LiBi2As2(PbO5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(10), one O(4), one O(6), and one O(9) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Pb(1)O6 pentagonal pyramids,  an edgeedge with one As(1)O4 tetrahedra, and  an edgeedge with one As(2)O4 tetrahedra. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to one O(10), one O(2), one O(3), one O(7), one O(8), and one O(9) atom to form distorted PbO6 pentagonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra, and  an edgeedge with one As(1)O4 tetrahedra. In the second Pb site, Pb(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), one O(7), and one O(8) atom. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(6), one O(7), one O(8), and one O(9) atom. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form AsO4 tetrahedra that share  an edgeedge with one Pb(1)O6 pentagonal pyramid and  an edgeedge with one Li(1)O4 tetrahedra. In the second As site, As(2) is bonded to one O(1), one O(10), one O(5), and one O(9) atom to form AsO4 tetrahedra that share corners with two equivalent Pb(1)O6 pentagonal pyramids and  an edgeedge with one Li(1)O4 tetrahedra. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Pb(2), one Bi(1), and one As(2) atom. In the second O site, O(2) is bonded in a 1-coordinate geometry to one Pb(1), one Pb(2), one Bi(2), and one As(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Pb(1), one Bi(2), and one As(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Pb(2), one Bi(1), and one As(1) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one Pb(2), one Bi(1), and one As(2) atom. In the sixth O site, O(6) is bonded in a distorted L-shaped geometry to one Li(1), one Pb(2), one Bi(2), and one As(1) atom. In the seventh O site, O(7) is bonded to one Pb(1), one Pb(2), one Bi(1), and one Bi(2) atom to form edge-sharing OBi2Pb2 tetrahedra. In the eighth O site, O(8) is bonded to one Pb(1), one Pb(2), one Bi(1), and one Bi(2) atom to form edge-sharing OBi2Pb2 tetrahedra. In the ninth O site, O(9) is bonded in a distorted L-shaped geometry to one Li(1), one Pb(1), one Bi(2), and one As(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(1), one Pb(1), and one As(2) atom.
LiBi2As2(PbO5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(10), one O(4), one O(6), and one O(9) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Pb(1)O6 pentagonal pyramids,  an edgeedge with one As(1)O4 tetrahedra, and  an edgeedge with one As(2)O4 tetrahedra. The Li(1)-O(10) bond length is 2.03 Å. The Li(1)-O(4) bond length is 2.04 Å. The Li(1)-O(6) bond length is 2.01 Å. The Li(1)-O(9) bond length is 2.05 Å. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to one O(10), one O(2), one O(3), one O(7), one O(8), and one O(9) atom to form distorted PbO6 pentagonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra, and  an edgeedge with one As(1)O4 tetrahedra. The Pb(1)-O(10) bond length is 2.60 Å. The Pb(1)-O(2) bond length is 2.72 Å. The Pb(1)-O(3) bond length is 2.63 Å. The Pb(1)-O(7) bond length is 2.62 Å. The Pb(1)-O(8) bond length is 2.44 Å. The Pb(1)-O(9) bond length is 2.74 Å. In the second Pb site, Pb(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. The Pb(2)-O(1) bond length is 2.72 Å. The Pb(2)-O(2) bond length is 2.89 Å. The Pb(2)-O(4) bond length is 2.71 Å. The Pb(2)-O(5) bond length is 2.80 Å. The Pb(2)-O(6) bond length is 2.74 Å. The Pb(2)-O(7) bond length is 2.54 Å. The Pb(2)-O(8) bond length is 2.43 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), one O(7), and one O(8) atom. The Bi(1)-O(1) bond length is 2.41 Å. The Bi(1)-O(4) bond length is 2.40 Å. The Bi(1)-O(5) bond length is 2.39 Å. The Bi(1)-O(7) bond length is 2.14 Å. The Bi(1)-O(8) bond length is 2.33 Å. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(6), one O(7), one O(8), and one O(9) atom. The Bi(2)-O(2) bond length is 2.50 Å. The Bi(2)-O(3) bond length is 2.41 Å. The Bi(2)-O(6) bond length is 2.66 Å. The Bi(2)-O(7) bond length is 2.20 Å. The Bi(2)-O(8) bond length is 2.26 Å. The Bi(2)-O(9) bond length is 2.69 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form AsO4 tetrahedra that share  an edgeedge with one Pb(1)O6 pentagonal pyramid and  an edgeedge with one Li(1)O4 tetrahedra. The As(1)-O(2) bond length is 1.78 Å. The As(1)-O(3) bond length is 1.81 Å. The As(1)-O(4) bond length is 1.82 Å. The As(1)-O(6) bond length is 1.80 Å. In the second As site, As(2) is bonded to one O(1), one O(10), one O(5), and one O(9) atom to form AsO4 tetrahedra that share corners with two equivalent Pb(1)O6 pentagonal pyramids and  an edgeedge with one Li(1)O4 tetrahedra. The As(2)-O(1) bond length is 1.72 Å. The As(2)-O(10) bond length is 1.73 Å. The As(2)-O(5) bond length is 1.74 Å. The As(2)-O(9) bond length is 1.74 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Pb(2), one Bi(1), and one As(2) atom. In the second O site, O(2) is bonded in a 1-coordinate geometry to one Pb(1), one Pb(2), one Bi(2), and one As(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Pb(1), one Bi(2), and one As(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Pb(2), one Bi(1), and one As(1) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one Pb(2), one Bi(1), and one As(2) atom. In the sixth O site, O(6) is bonded in a distorted L-shaped geometry to one Li(1), one Pb(2), one Bi(2), and one As(1) atom. In the seventh O site, O(7) is bonded to one Pb(1), one Pb(2), one Bi(1), and one Bi(2) atom to form edge-sharing OBi2Pb2 tetrahedra. In the eighth O site, O(8) is bonded to one Pb(1), one Pb(2), one Bi(1), and one Bi(2) atom to form edge-sharing OBi2Pb2 tetrahedra. In the ninth O site, O(9) is bonded in a distorted L-shaped geometry to one Li(1), one Pb(1), one Bi(2), and one As(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(1), one Pb(1), and one As(2) atom.