LiBiP2O7 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(6), one O(7), and two equivalent O(4) atoms. Bi(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form BiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(4), and one O(5) 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 19-58°. In the second P site, P(2) is bonded to one O(3), one O(5), 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(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-65°. 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(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Bi(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Bi(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Bi(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(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(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar 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 in a 5-coordinate geometry to one O(1), one O(6), one O(7), and two equivalent O(4) atoms. The Li(1)-O(1) bond length is 2.22 Å. The Li(1)-O(6) bond length is 2.17 Å. The Li(1)-O(7) bond length is 2.26 Å. There is one shorter (2.19 Å) and one longer (2.52 Å) Li(1)-O(4) bond length. Bi(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form BiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. The Bi(1)-O(1) bond length is 2.34 Å. The Bi(1)-O(2) bond length is 2.37 Å. The Bi(1)-O(3) bond length is 2.33 Å. The Bi(1)-O(4) bond length is 2.41 Å. The Bi(1)-O(6) bond length is 2.48 Å. The Bi(1)-O(7) bond length is 2.33 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(4), and one O(5) 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 19-58°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.50 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.63 Å. In the second P site, P(2) is bonded to one O(3), one O(5), 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(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-65°. The P(2)-O(3) bond length is 1.53 Å. The P(2)-O(5) bond length is 1.63 Å. The P(2)-O(6) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.54 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(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Bi(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Bi(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Bi(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(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(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Bi(1), and one P(2) atom.