LiBiP2O7 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. Bi(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form distorted BiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Bi(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-69°. In the second P site, P(2) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Bi(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles are 38°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Bi(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Bi(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Bi(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Bi(1) and one P(1) atom.
LiBiP2O7 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Li(1)-O(1) bond length is 2.18 Å. The Li(1)-O(2) bond length is 2.05 Å. The Li(1)-O(3) bond length is 2.16 Å. The Li(1)-O(4) bond length is 2.37 Å. Bi(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form distorted BiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The Bi(1)-O(1) bond length is 2.54 Å. The Bi(1)-O(2) bond length is 2.33 Å. The Bi(1)-O(3) bond length is 2.64 Å. The Bi(1)-O(4) bond length is 2.46 Å. The Bi(1)-O(5) bond length is 2.27 Å. The Bi(1)-O(7) bond length is 2.27 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Bi(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-69°. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.63 Å. The P(1)-O(7) 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(6) atom to form PO4 tetrahedra that share  a cornercorner with one Bi(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles are 38°. The P(2)-O(1) bond length is 1.53 Å. The P(2)-O(2) bond length is 1.56 Å. The P(2)-O(5) bond length is 1.52 Å. The P(2)-O(6) bond length is 1.62 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Bi(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Bi(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Bi(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Bi(1) and one P(1) atom.