LaBi5O9 crystallizes in the monoclinic Cm space group. La(1) is bonded in a distorted body-centered cubic geometry to one O(1), one O(4), one O(6), one O(7), two equivalent O(2), and two equivalent O(8) atoms. There are five inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(4), and two equivalent O(9) atoms to form corner-sharing BiO4 trigonal pyramids. In the second Bi site, Bi(2) is bonded to one O(2), one O(3), one O(5), and two equivalent O(6) atoms to form distorted BiO5 trigonal bipyramids that share corners with two equivalent Bi(2)O5 trigonal bipyramids and corners with four equivalent Bi(3)O4 trigonal pyramids. In the third Bi site, Bi(3) is bonded to one O(6), one O(7), and two equivalent O(3) atoms to form distorted BiO4 trigonal pyramids that share corners with four equivalent Bi(2)O5 trigonal bipyramids and corners with two equivalent Bi(3)O4 trigonal pyramids. In the fourth Bi site, Bi(4) is bonded in a 6-coordinate geometry to one O(8), one O(9), two equivalent O(1), and two equivalent O(5) atoms. In the fifth Bi site, Bi(5) is bonded in a 8-coordinate geometry to one O(2), one O(3), one O(8), one O(9), two equivalent O(4), and two equivalent O(7) atoms. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one La(1), one Bi(1), and two equivalent Bi(4) atoms to form OLaBi3 tetrahedra that share  a cornercorner with one O(6)LaBi3 tetrahedra,  a cornercorner with one O(7)LaBi3 tetrahedra, corners with two equivalent O(2)La2Bi2 tetrahedra, corners with two equivalent O(1)LaBi3 tetrahedra,  an edgeedge with one O(4)LaBi3 tetrahedra, and edges with two equivalent O(8)La2Bi2 tetrahedra. In the second O site, O(2) is bonded to two equivalent La(1), one Bi(2), and one Bi(5) atom to form OLa2Bi2 tetrahedra that share corners with two equivalent O(2)La2Bi2 tetrahedra, corners with two equivalent O(1)LaBi3 tetrahedra, corners with three equivalent O(8)La2Bi2 tetrahedra, corners with four equivalent O(7)LaBi3 tetrahedra,  an edgeedge with one O(8)La2Bi2 tetrahedra, edges with two equivalent O(4)LaBi3 tetrahedra, edges with two equivalent O(6)LaBi3 tetrahedra, and  an edgeedge with one O(3)Bi4 trigonal pyramid. In the third O site, O(3) is bonded to one Bi(2), one Bi(5), and two equivalent Bi(3) atoms to form distorted OBi4 trigonal pyramids that share  a cornercorner with one O(8)La2Bi2 tetrahedra, corners with two equivalent O(4)LaBi3 tetrahedra, corners with four equivalent O(6)LaBi3 tetrahedra, corners with two equivalent O(3)Bi4 trigonal pyramids,  an edgeedge with one O(2)La2Bi2 tetrahedra, and edges with two equivalent O(7)LaBi3 tetrahedra. In the fourth O site, O(4) is bonded to one La(1), one Bi(1), and two equivalent Bi(5) atoms to form OLaBi3 tetrahedra that share  a cornercorner with one O(6)LaBi3 tetrahedra, corners with two equivalent O(4)LaBi3 tetrahedra, corners with three equivalent O(7)LaBi3 tetrahedra, corners with four equivalent O(8)La2Bi2 tetrahedra, corners with two equivalent O(3)Bi4 trigonal pyramids,  an edgeedge with one O(1)LaBi3 tetrahedra,  an edgeedge with one O(7)LaBi3 tetrahedra, and edges with two equivalent O(2)La2Bi2 tetrahedra. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(4) atoms. In the sixth O site, O(6) is bonded to one La(1), one Bi(3), and two equivalent Bi(2) atoms to form distorted OLaBi3 tetrahedra that share  a cornercorner with one O(1)LaBi3 tetrahedra,  a cornercorner with one O(4)LaBi3 tetrahedra, corners with two equivalent O(8)La2Bi2 tetrahedra, corners with two equivalent O(6)LaBi3 tetrahedra, corners with four equivalent O(3)Bi4 trigonal pyramids,  an edgeedge with one O(7)LaBi3 tetrahedra, and edges with two equivalent O(2)La2Bi2 tetrahedra. In the seventh O site, O(7) is bonded to one La(1), one Bi(3), and two equivalent Bi(5) atoms to form OLaBi3 tetrahedra that share  a cornercorner with one O(1)LaBi3 tetrahedra, corners with two equivalent O(7)LaBi3 tetrahedra, corners with three equivalent O(4)LaBi3 tetrahedra, corners with four equivalent O(2)La2Bi2 tetrahedra,  an edgeedge with one O(4)LaBi3 tetrahedra,  an edgeedge with one O(6)LaBi3 tetrahedra, edges with two equivalent O(8)La2Bi2 tetrahedra, and edges with two equivalent O(3)Bi4 trigonal pyramids. In the eighth O site, O(8) is bonded to two equivalent La(1), one Bi(4), and one Bi(5) atom to form OLa2Bi2 tetrahedra that share corners with two equivalent O(8)La2Bi2 tetrahedra, corners with two equivalent O(6)LaBi3 tetrahedra, corners with three equivalent O(2)La2Bi2 tetrahedra, corners with four equivalent O(4)LaBi3 tetrahedra,  a cornercorner with one O(3)Bi4 trigonal pyramid,  an edgeedge with one O(2)La2Bi2 tetrahedra, edges with two equivalent O(1)LaBi3 tetrahedra, and edges with two equivalent O(7)LaBi3 tetrahedra. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Bi(4), one Bi(5), and two equivalent Bi(1) atoms.
LaBi5O9 crystallizes in the monoclinic Cm space group. La(1) is bonded in a distorted body-centered cubic geometry to one O(1), one O(4), one O(6), one O(7), two equivalent O(2), and two equivalent O(8) atoms. The La(1)-O(1) bond length is 2.46 Å. The La(1)-O(4) bond length is 2.66 Å. The La(1)-O(6) bond length is 2.79 Å. The La(1)-O(7) bond length is 2.53 Å. Both La(1)-O(2) bond lengths are 2.45 Å. Both La(1)-O(8) bond lengths are 2.56 Å. There are five inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(4), and two equivalent O(9) atoms to form corner-sharing BiO4 trigonal pyramids. The Bi(1)-O(1) bond length is 2.24 Å. The Bi(1)-O(4) bond length is 2.14 Å. Both Bi(1)-O(9) bond lengths are 2.27 Å. In the second Bi site, Bi(2) is bonded to one O(2), one O(3), one O(5), and two equivalent O(6) atoms to form distorted BiO5 trigonal bipyramids that share corners with two equivalent Bi(2)O5 trigonal bipyramids and corners with four equivalent Bi(3)O4 trigonal pyramids. The Bi(2)-O(2) bond length is 2.18 Å. The Bi(2)-O(3) bond length is 2.51 Å. The Bi(2)-O(5) bond length is 2.46 Å. Both Bi(2)-O(6) bond lengths are 2.26 Å. In the third Bi site, Bi(3) is bonded to one O(6), one O(7), and two equivalent O(3) atoms to form distorted BiO4 trigonal pyramids that share corners with four equivalent Bi(2)O5 trigonal bipyramids and corners with two equivalent Bi(3)O4 trigonal pyramids. The Bi(3)-O(6) bond length is 2.32 Å. The Bi(3)-O(7) bond length is 2.14 Å. Both Bi(3)-O(3) bond lengths are 2.34 Å. In the fourth Bi site, Bi(4) is bonded in a 6-coordinate geometry to one O(8), one O(9), two equivalent O(1), and two equivalent O(5) atoms. The Bi(4)-O(8) bond length is 2.24 Å. The Bi(4)-O(9) bond length is 2.26 Å. Both Bi(4)-O(1) bond lengths are 2.58 Å. Both Bi(4)-O(5) bond lengths are 2.49 Å. In the fifth Bi site, Bi(5) is bonded in a 8-coordinate geometry to one O(2), one O(3), one O(8), one O(9), two equivalent O(4), and two equivalent O(7) atoms. The Bi(5)-O(2) bond length is 2.65 Å. The Bi(5)-O(3) bond length is 2.81 Å. The Bi(5)-O(8) bond length is 2.29 Å. The Bi(5)-O(9) bond length is 2.85 Å. Both Bi(5)-O(4) bond lengths are 2.44 Å. Both Bi(5)-O(7) bond lengths are 2.48 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one La(1), one Bi(1), and two equivalent Bi(4) atoms to form OLaBi3 tetrahedra that share  a cornercorner with one O(6)LaBi3 tetrahedra,  a cornercorner with one O(7)LaBi3 tetrahedra, corners with two equivalent O(2)La2Bi2 tetrahedra, corners with two equivalent O(1)LaBi3 tetrahedra,  an edgeedge with one O(4)LaBi3 tetrahedra, and edges with two equivalent O(8)La2Bi2 tetrahedra. In the second O site, O(2) is bonded to two equivalent La(1), one Bi(2), and one Bi(5) atom to form OLa2Bi2 tetrahedra that share corners with two equivalent O(2)La2Bi2 tetrahedra, corners with two equivalent O(1)LaBi3 tetrahedra, corners with three equivalent O(8)La2Bi2 tetrahedra, corners with four equivalent O(7)LaBi3 tetrahedra,  an edgeedge with one O(8)La2Bi2 tetrahedra, edges with two equivalent O(4)LaBi3 tetrahedra, edges with two equivalent O(6)LaBi3 tetrahedra, and  an edgeedge with one O(3)Bi4 trigonal pyramid. In the third O site, O(3) is bonded to one Bi(2), one Bi(5), and two equivalent Bi(3) atoms to form distorted OBi4 trigonal pyramids that share  a cornercorner with one O(8)La2Bi2 tetrahedra, corners with two equivalent O(4)LaBi3 tetrahedra, corners with four equivalent O(6)LaBi3 tetrahedra, corners with two equivalent O(3)Bi4 trigonal pyramids,  an edgeedge with one O(2)La2Bi2 tetrahedra, and edges with two equivalent O(7)LaBi3 tetrahedra. In the fourth O site, O(4) is bonded to one La(1), one Bi(1), and two equivalent Bi(5) atoms to form OLaBi3 tetrahedra that share  a cornercorner with one O(6)LaBi3 tetrahedra, corners with two equivalent O(4)LaBi3 tetrahedra, corners with three equivalent O(7)LaBi3 tetrahedra, corners with four equivalent O(8)La2Bi2 tetrahedra, corners with two equivalent O(3)Bi4 trigonal pyramids,  an edgeedge with one O(1)LaBi3 tetrahedra,  an edgeedge with one O(7)LaBi3 tetrahedra, and edges with two equivalent O(2)La2Bi2 tetrahedra. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(4) atoms. In the sixth O site, O(6) is bonded to one La(1), one Bi(3), and two equivalent Bi(2) atoms to form distorted OLaBi3 tetrahedra that share  a cornercorner with one O(1)LaBi3 tetrahedra,  a cornercorner with one O(4)LaBi3 tetrahedra, corners with two equivalent O(8)La2Bi2 tetrahedra, corners with two equivalent O(6)LaBi3 tetrahedra, corners with four equivalent O(3)Bi4 trigonal pyramids,  an edgeedge with one O(7)LaBi3 tetrahedra, and edges with two equivalent O(2)La2Bi2 tetrahedra. In the seventh O site, O(7) is bonded to one La(1), one Bi(3), and two equivalent Bi(5) atoms to form OLaBi3 tetrahedra that share  a cornercorner with one O(1)LaBi3 tetrahedra, corners with two equivalent O(7)LaBi3 tetrahedra, corners with three equivalent O(4)LaBi3 tetrahedra, corners with four equivalent O(2)La2Bi2 tetrahedra,  an edgeedge with one O(4)LaBi3 tetrahedra,  an edgeedge with one O(6)LaBi3 tetrahedra, edges with two equivalent O(8)La2Bi2 tetrahedra, and edges with two equivalent O(3)Bi4 trigonal pyramids. In the eighth O site, O(8) is bonded to two equivalent La(1), one Bi(4), and one Bi(5) atom to form OLa2Bi2 tetrahedra that share corners with two equivalent O(8)La2Bi2 tetrahedra, corners with two equivalent O(6)LaBi3 tetrahedra, corners with three equivalent O(2)La2Bi2 tetrahedra, corners with four equivalent O(4)LaBi3 tetrahedra,  a cornercorner with one O(3)Bi4 trigonal pyramid,  an edgeedge with one O(2)La2Bi2 tetrahedra, edges with two equivalent O(1)LaBi3 tetrahedra, and edges with two equivalent O(7)LaBi3 tetrahedra. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Bi(4), one Bi(5), and two equivalent Bi(1) atoms.