Ba8Bi4O17 crystallizes in the monoclinic Cm space group. There are five inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one O(1), one O(11), one O(12), one O(13), one O(2), one O(4), one O(8), and one O(9) atom. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to one O(1), one O(10), one O(13), one O(14), one O(3), one O(5), one O(6), one O(7), one O(8), and one O(9) atom. In the third Ba site, Ba(3) is bonded in a 10-coordinate geometry to one O(10), one O(11), one O(12), one O(14), one O(4), one O(5), one O(6), one O(7), and two equivalent O(8) atoms. In the fourth Ba site, Ba(4) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(3), and two equivalent O(7) atoms. In the fifth Ba site, Ba(5) is bonded to one O(11), one O(12), one O(13), one O(9), and two equivalent O(1) atoms to form BaO6 octahedra that share corners with two equivalent Bi(3)O6 octahedra, corners with two equivalent Bi(4)O6 octahedra, and corners with two equivalent Bi(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 1-10°. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(8) atoms to form BiO6 octahedra that share corners with two equivalent Bi(3)O6 octahedra, corners with two equivalent Bi(4)O6 octahedra, and corners with two equivalent Bi(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-10°. In the second Bi site, Bi(2) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted BiO5 trigonal bipyramids that share corners with two equivalent Ba(5)O6 octahedra and corners with two equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-42°. In the third Bi site, Bi(3) is bonded to one O(10), one O(11), one O(12), one O(14), and two equivalent O(8) atoms to form BiO6 octahedra that share corners with two equivalent Ba(5)O6 octahedra and corners with two equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. In the fourth Bi site, Bi(4) is bonded to one O(13), one O(5), one O(6), one O(9), and two equivalent O(7) atoms to form BiO6 octahedra that share corners with two equivalent Ba(5)O6 octahedra and corners with two equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded to one Ba(1), one Ba(2), one Ba(5), and one Bi(2) atom to form distorted OBa3Bi trigonal pyramids that share  a cornercorner with one O(5)Ba4Bi2 octahedra,  a cornercorner with one O(10)Ba5Bi octahedra, corners with two equivalent O(8)Ba4Bi2 octahedra, corners with two equivalent O(12)Ba5Bi octahedra, corners with two equivalent O(1)Ba3Bi trigonal pyramids, and  an edgeedge with one O(3)Ba3Bi tetrahedra. The corner-sharing octahedral tilt angles range from 24-81°. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to two equivalent Ba(1), one Bi(1), and one Bi(2) atom. In the third O site, O(3) is bonded to one Ba(4), two equivalent Ba(2), and one Bi(2) atom to form distorted OBa3Bi tetrahedra that share  a cornercorner with one O(10)Ba5Bi octahedra, corners with two equivalent O(5)Ba4Bi2 octahedra, corners with two equivalent O(8)Ba4Bi2 octahedra,  an edgeedge with one O(10)Ba5Bi octahedra, and edges with two equivalent O(1)Ba3Bi trigonal pyramids. The corner-sharing octahedral tilt angles range from 17-60°. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Ba(3), one Bi(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded to two equivalent Ba(2), two equivalent Ba(3), one Bi(1), and one Bi(4) atom to form distorted OBa4Bi2 octahedra that share corners with two equivalent O(8)Ba4Bi2 octahedra, corners with two equivalent O(12)Ba5Bi octahedra, corners with two equivalent O(3)Ba3Bi tetrahedra, corners with two equivalent O(1)Ba3Bi trigonal pyramids, edges with two equivalent O(10)Ba5Bi octahedra, and faces with two equivalent O(8)Ba4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 59-62°. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to two equivalent Ba(2), two equivalent Ba(3), one Bi(1), and one Bi(4) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Ba(2), one Ba(3), one Ba(4), and one Bi(4) atom. In the eighth O site, O(8) is bonded to one Ba(1), one Ba(2), two equivalent Ba(3), one Bi(1), and one Bi(3) atom to form distorted OBa4Bi2 octahedra that share  a cornercorner with one O(5)Ba4Bi2 octahedra,  a cornercorner with one O(10)Ba5Bi octahedra,  a cornercorner with one O(12)Ba5Bi octahedra, corners with four equivalent O(8)Ba4Bi2 octahedra,  a cornercorner with one O(3)Ba3Bi tetrahedra, corners with two equivalent O(1)Ba3Bi trigonal pyramids,  a faceface with one O(5)Ba4Bi2 octahedra,  a faceface with one O(10)Ba5Bi octahedra, and  a faceface with one O(12)Ba5Bi octahedra. The corner-sharing octahedral tilt angles range from 3-61°. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Ba(5), two equivalent Ba(1), two equivalent Ba(2), and one Bi(4) atom. In the tenth O site, O(10) is bonded to one Ba(4), two equivalent Ba(2), two equivalent Ba(3), and one Bi(3) atom to form distorted OBa5Bi octahedra that share corners with two equivalent O(8)Ba4Bi2 octahedra,  a cornercorner with one O(3)Ba3Bi tetrahedra, corners with two equivalent O(1)Ba3Bi trigonal pyramids, edges with two equivalent O(5)Ba4Bi2 octahedra,  an edgeedge with one O(3)Ba3Bi tetrahedra,  a faceface with one O(12)Ba5Bi octahedra, and faces with two equivalent O(8)Ba4Bi2 octahedra. The corner-sharing octahedral tilt angles are 51°. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Ba(5), two equivalent Ba(1), two equivalent Ba(3), and one Bi(3) atom. In the twelfth O site, O(12) is bonded to one Ba(5), two equivalent Ba(1), two equivalent Ba(3), and one Bi(3) atom to form distorted OBa5Bi octahedra that share corners with two equivalent O(5)Ba4Bi2 octahedra, corners with two equivalent O(8)Ba4Bi2 octahedra, corners with four equivalent O(1)Ba3Bi trigonal pyramids,  a faceface with one O(10)Ba5Bi octahedra, and faces with two equivalent O(8)Ba4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 61-62°. In the thirteenth O site, O(13) is bonded in a distorted linear geometry to one Ba(5), two equivalent Ba(1), two equivalent Ba(2), and one Bi(4) atom. In the fourteenth O site, O(14) is bonded in a 6-coordinate geometry to one Ba(4), two equivalent Ba(2), two equivalent Ba(3), and one Bi(3) atom.
Ba8Bi4O17 crystallizes in the monoclinic Cm space group. There are five inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one O(1), one O(11), one O(12), one O(13), one O(2), one O(4), one O(8), and one O(9) atom. The Ba(1)-O(1) bond length is 2.68 Å. The Ba(1)-O(11) bond length is 2.76 Å. The Ba(1)-O(12) bond length is 2.98 Å. The Ba(1)-O(13) bond length is 3.32 Å. The Ba(1)-O(2) bond length is 2.74 Å. The Ba(1)-O(4) bond length is 3.38 Å. The Ba(1)-O(8) bond length is 2.84 Å. The Ba(1)-O(9) bond length is 3.51 Å. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to one O(1), one O(10), one O(13), one O(14), one O(3), one O(5), one O(6), one O(7), one O(8), and one O(9) atom. The Ba(2)-O(1) bond length is 2.86 Å. The Ba(2)-O(10) bond length is 3.13 Å. The Ba(2)-O(13) bond length is 3.26 Å. The Ba(2)-O(14) bond length is 3.27 Å. The Ba(2)-O(3) bond length is 2.93 Å. The Ba(2)-O(5) bond length is 3.17 Å. The Ba(2)-O(6) bond length is 3.17 Å. The Ba(2)-O(7) bond length is 2.89 Å. The Ba(2)-O(8) bond length is 3.12 Å. The Ba(2)-O(9) bond length is 2.88 Å. In the third Ba site, Ba(3) is bonded in a 10-coordinate geometry to one O(10), one O(11), one O(12), one O(14), one O(4), one O(5), one O(6), one O(7), and two equivalent O(8) atoms. The Ba(3)-O(10) bond length is 3.07 Å. The Ba(3)-O(11) bond length is 3.36 Å. The Ba(3)-O(12) bond length is 3.14 Å. The Ba(3)-O(14) bond length is 2.84 Å. The Ba(3)-O(4) bond length is 3.33 Å. The Ba(3)-O(5) bond length is 3.09 Å. The Ba(3)-O(6) bond length is 3.04 Å. The Ba(3)-O(7) bond length is 2.61 Å. There is one shorter (3.19 Å) and one longer (3.24 Å) Ba(3)-O(8) bond length. In the fourth Ba site, Ba(4) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(3), and two equivalent O(7) atoms. The Ba(4)-O(10) bond length is 2.57 Å. The Ba(4)-O(14) bond length is 2.70 Å. The Ba(4)-O(3) bond length is 2.55 Å. Both Ba(4)-O(7) bond lengths are 2.51 Å. In the fifth Ba site, Ba(5) is bonded to one O(11), one O(12), one O(13), one O(9), and two equivalent O(1) atoms to form BaO6 octahedra that share corners with two equivalent Bi(3)O6 octahedra, corners with two equivalent Bi(4)O6 octahedra, and corners with two equivalent Bi(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 1-10°. The Ba(5)-O(11) bond length is 2.52 Å. The Ba(5)-O(12) bond length is 2.55 Å. The Ba(5)-O(13) bond length is 2.47 Å. The Ba(5)-O(9) bond length is 2.51 Å. Both Ba(5)-O(1) bond lengths are 2.69 Å. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(8) atoms to form BiO6 octahedra that share corners with two equivalent Bi(3)O6 octahedra, corners with two equivalent Bi(4)O6 octahedra, and corners with two equivalent Bi(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-10°. The Bi(1)-O(2) bond length is 2.48 Å. The Bi(1)-O(4) bond length is 2.57 Å. The Bi(1)-O(5) bond length is 2.25 Å. The Bi(1)-O(6) bond length is 2.19 Å. Both Bi(1)-O(8) bond lengths are 2.30 Å. In the second Bi site, Bi(2) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted BiO5 trigonal bipyramids that share corners with two equivalent Ba(5)O6 octahedra and corners with two equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-42°. The Bi(2)-O(2) bond length is 2.18 Å. The Bi(2)-O(3) bond length is 2.11 Å. The Bi(2)-O(4) bond length is 2.08 Å. Both Bi(2)-O(1) bond lengths are 2.10 Å. In the third Bi site, Bi(3) is bonded to one O(10), one O(11), one O(12), one O(14), and two equivalent O(8) atoms to form BiO6 octahedra that share corners with two equivalent Ba(5)O6 octahedra and corners with two equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. The Bi(3)-O(10) bond length is 2.12 Å. The Bi(3)-O(11) bond length is 2.14 Å. The Bi(3)-O(12) bond length is 2.15 Å. The Bi(3)-O(14) bond length is 2.12 Å. Both Bi(3)-O(8) bond lengths are 2.19 Å. In the fourth Bi site, Bi(4) is bonded to one O(13), one O(5), one O(6), one O(9), and two equivalent O(7) atoms to form BiO6 octahedra that share corners with two equivalent Ba(5)O6 octahedra and corners with two equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. The Bi(4)-O(13) bond length is 2.05 Å. The Bi(4)-O(5) bond length is 2.23 Å. The Bi(4)-O(6) bond length is 2.28 Å. The Bi(4)-O(9) bond length is 2.12 Å. Both Bi(4)-O(7) bond lengths are 2.11 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded to one Ba(1), one Ba(2), one Ba(5), and one Bi(2) atom to form distorted OBa3Bi trigonal pyramids that share  a cornercorner with one O(5)Ba4Bi2 octahedra,  a cornercorner with one O(10)Ba5Bi octahedra, corners with two equivalent O(8)Ba4Bi2 octahedra, corners with two equivalent O(12)Ba5Bi octahedra, corners with two equivalent O(1)Ba3Bi trigonal pyramids, and  an edgeedge with one O(3)Ba3Bi tetrahedra. The corner-sharing octahedral tilt angles range from 24-81°. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to two equivalent Ba(1), one Bi(1), and one Bi(2) atom. In the third O site, O(3) is bonded to one Ba(4), two equivalent Ba(2), and one Bi(2) atom to form distorted OBa3Bi tetrahedra that share  a cornercorner with one O(10)Ba5Bi octahedra, corners with two equivalent O(5)Ba4Bi2 octahedra, corners with two equivalent O(8)Ba4Bi2 octahedra,  an edgeedge with one O(10)Ba5Bi octahedra, and edges with two equivalent O(1)Ba3Bi trigonal pyramids. The corner-sharing octahedral tilt angles range from 17-60°. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Ba(3), one Bi(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded to two equivalent Ba(2), two equivalent Ba(3), one Bi(1), and one Bi(4) atom to form distorted OBa4Bi2 octahedra that share corners with two equivalent O(8)Ba4Bi2 octahedra, corners with two equivalent O(12)Ba5Bi octahedra, corners with two equivalent O(3)Ba3Bi tetrahedra, corners with two equivalent O(1)Ba3Bi trigonal pyramids, edges with two equivalent O(10)Ba5Bi octahedra, and faces with two equivalent O(8)Ba4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 59-62°. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to two equivalent Ba(2), two equivalent Ba(3), one Bi(1), and one Bi(4) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Ba(2), one Ba(3), one Ba(4), and one Bi(4) atom. In the eighth O site, O(8) is bonded to one Ba(1), one Ba(2), two equivalent Ba(3), one Bi(1), and one Bi(3) atom to form distorted OBa4Bi2 octahedra that share  a cornercorner with one O(5)Ba4Bi2 octahedra,  a cornercorner with one O(10)Ba5Bi octahedra,  a cornercorner with one O(12)Ba5Bi octahedra, corners with four equivalent O(8)Ba4Bi2 octahedra,  a cornercorner with one O(3)Ba3Bi tetrahedra, corners with two equivalent O(1)Ba3Bi trigonal pyramids,  a faceface with one O(5)Ba4Bi2 octahedra,  a faceface with one O(10)Ba5Bi octahedra, and  a faceface with one O(12)Ba5Bi octahedra. The corner-sharing octahedral tilt angles range from 3-61°. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Ba(5), two equivalent Ba(1), two equivalent Ba(2), and one Bi(4) atom. In the tenth O site, O(10) is bonded to one Ba(4), two equivalent Ba(2), two equivalent Ba(3), and one Bi(3) atom to form distorted OBa5Bi octahedra that share corners with two equivalent O(8)Ba4Bi2 octahedra,  a cornercorner with one O(3)Ba3Bi tetrahedra, corners with two equivalent O(1)Ba3Bi trigonal pyramids, edges with two equivalent O(5)Ba4Bi2 octahedra,  an edgeedge with one O(3)Ba3Bi tetrahedra,  a faceface with one O(12)Ba5Bi octahedra, and faces with two equivalent O(8)Ba4Bi2 octahedra. The corner-sharing octahedral tilt angles are 51°. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Ba(5), two equivalent Ba(1), two equivalent Ba(3), and one Bi(3) atom. In the twelfth O site, O(12) is bonded to one Ba(5), two equivalent Ba(1), two equivalent Ba(3), and one Bi(3) atom to form distorted OBa5Bi octahedra that share corners with two equivalent O(5)Ba4Bi2 octahedra, corners with two equivalent O(8)Ba4Bi2 octahedra, corners with four equivalent O(1)Ba3Bi trigonal pyramids,  a faceface with one O(10)Ba5Bi octahedra, and faces with two equivalent O(8)Ba4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 61-62°. In the thirteenth O site, O(13) is bonded in a distorted linear geometry to one Ba(5), two equivalent Ba(1), two equivalent Ba(2), and one Bi(4) atom. In the fourteenth O site, O(14) is bonded in a 6-coordinate geometry to one Ba(4), two equivalent Ba(2), two equivalent Ba(3), and one Bi(3) atom.