Li2BiP3O10 crystallizes in the monoclinic P2_1/m space group. Li(1) is bonded in a distorted trigonal non-coplanar geometry to one O(4) and two equivalent O(3) atoms. Bi(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form BiO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with four equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 59°. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(6), one O(7), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with two equivalent Bi(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. In the second P site, P(2) is bonded to one O(4), one O(7), and two equivalent O(3) atoms to form corner-sharing PO4 tetrahedra. In the third P site, P(3) is bonded to one O(2), one O(6), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with four equivalent Bi(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-69°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Bi(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Bi(1) and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to two equivalent Li(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Bi(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.
Li2BiP3O10 crystallizes in the monoclinic P2_1/m space group. Li(1) is bonded in a distorted trigonal non-coplanar geometry to one O(4) and two equivalent O(3) atoms. The Li(1)-O(4) bond length is 1.92 Å. There is one shorter (1.94 Å) and one longer (1.95 Å) Li(1)-O(3) bond length. Bi(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form BiO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with four equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 59°. Both Bi(1)-O(1) bond lengths are 2.30 Å. Both Bi(1)-O(2) bond lengths are 2.58 Å. Both Bi(1)-O(5) bond lengths are 2.38 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(6), one O(7), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with two equivalent Bi(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. The P(1)-O(6) bond length is 1.61 Å. The P(1)-O(7) bond length is 1.54 Å. Both P(1)-O(1) bond lengths are 1.52 Å. In the second P site, P(2) is bonded to one O(4), one O(7), and two equivalent O(3) atoms to form corner-sharing PO4 tetrahedra. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.68 Å. Both P(2)-O(3) bond lengths are 1.52 Å. In the third P site, P(3) is bonded to one O(2), one O(6), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with four equivalent Bi(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-69°. The P(3)-O(2) bond length is 1.56 Å. The P(3)-O(6) bond length is 1.63 Å. Both P(3)-O(5) bond lengths are 1.53 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Bi(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Bi(1) and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to two equivalent Li(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Bi(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.