Ba4Bi3O11 crystallizes in the orthorhombic Amm2 space group. Ba(1) is bonded in a 10-coordinate geometry to one O(3), one O(4), one O(6), one O(7), two equivalent O(1), two equivalent O(2), 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 corner-sharing BiO5 trigonal bipyramids. The corner-sharing octahedra are not tilted. 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 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-5°. 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 corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Ba(1), one Bi(1), and one Bi(2) atom to form distorted OBa4Bi2 octahedra that share corners with two equivalent O(7)Ba4Bi2 octahedra, corners with four equivalent O(2)Ba4Bi2 octahedra, corners with six equivalent O(1)Ba4Bi2 octahedra, edges with four equivalent O(5)Ba4Bi square pyramids,  a faceface with one O(7)Ba4Bi2 octahedra, and faces with two equivalent O(2)Ba4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 0-63°. 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(1)Ba4Bi2 octahedra, corners with four equivalent O(5)Ba4Bi square pyramids, edges with two equivalent O(2)Ba4Bi2 octahedra, faces with two equivalent O(1)Ba4Bi2 octahedra, faces with two equivalent O(7)Ba4Bi2 octahedra, and faces with two equivalent O(5)Ba4Bi square pyramids. The corner-sharing octahedral tilt angles range from 3-63°. 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 in a trigonal planar geometry to two equivalent Ba(1) and one Bi(1) atom. In the fifth O site, O(5) is bonded to four equivalent Ba(1) and one Bi(3) atom to form distorted OBa4Bi square pyramids that share corners with two equivalent O(7)Ba4Bi2 octahedra, corners with four equivalent O(2)Ba4Bi2 octahedra, corners with five equivalent O(5)Ba4Bi square pyramids, edges with four equivalent O(1)Ba4Bi2 octahedra,  a faceface with one O(7)Ba4Bi2 octahedra, and faces with two equivalent O(2)Ba4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 58-66°. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to 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(1)Ba4Bi2 octahedra, corners with four equivalent O(5)Ba4Bi square pyramids, faces with two equivalent O(1)Ba4Bi2 octahedra, faces with four equivalent O(2)Ba4Bi2 octahedra, and faces with two equivalent O(5)Ba4Bi square pyramids. The corner-sharing octahedral tilt angles are 56°.
Ba4Bi3O11 crystallizes in the orthorhombic Amm2 space group. Ba(1) is bonded in a 10-coordinate geometry to one O(3), one O(4), one O(6), one O(7), two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms. The Ba(1)-O(3) bond length is 3.23 Å. The Ba(1)-O(4) bond length is 2.59 Å. The Ba(1)-O(6) bond length is 3.07 Å. The Ba(1)-O(7) bond length is 2.98 Å. There is one shorter (3.10 Å) and one longer (3.13 Å) Ba(1)-O(1) bond length. There is one shorter (2.96 Å) and one longer (3.25 Å) Ba(1)-O(2) bond length. There is one shorter (2.87 Å) and one longer (3.35 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 corner-sharing BiO5 trigonal bipyramids. The corner-sharing octahedra are not tilted. The Bi(1)-O(6) bond length is 2.03 Å. Both Bi(1)-O(1) bond lengths are 2.23 Å. Both Bi(1)-O(4) bond lengths are 2.04 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 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-5°. The Bi(2)-O(3) bond length is 2.17 Å. The Bi(2)-O(7) bond length is 2.20 Å. Both Bi(2)-O(1) bond lengths are 2.24 Å. Both Bi(2)-O(2) bond lengths are 2.19 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 corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. The Bi(3)-O(3) bond length is 2.15 Å. The Bi(3)-O(7) bond length is 2.27 Å. Both Bi(3)-O(2) bond lengths are 2.21 Å. Both Bi(3)-O(5) bond lengths are 2.07 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Ba(1), one Bi(1), and one Bi(2) atom to form distorted OBa4Bi2 octahedra that share corners with two equivalent O(7)Ba4Bi2 octahedra, corners with four equivalent O(2)Ba4Bi2 octahedra, corners with six equivalent O(1)Ba4Bi2 octahedra, edges with four equivalent O(5)Ba4Bi square pyramids,  a faceface with one O(7)Ba4Bi2 octahedra, and faces with two equivalent O(2)Ba4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 0-63°. 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(1)Ba4Bi2 octahedra, corners with four equivalent O(5)Ba4Bi square pyramids, edges with two equivalent O(2)Ba4Bi2 octahedra, faces with two equivalent O(1)Ba4Bi2 octahedra, faces with two equivalent O(7)Ba4Bi2 octahedra, and faces with two equivalent O(5)Ba4Bi square pyramids. The corner-sharing octahedral tilt angles range from 3-63°. 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 in a trigonal planar geometry to two equivalent Ba(1) and one Bi(1) atom. In the fifth O site, O(5) is bonded to four equivalent Ba(1) and one Bi(3) atom to form distorted OBa4Bi square pyramids that share corners with two equivalent O(7)Ba4Bi2 octahedra, corners with four equivalent O(2)Ba4Bi2 octahedra, corners with five equivalent O(5)Ba4Bi square pyramids, edges with four equivalent O(1)Ba4Bi2 octahedra,  a faceface with one O(7)Ba4Bi2 octahedra, and faces with two equivalent O(2)Ba4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 58-66°. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to 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(1)Ba4Bi2 octahedra, corners with four equivalent O(5)Ba4Bi square pyramids, faces with two equivalent O(1)Ba4Bi2 octahedra, faces with four equivalent O(2)Ba4Bi2 octahedra, and faces with two equivalent O(5)Ba4Bi square pyramids. The corner-sharing octahedral tilt angles are 56°.