Ba4Bi3LiO11 crystallizes in the orthorhombic Amm2 space group. Li(1) is bonded to one O(6), two equivalent O(4), and two equivalent O(5) atoms to form LiO5 square pyramids that share corners with two equivalent Bi(3)O6 octahedra and corners with three equivalent Bi(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 8°. Ba(1) is bonded in a distorted q6 geometry to one O(3), one O(6), one O(7), two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(6), two equivalent O(1), and two equivalent O(4) atoms to form BiO5 square pyramids that share corners with two equivalent Bi(2)O6 octahedra and corners with three equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 13°. In the second Bi site, Bi(2) is bonded to one O(3), one O(7), two equivalent O(1), and two equivalent O(2) atoms to form BiO6 octahedra that share corners with four equivalent Bi(3)O6 octahedra and corners with two equivalent Bi(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. In the third Bi site, Bi(3) is bonded to one O(3), one O(7), two equivalent O(2), and two equivalent O(5) atoms to form BiO6 octahedra that share corners with four equivalent Bi(2)O6 octahedra and corners with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to four equivalent Ba(1), one Bi(1), and one Bi(2) atom. In the second O site, O(2) is bonded to four equivalent Ba(1), one Bi(2), and one Bi(3) atom to form distorted OBa4Bi2 octahedra that share corners with two equivalent O(2)Ba4Bi2 octahedra, corners with four equivalent O(4)Ba4LiBi octahedra, corners with four equivalent O(5)Ba4LiBi octahedra, edges with two equivalent O(2)Ba4Bi2 octahedra, edges with two equivalent O(4)Ba4LiBi octahedra, faces with two equivalent O(7)Ba4Bi2 octahedra, and faces with two equivalent O(5)Ba4LiBi octahedra. The corner-sharing octahedral tilt angles range from 1-64°. In the third O site, O(3) is bonded in a distorted linear geometry to four equivalent Ba(1), one Bi(2), and one Bi(3) atom. In the fourth O site, O(4) is bonded to one Li(1), four equivalent Ba(1), and one Bi(1) atom to form distorted OBa4LiBi octahedra that share corners with two equivalent O(4)Ba4LiBi octahedra, corners with four equivalent O(2)Ba4Bi2 octahedra, corners with four equivalent O(7)Ba4Bi2 octahedra, corners with four equivalent O(5)Ba4LiBi octahedra, edges with two equivalent O(2)Ba4Bi2 octahedra, edges with two equivalent O(4)Ba4LiBi octahedra, and faces with two equivalent O(5)Ba4LiBi octahedra. The corner-sharing octahedral tilt angles range from 5-62°. In the fifth O site, O(5) is bonded to one Li(1), four equivalent Ba(1), and one Bi(3) atom to form distorted OBa4LiBi octahedra that share corners with two equivalent O(7)Ba4Bi2 octahedra, corners with four equivalent O(2)Ba4Bi2 octahedra, corners with four equivalent O(4)Ba4LiBi octahedra, corners with six equivalent O(5)Ba4LiBi octahedra,  a faceface with one O(7)Ba4Bi2 octahedra, faces with two equivalent O(2)Ba4Bi2 octahedra, and faces with two equivalent O(4)Ba4LiBi octahedra. The corner-sharing octahedral tilt angles range from 2-64°. In the sixth O site, O(6) is bonded in a distorted linear geometry to one Li(1), four equivalent Ba(1), and one Bi(1) atom. In the seventh O site, O(7) is bonded to four equivalent Ba(1), one Bi(2), and one Bi(3) atom to form distorted OBa4Bi2 octahedra that share corners with four equivalent O(5)Ba4LiBi octahedra, corners with eight equivalent O(4)Ba4LiBi octahedra, faces with two equivalent O(5)Ba4LiBi octahedra, and faces with four equivalent O(2)Ba4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 55-63°.
Ba4Bi3LiO11 crystallizes in the orthorhombic Amm2 space group. Li(1) is bonded to one O(6), two equivalent O(4), and two equivalent O(5) atoms to form LiO5 square pyramids that share corners with two equivalent Bi(3)O6 octahedra and corners with three equivalent Bi(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 8°. The Li(1)-O(6) bond length is 1.90 Å. Both Li(1)-O(4) bond lengths are 2.23 Å. Both Li(1)-O(5) bond lengths are 2.25 Å. Ba(1) is bonded in a distorted q6 geometry to one O(3), one O(6), one O(7), two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms. The Ba(1)-O(3) bond length is 3.19 Å. The Ba(1)-O(6) bond length is 2.99 Å. The Ba(1)-O(7) bond length is 3.05 Å. There is one shorter (2.95 Å) and one longer (3.24 Å) Ba(1)-O(1) bond length. There is one shorter (3.03 Å) and one longer (3.17 Å) Ba(1)-O(2) bond length. There is one shorter (2.97 Å) and one longer (3.13 Å) Ba(1)-O(4) bond length. There is one shorter (2.96 Å) and one longer (3.21 Å) Ba(1)-O(5) bond length. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(6), two equivalent O(1), and two equivalent O(4) atoms to form BiO5 square pyramids that share corners with two equivalent Bi(2)O6 octahedra and corners with three equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 13°. The Bi(1)-O(6) bond length is 2.06 Å. Both Bi(1)-O(1) bond lengths are 2.18 Å. Both Bi(1)-O(4) bond lengths are 2.17 Å. In the second Bi site, Bi(2) is bonded to one O(3), one O(7), two equivalent O(1), and two equivalent O(2) atoms to form BiO6 octahedra that share corners with four equivalent Bi(3)O6 octahedra and corners with two equivalent Bi(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. The Bi(2)-O(3) bond length is 2.15 Å. The Bi(2)-O(7) bond length is 2.22 Å. Both Bi(2)-O(1) bond lengths are 2.21 Å. Both Bi(2)-O(2) bond lengths are 2.21 Å. In the third Bi site, Bi(3) is bonded to one O(3), one O(7), two equivalent O(2), and two equivalent O(5) atoms to form BiO6 octahedra that share corners with four equivalent Bi(2)O6 octahedra and corners with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. The Bi(3)-O(3) bond length is 2.11 Å. The Bi(3)-O(7) bond length is 2.19 Å. Both Bi(3)-O(2) bond lengths are 2.17 Å. Both Bi(3)-O(5) bond lengths are 2.12 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to four equivalent Ba(1), one Bi(1), and one Bi(2) atom. In the second O site, O(2) is bonded to four equivalent Ba(1), one Bi(2), and one Bi(3) atom to form distorted OBa4Bi2 octahedra that share corners with two equivalent O(2)Ba4Bi2 octahedra, corners with four equivalent O(4)Ba4LiBi octahedra, corners with four equivalent O(5)Ba4LiBi octahedra, edges with two equivalent O(2)Ba4Bi2 octahedra, edges with two equivalent O(4)Ba4LiBi octahedra, faces with two equivalent O(7)Ba4Bi2 octahedra, and faces with two equivalent O(5)Ba4LiBi octahedra. The corner-sharing octahedral tilt angles range from 1-64°. In the third O site, O(3) is bonded in a distorted linear geometry to four equivalent Ba(1), one Bi(2), and one Bi(3) atom. In the fourth O site, O(4) is bonded to one Li(1), four equivalent Ba(1), and one Bi(1) atom to form distorted OBa4LiBi octahedra that share corners with two equivalent O(4)Ba4LiBi octahedra, corners with four equivalent O(2)Ba4Bi2 octahedra, corners with four equivalent O(7)Ba4Bi2 octahedra, corners with four equivalent O(5)Ba4LiBi octahedra, edges with two equivalent O(2)Ba4Bi2 octahedra, edges with two equivalent O(4)Ba4LiBi octahedra, and faces with two equivalent O(5)Ba4LiBi octahedra. The corner-sharing octahedral tilt angles range from 5-62°. In the fifth O site, O(5) is bonded to one Li(1), four equivalent Ba(1), and one Bi(3) atom to form distorted OBa4LiBi octahedra that share corners with two equivalent O(7)Ba4Bi2 octahedra, corners with four equivalent O(2)Ba4Bi2 octahedra, corners with four equivalent O(4)Ba4LiBi octahedra, corners with six equivalent O(5)Ba4LiBi octahedra,  a faceface with one O(7)Ba4Bi2 octahedra, faces with two equivalent O(2)Ba4Bi2 octahedra, and faces with two equivalent O(4)Ba4LiBi octahedra. The corner-sharing octahedral tilt angles range from 2-64°. In the sixth O site, O(6) is bonded in a distorted linear geometry to one Li(1), four equivalent Ba(1), and one Bi(1) atom. In the seventh O site, O(7) is bonded to four equivalent Ba(1), one Bi(2), and one Bi(3) atom to form distorted OBa4Bi2 octahedra that share corners with four equivalent O(5)Ba4LiBi octahedra, corners with eight equivalent O(4)Ba4LiBi octahedra, faces with two equivalent O(5)Ba4LiBi octahedra, and faces with four equivalent O(2)Ba4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 55-63°.