Li2B2Bi2O7 crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(10), one O(3), one O(5), and one O(7) atom to form LiO4 tetrahedra that share corners with two equivalent Bi(2)O5 square pyramids and  a cornercorner with one Li(3)O4 trigonal pyramid. In the second Li site, Li(2) is bonded to one O(1), one O(11), one O(4), and one O(8) atom to form LiO4 trigonal pyramids that share  a cornercorner with one Li(2)O4 trigonal pyramid and edges with two equivalent Bi(2)O5 square pyramids. In the third Li site, Li(3) is bonded to one O(2), one O(6), one O(7), and one O(9) atom to form corner-sharing LiO4 trigonal pyramids. There are three inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(10), one O(2), and one O(4) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(6) atom. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(11), one O(5), and one O(9) atom. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(7), and one O(9) atom. In the second Bi site, Bi(2) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(8) atom to form distorted BiO5 square pyramids that share  a cornercorner with one Bi(2)O5 square pyramid, corners with two equivalent Li(1)O4 tetrahedra, and edges with two equivalent Li(2)O4 trigonal pyramids. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to two equivalent O(10), two equivalent O(11), and two equivalent O(6) atoms. In the fourth Bi site, Bi(4) is bonded in a 4-coordinate geometry to two equivalent O(6) and two equivalent O(7) atoms. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), one B(2), one Bi(1), and one Bi(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(3), one B(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one B(2), and one Bi(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one B(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one B(3), and one Bi(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(3), one B(2), one Bi(3), and one Bi(4) atom. In the seventh O site, O(7) is bonded to one Li(1), one Li(3), one Bi(1), and one Bi(4) atom to form distorted corner-sharing OLi2Bi2 trigonal pyramids. In the eighth O site, O(8) is bonded in a distorted see-saw-like geometry to two equivalent Li(2) and two equivalent Bi(2) atoms. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(3), one B(3), and one Bi(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one B(1), and one Bi(3) atom. In the eleventh O site, O(11) is bonded in a 2-coordinate geometry to one Li(2), one B(3), and one Bi(3) atom.
Li2B2Bi2O7 crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(10), one O(3), one O(5), and one O(7) atom to form LiO4 tetrahedra that share corners with two equivalent Bi(2)O5 square pyramids and  a cornercorner with one Li(3)O4 trigonal pyramid. The Li(1)-O(10) bond length is 1.95 Å. The Li(1)-O(3) bond length is 2.04 Å. The Li(1)-O(5) bond length is 1.96 Å. The Li(1)-O(7) bond length is 1.97 Å. In the second Li site, Li(2) is bonded to one O(1), one O(11), one O(4), and one O(8) atom to form LiO4 trigonal pyramids that share  a cornercorner with one Li(2)O4 trigonal pyramid and edges with two equivalent Bi(2)O5 square pyramids. The Li(2)-O(1) bond length is 2.17 Å. The Li(2)-O(11) bond length is 1.92 Å. The Li(2)-O(4) bond length is 1.93 Å. The Li(2)-O(8) bond length is 1.93 Å. In the third Li site, Li(3) is bonded to one O(2), one O(6), one O(7), and one O(9) atom to form corner-sharing LiO4 trigonal pyramids. The Li(3)-O(2) bond length is 1.95 Å. The Li(3)-O(6) bond length is 2.03 Å. The Li(3)-O(7) bond length is 2.03 Å. The Li(3)-O(9) bond length is 1.91 Å. There are three inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(10), one O(2), and one O(4) atom. The B(1)-O(10) bond length is 1.37 Å. The B(1)-O(2) bond length is 1.40 Å. The B(1)-O(4) bond length is 1.40 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(6) atom. The B(2)-O(1) bond length is 1.41 Å. The B(2)-O(3) bond length is 1.37 Å. The B(2)-O(6) bond length is 1.40 Å. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(11), one O(5), and one O(9) atom. The B(3)-O(11) bond length is 1.39 Å. The B(3)-O(5) bond length is 1.38 Å. The B(3)-O(9) bond length is 1.40 Å. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(7), and one O(9) atom. The Bi(1)-O(1) bond length is 2.44 Å. The Bi(1)-O(2) bond length is 2.17 Å. The Bi(1)-O(7) bond length is 2.16 Å. The Bi(1)-O(9) bond length is 2.28 Å. In the second Bi site, Bi(2) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(8) atom to form distorted BiO5 square pyramids that share  a cornercorner with one Bi(2)O5 square pyramid, corners with two equivalent Li(1)O4 tetrahedra, and edges with two equivalent Li(2)O4 trigonal pyramids. The Bi(2)-O(1) bond length is 2.56 Å. The Bi(2)-O(3) bond length is 2.26 Å. The Bi(2)-O(4) bond length is 2.31 Å. The Bi(2)-O(5) bond length is 2.36 Å. The Bi(2)-O(8) bond length is 2.22 Å. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to two equivalent O(10), two equivalent O(11), and two equivalent O(6) atoms. Both Bi(3)-O(10) bond lengths are 2.37 Å. Both Bi(3)-O(11) bond lengths are 2.50 Å. Both Bi(3)-O(6) bond lengths are 2.49 Å. In the fourth Bi site, Bi(4) is bonded in a 4-coordinate geometry to two equivalent O(6) and two equivalent O(7) atoms. Both Bi(4)-O(6) bond lengths are 2.45 Å. Both Bi(4)-O(7) bond lengths are 2.20 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), one B(2), one Bi(1), and one Bi(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(3), one B(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one B(2), and one Bi(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one B(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one B(3), and one Bi(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(3), one B(2), one Bi(3), and one Bi(4) atom. In the seventh O site, O(7) is bonded to one Li(1), one Li(3), one Bi(1), and one Bi(4) atom to form distorted corner-sharing OLi2Bi2 trigonal pyramids. In the eighth O site, O(8) is bonded in a distorted see-saw-like geometry to two equivalent Li(2) and two equivalent Bi(2) atoms. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(3), one B(3), and one Bi(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one B(1), and one Bi(3) atom. In the eleventh O site, O(11) is bonded in a 2-coordinate geometry to one Li(2), one B(3), and one Bi(3) atom.