Li3Bi2(PO4)3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(2) atoms. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(2), one O(4), one O(5), and one O(6) atom. Bi(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted BiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share corners with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-69°. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-55°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees 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 rectangular see-saw-like geometry to one Li(1), one Li(2), one Bi(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to 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(2), one Bi(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Bi(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one Bi(1), and one P(1) atom.
Li3Bi2(PO4)3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Li(1)-O(1) bond lengths are 1.92 Å. Both Li(1)-O(2) bond lengths are 2.34 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(2), one O(4), one O(5), and one O(6) atom. The Li(2)-O(2) bond length is 2.12 Å. The Li(2)-O(4) bond length is 1.92 Å. The Li(2)-O(5) bond length is 2.07 Å. The Li(2)-O(6) bond length is 2.00 Å. Bi(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted BiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. The Bi(1)-O(1) bond length is 2.45 Å. The Bi(1)-O(2) bond length is 2.37 Å. The Bi(1)-O(3) bond length is 2.40 Å. The Bi(1)-O(4) bond length is 2.32 Å. The Bi(1)-O(5) bond length is 2.45 Å. The Bi(1)-O(6) bond length is 2.30 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share corners with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-69°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.56 Å. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-55°. Both P(2)-O(2) bond lengths are 1.58 Å. Both P(2)-O(5) bond lengths are 1.55 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees 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 rectangular see-saw-like geometry to one Li(1), one Li(2), one Bi(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to 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(2), one Bi(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Bi(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one Bi(1), and one P(1) atom.