Li5(BiO3)4 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(3), one O(6), and one O(9) atom. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(4), one O(6), one O(7), and one O(9) atom. In the third Li site, Li(3) is bonded to one O(10), one O(12), one O(2), one O(3), and one O(4) atom to form distorted LiO5 square pyramids that share  a cornercorner with one Li(5)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, corners with two equivalent Li(4)O5 trigonal bipyramids,  an edgeedge with one Bi(2)O6 octahedra, and edges with three equivalent Bi(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-84°. In the fourth Li site, Li(4) is bonded to one O(1), one O(10), one O(11), one O(2), and one O(5) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Bi(1)O6 octahedra,  a cornercorner with one Bi(2)O6 octahedra,  a cornercorner with one Bi(3)O6 octahedra,  a cornercorner with one Bi(4)O6 octahedra, corners with two equivalent Li(3)O5 square pyramids,  an edgeedge with one Li(5)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra, and edges with two equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-73°. In the fifth Li site, Li(5) is bonded to one O(11), one O(12), one O(5), one O(7), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Bi(1)O6 octahedra,  a cornercorner with one Bi(2)O6 octahedra,  a cornercorner with one Bi(3)O6 octahedra,  a cornercorner with one Bi(4)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  an edgeedge with one Li(5)O6 octahedra,  an edgeedge with one Bi(2)O6 octahedra, edges with three equivalent Bi(1)O6 octahedra, and  an edgeedge with one Li(4)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 17-66°. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(11), one O(5), one O(7), and two equivalent O(8) atoms to form BiO6 octahedra that share  a cornercorner with one Li(5)O6 octahedra, corners with two equivalent Bi(4)O6 octahedra,  a cornercorner with one Li(4)O5 trigonal bipyramid,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Bi(2)O6 octahedra, edges with three equivalent Li(5)O6 octahedra, and  an edgeedge with one Li(4)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-62°. In the second Bi site, Bi(2) is bonded to one O(10), one O(11), one O(12), one O(5), and two equivalent O(2) atoms to form BiO6 octahedra that share  a cornercorner with one Li(5)O6 octahedra, corners with two equivalent Li(3)O5 square pyramids,  a cornercorner with one Li(4)O5 trigonal bipyramid,  an edgeedge with one Li(5)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Bi(2)O6 octahedra,  an edgeedge with one Bi(3)O6 octahedra,  an edgeedge with one Li(3)O5 square pyramid, and edges with two equivalent Li(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 20°. In the third Bi site, Bi(3) is bonded to one O(10), one O(12), two equivalent O(3), and two equivalent O(4) atoms to form BiO6 octahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one Li(4)O5 trigonal bipyramid,  an edgeedge with one Bi(2)O6 octahedra, edges with two equivalent Bi(3)O6 octahedra, and edges with three equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles are 17°. In the fourth Bi site, Bi(4) is bonded to one O(1), one O(7), two equivalent O(6), and two equivalent O(9) atoms to form distorted BiO6 octahedra that share  a cornercorner with one Li(5)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra,  a cornercorner with one Li(4)O5 trigonal bipyramid, and edges with two equivalent Bi(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-66°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one Bi(1), and one Bi(4) atom to form a mixture of distorted corner and edge-sharing OLi2Bi2 tetrahedra. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), and two equivalent Bi(2) atoms. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), and two equivalent Bi(3) atoms. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), and two equivalent Bi(3) atoms. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Li(5), one Bi(1), and one Bi(2) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), and two equivalent Bi(4) atoms to form a mixture of distorted corner and edge-sharing OLi2Bi2 trigonal pyramids. In the seventh O site, O(7) is bonded to one Li(2), one Li(5), one Bi(1), and one Bi(4) atom to form a mixture of distorted corner and edge-sharing OLi2Bi2 tetrahedra. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to two equivalent Li(5) and two equivalent Bi(1) atoms. In the ninth O site, O(9) is bonded to one Li(1), one Li(2), and two equivalent Bi(4) atoms to form a mixture of distorted corner and edge-sharing OLi2Bi2 trigonal pyramids. In the tenth O site, O(10) is bonded to one Li(3), one Li(4), one Bi(2), and one Bi(3) atom to form distorted corner-sharing OLi2Bi2 trigonal pyramids. In the eleventh O site, O(11) is bonded to one Li(4), one Li(5), one Bi(1), and one Bi(2) atom to form distorted corner-sharing OLi2Bi2 trigonal pyramids. In the twelfth O site, O(12) is bonded in a distorted see-saw-like geometry to one Li(3), one Li(5), one Bi(2), and one Bi(3) atom.
Li5(BiO3)4 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(3), one O(6), and one O(9) atom. The Li(1)-O(1) bond length is 2.01 Å. The Li(1)-O(3) bond length is 1.99 Å. The Li(1)-O(6) bond length is 2.02 Å. The Li(1)-O(9) bond length is 1.92 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(4), one O(6), one O(7), and one O(9) atom. The Li(2)-O(4) bond length is 1.98 Å. The Li(2)-O(6) bond length is 1.91 Å. The Li(2)-O(7) bond length is 2.01 Å. The Li(2)-O(9) bond length is 2.02 Å. In the third Li site, Li(3) is bonded to one O(10), one O(12), one O(2), one O(3), and one O(4) atom to form distorted LiO5 square pyramids that share  a cornercorner with one Li(5)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, corners with two equivalent Li(4)O5 trigonal bipyramids,  an edgeedge with one Bi(2)O6 octahedra, and edges with three equivalent Bi(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-84°. The Li(3)-O(10) bond length is 2.06 Å. The Li(3)-O(12) bond length is 2.11 Å. The Li(3)-O(2) bond length is 2.30 Å. The Li(3)-O(3) bond length is 2.14 Å. The Li(3)-O(4) bond length is 2.32 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(10), one O(11), one O(2), and one O(5) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Bi(1)O6 octahedra,  a cornercorner with one Bi(2)O6 octahedra,  a cornercorner with one Bi(3)O6 octahedra,  a cornercorner with one Bi(4)O6 octahedra, corners with two equivalent Li(3)O5 square pyramids,  an edgeedge with one Li(5)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra, and edges with two equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-73°. The Li(4)-O(1) bond length is 2.03 Å. The Li(4)-O(10) bond length is 2.39 Å. The Li(4)-O(11) bond length is 2.01 Å. The Li(4)-O(2) bond length is 2.39 Å. The Li(4)-O(5) bond length is 2.14 Å. In the fifth Li site, Li(5) is bonded to one O(11), one O(12), one O(5), one O(7), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Bi(1)O6 octahedra,  a cornercorner with one Bi(2)O6 octahedra,  a cornercorner with one Bi(3)O6 octahedra,  a cornercorner with one Bi(4)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  an edgeedge with one Li(5)O6 octahedra,  an edgeedge with one Bi(2)O6 octahedra, edges with three equivalent Bi(1)O6 octahedra, and  an edgeedge with one Li(4)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 17-66°. The Li(5)-O(11) bond length is 2.42 Å. The Li(5)-O(12) bond length is 2.54 Å. The Li(5)-O(5) bond length is 2.53 Å. The Li(5)-O(7) bond length is 2.04 Å. There is one shorter (2.05 Å) and one longer (2.23 Å) Li(5)-O(8) bond length. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(11), one O(5), one O(7), and two equivalent O(8) atoms to form BiO6 octahedra that share  a cornercorner with one Li(5)O6 octahedra, corners with two equivalent Bi(4)O6 octahedra,  a cornercorner with one Li(4)O5 trigonal bipyramid,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Bi(2)O6 octahedra, edges with three equivalent Li(5)O6 octahedra, and  an edgeedge with one Li(4)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-62°. The Bi(1)-O(1) bond length is 2.13 Å. The Bi(1)-O(11) bond length is 2.19 Å. The Bi(1)-O(5) bond length is 2.27 Å. The Bi(1)-O(7) bond length is 2.13 Å. There is one shorter (2.16 Å) and one longer (2.19 Å) Bi(1)-O(8) bond length. In the second Bi site, Bi(2) is bonded to one O(10), one O(11), one O(12), one O(5), and two equivalent O(2) atoms to form BiO6 octahedra that share  a cornercorner with one Li(5)O6 octahedra, corners with two equivalent Li(3)O5 square pyramids,  a cornercorner with one Li(4)O5 trigonal bipyramid,  an edgeedge with one Li(5)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Bi(2)O6 octahedra,  an edgeedge with one Bi(3)O6 octahedra,  an edgeedge with one Li(3)O5 square pyramid, and edges with two equivalent Li(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 20°. The Bi(2)-O(10) bond length is 2.18 Å. The Bi(2)-O(11) bond length is 2.13 Å. The Bi(2)-O(12) bond length is 2.18 Å. The Bi(2)-O(5) bond length is 2.11 Å. There is one shorter (2.16 Å) and one longer (2.17 Å) Bi(2)-O(2) bond length. In the third Bi site, Bi(3) is bonded to one O(10), one O(12), two equivalent O(3), and two equivalent O(4) atoms to form BiO6 octahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one Li(4)O5 trigonal bipyramid,  an edgeedge with one Bi(2)O6 octahedra, edges with two equivalent Bi(3)O6 octahedra, and edges with three equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles are 17°. The Bi(3)-O(10) bond length is 2.18 Å. The Bi(3)-O(12) bond length is 2.15 Å. There is one shorter (2.15 Å) and one longer (2.19 Å) Bi(3)-O(3) bond length. There is one shorter (2.15 Å) and one longer (2.17 Å) Bi(3)-O(4) bond length. In the fourth Bi site, Bi(4) is bonded to one O(1), one O(7), two equivalent O(6), and two equivalent O(9) atoms to form distorted BiO6 octahedra that share  a cornercorner with one Li(5)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra,  a cornercorner with one Li(4)O5 trigonal bipyramid, and edges with two equivalent Bi(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-66°. The Bi(4)-O(1) bond length is 2.36 Å. The Bi(4)-O(7) bond length is 2.41 Å. There is one shorter (2.19 Å) and one longer (2.25 Å) Bi(4)-O(6) bond length. There is one shorter (2.18 Å) and one longer (2.24 Å) Bi(4)-O(9) bond length. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one Bi(1), and one Bi(4) atom to form a mixture of distorted corner and edge-sharing OLi2Bi2 tetrahedra. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), and two equivalent Bi(2) atoms. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), and two equivalent Bi(3) atoms. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), and two equivalent Bi(3) atoms. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Li(5), one Bi(1), and one Bi(2) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), and two equivalent Bi(4) atoms to form a mixture of distorted corner and edge-sharing OLi2Bi2 trigonal pyramids. In the seventh O site, O(7) is bonded to one Li(2), one Li(5), one Bi(1), and one Bi(4) atom to form a mixture of distorted corner and edge-sharing OLi2Bi2 tetrahedra. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to two equivalent Li(5) and two equivalent Bi(1) atoms. In the ninth O site, O(9) is bonded to one Li(1), one Li(2), and two equivalent Bi(4) atoms to form a mixture of distorted corner and edge-sharing OLi2Bi2 trigonal pyramids. In the tenth O site, O(10) is bonded to one Li(3), one Li(4), one Bi(2), and one Bi(3) atom to form distorted corner-sharing OLi2Bi2 trigonal pyramids. In the eleventh O site, O(11) is bonded to one Li(4), one Li(5), one Bi(1), and one Bi(2) atom to form distorted corner-sharing OLi2Bi2 trigonal pyramids. In the twelfth O site, O(12) is bonded in a distorted see-saw-like geometry to one Li(3), one Li(5), one Bi(2), and one Bi(3) atom.