetrahedra, and corners with four equivalent Li(1)O4 tetrahedra. In the third Li site, Li(3) is bonded to one O(1), one O(4), and two equivalent O(6) atoms to form LiO4 tetrahedra that share corners with two equivalent B(1)O4 tetrahedra, corners with two equivalent B(2)O4 tetrahedra, and edges with two equivalent Li(1)O4 tetrahedra. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(3), one O(4), one O(5), and one O(6) atom. In the fifth Li site, Li(5) is bonded in a distorted square co-planar geometry to two equivalent O(2) and two equivalent O(5) atoms. In the sixth Li site, Li(6) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(4) atoms. There are two inequivalent B sites. In the first B site, B(1) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form BO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, and corners with four equivalent Li(1)O4 tetrahedra. In the second B site, B(2) is bonded to one O(2), one O(5), and two equivalent O(6) atoms to form BO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, and edges with two equivalent Li(1)O4 tetrahedra. Bi(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and two equivalent O(6) atoms. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(3), one Li(6), two equivalent Li(1), and one B(1) atom. In the second O site, O(2) is bonded to one Li(2), one Li(5), two equivalent Li(1), and one B(2) atom to form distorted corner-sharing OLi4B trigonal bipyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(4), one B(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded to one Li(3), one Li(6), two equivalent Li(4), and one B(1) atom to form corner-sharing OLi4B trigonal bipyramids. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(2), one Li(5), two equivalent Li(4), and one B(2) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Li(1), one Li(3), one Li(4), one B(2), and one Bi(1) atom.
Li7Bi(BO4)2 crystallizes in the monoclinic C2/m space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent B(1)O4 tetrahedra,  an edgeedge with one Li(3)O4 tetrahedra, and  an edgeedge with one B(2)O4 tetrahedra. The Li(1)-O(1) bond length is 1.88 Å. The Li(1)-O(2) bond length is 1.91 Å. The Li(1)-O(3) bond length is 2.07 Å. The Li(1)-O(6) bond length is 2.19 Å. In the second Li site, Li(2) is bonded to one O(2), one O(5), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent B(1)O4 tetrahedra, corners with two equivalent B(2)O4 tetrahedra, and corners with four equivalent Li(1)O4 tetrahedra. The Li(2)-O(2) bond length is 1.87 Å. The Li(2)-O(5) bond length is 1.99 Å. Both Li(2)-O(3) bond lengths are 2.16 Å. In the third Li site, Li(3) is bonded to one O(1), one O(4), and two equivalent O(6) atoms to form LiO4 tetrahedra that share corners with two equivalent B(1)O4 tetrahedra, corners with two equivalent B(2)O4 tetrahedra, and edges with two equivalent Li(1)O4 tetrahedra. The Li(3)-O(1) bond length is 1.95 Å. The Li(3)-O(4) bond length is 1.86 Å. Both Li(3)-O(6) bond lengths are 2.17 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(3), one O(4), one O(5), and one O(6) atom. The Li(4)-O(3) bond length is 2.13 Å. The Li(4)-O(4) bond length is 1.88 Å. The Li(4)-O(5) bond length is 1.88 Å. The Li(4)-O(6) bond length is 2.03 Å. In the fifth Li site, Li(5) is bonded in a distorted square co-planar geometry to two equivalent O(2) and two equivalent O(5) atoms. Both Li(5)-O(2) bond lengths are 1.97 Å. Both Li(5)-O(5) bond lengths are 1.97 Å. In the sixth Li site, Li(6) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(4) atoms. Both Li(6)-O(1) bond lengths are 1.98 Å. Both Li(6)-O(4) bond lengths are 1.88 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form BO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, and corners with four equivalent Li(1)O4 tetrahedra. The B(1)-O(1) bond length is 1.43 Å. The B(1)-O(4) bond length is 1.46 Å. Both B(1)-O(3) bond lengths are 1.61 Å. In the second B site, B(2) is bonded to one O(2), one O(5), and two equivalent O(6) atoms to form BO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, and edges with two equivalent Li(1)O4 tetrahedra. The B(2)-O(2) bond length is 1.46 Å. The B(2)-O(5) bond length is 1.44 Å. Both B(2)-O(6) bond lengths are 1.60 Å. Bi(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and two equivalent O(6) atoms. Both Bi(1)-O(3) bond lengths are 2.25 Å. Both Bi(1)-O(6) bond lengths are 2.25 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(3), one Li(6), two equivalent Li(1), and one B(1) atom. In the second O site, O(2) is bonded to one Li(2), one Li(5), two equivalent Li(1), and one B(2) atom to form distorted corner-sharing OLi4B trigonal bipyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(4), one B(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded to one Li(3), one Li(6), two equivalent Li(4), and one B(1) atom to form corner-sharing OLi4B trigonal bipyramids. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(2), one Li(5), two equivalent Li(4), and one B(2) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Li(1), one Li(3), one Li(4), one B(2), and one Bi(1) atom.