LiBiP2O7 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(3), one O(5), one O(6), and one O(7) atom to form distorted LiO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. Bi(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra and corners with two equivalent Li(1)O4 tetrahedra. In the second P site, P(2) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra and corners with two equivalent Li(1)O4 tetrahedra. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Bi(1) and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Bi(1), one P(1), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Bi(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Bi(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Bi(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Bi(1), and one P(2) atom.
LiBiP2O7 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(3), one O(5), one O(6), and one O(7) atom to form distorted LiO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. The Li(1)-O(3) bond length is 1.93 Å. The Li(1)-O(5) bond length is 2.17 Å. The Li(1)-O(6) bond length is 2.29 Å. The Li(1)-O(7) bond length is 2.04 Å. Bi(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. The Bi(1)-O(1) bond length is 2.23 Å. The Bi(1)-O(2) bond length is 2.78 Å. The Bi(1)-O(3) bond length is 2.48 Å. The Bi(1)-O(4) bond length is 2.32 Å. The Bi(1)-O(5) bond length is 2.42 Å. The Bi(1)-O(6) bond length is 2.27 Å. The Bi(1)-O(7) bond length is 2.71 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra and corners with two equivalent Li(1)O4 tetrahedra. The P(1)-O(2) bond length is 1.63 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.52 Å. The P(1)-O(6) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra and corners with two equivalent Li(1)O4 tetrahedra. The P(2)-O(1) bond length is 1.52 Å. The P(2)-O(2) bond length is 1.63 Å. The P(2)-O(5) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.53 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Bi(1) and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Bi(1), one P(1), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Bi(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Bi(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Bi(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Bi(1), and one P(2) atom.