Li2B2Bi2O7 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(3), one O(5), one O(6), and one O(7) atom. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(5), one O(6), and one O(7) atom. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(2), one O(5), and one O(7) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(3), one O(4), and one O(6) atom. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(6), one O(7), and two equivalent O(1) atoms. There are seven inequivalent O sites. In the first O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), one B(1), and one Bi(2) atom. In the second O site, O(1) is bonded to two equivalent Bi(1) and two equivalent Bi(2) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the third O site, O(2) is bonded in a distorted single-bond geometry to one B(1), one Bi(2), and two equivalent Bi(1) atoms. In the fourth O site, O(3) is bonded in a 1-coordinate geometry to one Li(1), one B(2), one Bi(2), and two equivalent Bi(1) atoms. In the fifth O site, O(4) is bonded in a distorted single-bond geometry to one B(2), one Bi(2), and two equivalent Bi(1) atoms. In the sixth O site, O(5) is bonded in a 1-coordinate geometry to one Li(1), one Li(2), one B(1), and one Bi(2) atom. In the seventh O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), one B(2), and one Bi(2) atom.
Li2B2Bi2O7 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(3), one O(5), one O(6), and one O(7) atom. The Li(1)-O(3) bond length is 2.39 Å. The Li(1)-O(5) bond length is 2.10 Å. The Li(1)-O(6) bond length is 1.98 Å. The Li(1)-O(7) bond length is 2.17 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(5), one O(6), and one O(7) atom. The Li(2)-O(5) bond length is 2.30 Å. The Li(2)-O(6) bond length is 2.04 Å. The Li(2)-O(7) bond length is 1.93 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(2), one O(5), and one O(7) atom. The B(1)-O(2) bond length is 1.43 Å. The B(1)-O(5) bond length is 1.37 Å. The B(1)-O(7) bond length is 1.38 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(3), one O(4), and one O(6) atom. The B(2)-O(3) bond length is 1.39 Å. The B(2)-O(4) bond length is 1.41 Å. The B(2)-O(6) bond length is 1.37 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. There is one shorter (2.28 Å) and one longer (2.50 Å) Bi(1)-O(1) bond length. There is one shorter (2.28 Å) and one longer (2.84 Å) Bi(1)-O(2) bond length. There is one shorter (2.58 Å) and one longer (2.78 Å) Bi(1)-O(3) bond length. There is one shorter (2.32 Å) and one longer (2.67 Å) Bi(1)-O(4) bond length. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(6), one O(7), and two equivalent O(1) atoms. The Bi(2)-O(2) bond length is 2.42 Å. The Bi(2)-O(3) bond length is 2.68 Å. The Bi(2)-O(4) bond length is 2.56 Å. The Bi(2)-O(5) bond length is 2.50 Å. The Bi(2)-O(6) bond length is 2.49 Å. The Bi(2)-O(7) bond length is 2.67 Å. There is one shorter (2.32 Å) and one longer (2.41 Å) Bi(2)-O(1) bond length. There are seven inequivalent O sites. In the first O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), one B(1), and one Bi(2) atom. In the second O site, O(1) is bonded to two equivalent Bi(1) and two equivalent Bi(2) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the third O site, O(2) is bonded in a distorted single-bond geometry to one B(1), one Bi(2), and two equivalent Bi(1) atoms. In the fourth O site, O(3) is bonded in a 1-coordinate geometry to one Li(1), one B(2), one Bi(2), and two equivalent Bi(1) atoms. In the fifth O site, O(4) is bonded in a distorted single-bond geometry to one B(2), one Bi(2), and two equivalent Bi(1) atoms. In the sixth O site, O(5) is bonded in a 1-coordinate geometry to one Li(1), one Li(2), one B(1), and one Bi(2) atom. In the seventh O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), one B(2), and one Bi(2) atom.