LiBi2PO6 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(5), and one O(6) atom. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(5), and one O(6) atom. In the second Bi site, Bi(2) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(6) atom to form distorted BiO5 square pyramids that share corners with three equivalent P(1)O4 tetrahedra. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with three equivalent Bi(2)O5 square pyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Bi(2), and one P(1) 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(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(2), 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 Bi(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one Bi(2) atom.
LiBi2PO6 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(5), and one O(6) atom. The Li(1)-O(1) bond length is 2.30 Å. The Li(1)-O(2) bond length is 2.35 Å. The Li(1)-O(5) bond length is 1.99 Å. The Li(1)-O(6) bond length is 1.98 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Bi(1)-O(2) bond length is 2.58 Å. The Bi(1)-O(3) bond length is 2.56 Å. The Bi(1)-O(4) bond length is 2.38 Å. The Bi(1)-O(5) bond length is 2.12 Å. The Bi(1)-O(6) bond length is 2.16 Å. In the second Bi site, Bi(2) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(6) atom to form distorted BiO5 square pyramids that share corners with three equivalent P(1)O4 tetrahedra. The Bi(2)-O(1) bond length is 2.56 Å. The Bi(2)-O(3) bond length is 2.38 Å. The Bi(2)-O(4) bond length is 2.57 Å. The Bi(2)-O(5) bond length is 2.16 Å. The Bi(2)-O(6) bond length is 2.12 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with three equivalent Bi(2)O5 square pyramids. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.56 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Bi(2), and one P(1) 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(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(2), 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 Bi(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one Bi(2) atom.