LiBi2As2(PbO5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded in a trigonal planar geometry to one Pb(1), one O(1), one O(2), and one O(6) atom. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 7-coordinate geometry to one Li(1), one O(10), one O(3), one O(5), one O(7), one O(8), and one O(9) atom. In the second Pb site, Pb(2) is bonded in a 5-coordinate geometry to 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(10), one O(5), one O(7), and one O(8) atom. In the second Bi site, Bi(2) is bonded to one O(2), one O(3), one O(7), one O(8), and one O(9) atom to form distorted BiO5 square pyramids that share  a cornercorner with one As(2)O4 tetrahedra and corners with two equivalent As(1)O4 tetrahedra. 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 corners with two equivalent Bi(2)O5 square pyramids. 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  a cornercorner with one Bi(2)O5 square pyramid. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one Li(1), one Bi(1), and one As(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Bi(2), and one As(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Pb(1), one Bi(2), and one As(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Pb(2) and one As(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Pb(1), one Pb(2), one Bi(1), and one As(2) atom. In the sixth O site, O(6) is bonded in a water-like geometry to one Li(1), one Pb(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 3-coordinate geometry to 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 Pb(1), one Bi(1), and one As(2) atom.
LiBi2As2(PbO5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded in a trigonal planar geometry to one Pb(1), one O(1), one O(2), and one O(6) atom. The Li(1)-Pb(1) bond length is 2.99 Å. The Li(1)-O(1) bond length is 1.92 Å. The Li(1)-O(2) bond length is 1.96 Å. The Li(1)-O(6) bond length is 1.93 Å. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 7-coordinate geometry to one Li(1), one O(10), one O(3), one O(5), one O(7), one O(8), and one O(9) atom. The Pb(1)-O(10) bond length is 2.58 Å. The Pb(1)-O(3) bond length is 2.73 Å. The Pb(1)-O(5) bond length is 2.86 Å. The Pb(1)-O(7) bond length is 2.43 Å. The Pb(1)-O(8) bond length is 2.39 Å. The Pb(1)-O(9) bond length is 2.75 Å. In the second Pb site, Pb(2) is bonded in a 5-coordinate geometry to one O(4), one O(5), one O(6), one O(7), and one O(8) atom. The Pb(2)-O(4) bond length is 2.42 Å. The Pb(2)-O(5) bond length is 2.80 Å. The Pb(2)-O(6) bond length is 2.83 Å. The Pb(2)-O(7) bond length is 2.61 Å. The Pb(2)-O(8) bond length is 2.46 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(10), one O(5), one O(7), and one O(8) atom. The Bi(1)-O(1) bond length is 2.60 Å. The Bi(1)-O(10) bond length is 2.38 Å. The Bi(1)-O(5) bond length is 2.65 Å. The Bi(1)-O(7) bond length is 2.30 Å. The Bi(1)-O(8) bond length is 2.24 Å. In the second Bi site, Bi(2) is bonded to one O(2), one O(3), one O(7), one O(8), and one O(9) atom to form distorted BiO5 square pyramids that share  a cornercorner with one As(2)O4 tetrahedra and corners with two equivalent As(1)O4 tetrahedra. The Bi(2)-O(2) bond length is 2.45 Å. The Bi(2)-O(3) bond length is 2.36 Å. The Bi(2)-O(7) bond length is 2.21 Å. The Bi(2)-O(8) bond length is 2.39 Å. The Bi(2)-O(9) bond length is 2.31 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 corners with two equivalent Bi(2)O5 square pyramids. The As(1)-O(2) bond length is 1.75 Å. The As(1)-O(3) bond length is 1.74 Å. The As(1)-O(4) bond length is 1.72 Å. The As(1)-O(6) bond length is 1.72 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  a cornercorner with one Bi(2)O5 square pyramid. The As(2)-O(1) bond length is 1.75 Å. The As(2)-O(10) bond length is 1.78 Å. The As(2)-O(5) bond length is 1.76 Å. The As(2)-O(9) bond length is 1.77 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one Li(1), one Bi(1), and one As(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Bi(2), and one As(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Pb(1), one Bi(2), and one As(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Pb(2) and one As(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Pb(1), one Pb(2), one Bi(1), and one As(2) atom. In the sixth O site, O(6) is bonded in a water-like geometry to one Li(1), one Pb(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 3-coordinate geometry to 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 Pb(1), one Bi(1), and one As(2) atom.