Ba4La4Co8O23 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to two equivalent O(3), two equivalent O(4), two equivalent O(5), two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms to form BaO12 cuboctahedra that share corners with four equivalent Ba(2)O12 cuboctahedra, faces with two equivalent Ba(1)O12 cuboctahedra, faces with two equivalent Ba(2)O12 cuboctahedra, faces with two equivalent Co(1)O6 octahedra, faces with two equivalent Co(2)O6 octahedra, faces with two equivalent Co(3)O6 octahedra, and faces with two equivalent Co(4)O5 square pyramids. In the second Ba site, Ba(2) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(5), two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms to form BaO12 cuboctahedra that share corners with four equivalent Ba(1)O12 cuboctahedra, faces with two equivalent Ba(1)O12 cuboctahedra, faces with two equivalent Ba(2)O12 cuboctahedra, faces with two equivalent Co(1)O6 octahedra, faces with two equivalent Co(2)O6 octahedra, faces with two equivalent Co(3)O6 octahedra, and faces with two equivalent Co(4)O5 square pyramids. La(1) is bonded in a 11-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(4), two equivalent O(5), two equivalent O(6), and two equivalent O(9) atoms. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(4), one O(8), one O(9), and two equivalent O(5) atoms to form CoO6 octahedra that share corners with two equivalent Co(3)O6 octahedra, corners with three equivalent Co(2)O6 octahedra,  a cornercorner with one Co(4)O5 square pyramid, faces with two equivalent Ba(1)O12 cuboctahedra, and faces with two equivalent Ba(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second Co site, Co(2) is bonded to one O(2), one O(3), one O(7), one O(9), and two equivalent O(5) atoms to form CoO6 octahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with three equivalent Co(1)O6 octahedra, corners with two equivalent Co(4)O5 square pyramids, faces with two equivalent Ba(1)O12 cuboctahedra, and faces with two equivalent Ba(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the third Co site, Co(3) is bonded to one O(1), one O(10), one O(3), one O(8), and two equivalent O(6) atoms to form CoO6 octahedra that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(4)O5 square pyramids, faces with two equivalent Ba(1)O12 cuboctahedra, and faces with two equivalent Ba(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the fourth Co site, Co(4) is bonded to one O(2), one O(4), one O(7), and two equivalent O(6) atoms to form CoO5 square pyramids that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, faces with two equivalent Ba(1)O12 cuboctahedra, and faces with two equivalent Ba(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 2-18°. There are ten inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ba(2), two equivalent La(1), one Co(1), and one Co(3) atom to form distorted OBa2La2Co2 octahedra that share  a cornercorner with one O(3)Ba2La2Co2 octahedra, corners with four equivalent O(7)Ba4Co2 octahedra,  an edgeedge with one O(1)Ba2La2Co2 octahedra,  an edgeedge with one O(3)Ba2La2Co2 octahedra, and faces with two equivalent O(8)Ba4Co2 octahedra. The corner-sharing octahedral tilt angles range from 7-63°. In the second O site, O(2) is bonded in a 6-coordinate geometry to two equivalent Ba(2), two equivalent La(1), one Co(2), and one Co(4) atom. In the third O site, O(3) is bonded to two equivalent Ba(1), two equivalent La(1), one Co(2), and one Co(3) atom to form distorted OBa2La2Co2 octahedra that share  a cornercorner with one O(1)Ba2La2Co2 octahedra, corners with two equivalent O(3)Ba2La2Co2 octahedra, corners with two equivalent O(7)Ba4Co2 octahedra, corners with two equivalent O(8)Ba4Co2 octahedra,  an edgeedge with one O(1)Ba2La2Co2 octahedra,  a faceface with one O(7)Ba4Co2 octahedra, and  a faceface with one O(8)Ba4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent La(1), one Co(1), and one Co(4) atom. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), two equivalent La(1), one Co(1), and one Co(2) atom. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), two equivalent La(1), one Co(3), and one Co(4) atom. In the seventh O site, O(7) is bonded to two equivalent Ba(1), two equivalent Ba(2), one Co(2), and one Co(4) atom to form distorted OBa4Co2 octahedra that share corners with two equivalent O(3)Ba2La2Co2 octahedra, corners with two equivalent O(7)Ba4Co2 octahedra, corners with two equivalent O(8)Ba4Co2 octahedra, corners with four equivalent O(1)Ba2La2Co2 octahedra,  an edgeedge with one O(7)Ba4Co2 octahedra, edges with three equivalent O(8)Ba4Co2 octahedra, and  a faceface with one O(3)Ba2La2Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-63°. In the eighth O site, O(8) is bonded to two equivalent Ba(1), two equivalent Ba(2), one Co(1), and one Co(3) atom to form distorted OBa4Co2 octahedra that share corners with two equivalent O(3)Ba2La2Co2 octahedra, corners with two equivalent O(7)Ba4Co2 octahedra, corners with two equivalent O(8)Ba4Co2 octahedra,  an edgeedge with one O(8)Ba4Co2 octahedra, edges with three equivalent O(7)Ba4Co2 octahedra,  a faceface with one O(3)Ba2La2Co2 octahedra, and faces with two equivalent O(1)Ba2La2Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-59°. In the ninth O site, O(9) is bonded in a distorted linear geometry to four equivalent La(1), one Co(1), and one Co(2) atom. In the tenth O site, O(10) is bonded in a distorted linear geometry to four equivalent La(1) and two equivalent Co(3) atoms.
Ba4La4Co8O23 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to two equivalent O(3), two equivalent O(4), two equivalent O(5), two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms to form BaO12 cuboctahedra that share corners with four equivalent Ba(2)O12 cuboctahedra, faces with two equivalent Ba(1)O12 cuboctahedra, faces with two equivalent Ba(2)O12 cuboctahedra, faces with two equivalent Co(1)O6 octahedra, faces with two equivalent Co(2)O6 octahedra, faces with two equivalent Co(3)O6 octahedra, and faces with two equivalent Co(4)O5 square pyramids. Both Ba(1)-O(3) bond lengths are 2.89 Å. Both Ba(1)-O(4) bond lengths are 3.00 Å. Both Ba(1)-O(5) bond lengths are 2.90 Å. Both Ba(1)-O(6) bond lengths are 3.00 Å. Both Ba(1)-O(7) bond lengths are 2.85 Å. Both Ba(1)-O(8) bond lengths are 2.79 Å. In the second Ba site, Ba(2) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(5), two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms to form BaO12 cuboctahedra that share corners with four equivalent Ba(1)O12 cuboctahedra, faces with two equivalent Ba(1)O12 cuboctahedra, faces with two equivalent Ba(2)O12 cuboctahedra, faces with two equivalent Co(1)O6 octahedra, faces with two equivalent Co(2)O6 octahedra, faces with two equivalent Co(3)O6 octahedra, and faces with two equivalent Co(4)O5 square pyramids. Both Ba(2)-O(1) bond lengths are 2.86 Å. Both Ba(2)-O(2) bond lengths are 3.04 Å. Both Ba(2)-O(5) bond lengths are 2.91 Å. Both Ba(2)-O(6) bond lengths are 3.01 Å. Both Ba(2)-O(7) bond lengths are 2.81 Å. Both Ba(2)-O(8) bond lengths are 2.80 Å. La(1) is bonded in a 11-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(4), two equivalent O(5), two equivalent O(6), and two equivalent O(9) atoms. The La(1)-O(1) bond length is 2.62 Å. The La(1)-O(10) bond length is 2.75 Å. The La(1)-O(2) bond length is 2.63 Å. The La(1)-O(3) bond length is 2.61 Å. The La(1)-O(4) bond length is 2.63 Å. There is one shorter (2.67 Å) and one longer (2.68 Å) La(1)-O(5) bond length. There is one shorter (2.59 Å) and one longer (2.60 Å) La(1)-O(6) bond length. There is one shorter (2.72 Å) and one longer (2.91 Å) La(1)-O(9) bond length. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(4), one O(8), one O(9), and two equivalent O(5) atoms to form CoO6 octahedra that share corners with two equivalent Co(3)O6 octahedra, corners with three equivalent Co(2)O6 octahedra,  a cornercorner with one Co(4)O5 square pyramid, faces with two equivalent Ba(1)O12 cuboctahedra, and faces with two equivalent Ba(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-9°. The Co(1)-O(1) bond length is 2.08 Å. The Co(1)-O(4) bond length is 2.09 Å. The Co(1)-O(8) bond length is 1.99 Å. The Co(1)-O(9) bond length is 2.05 Å. Both Co(1)-O(5) bond lengths are 1.88 Å. In the second Co site, Co(2) is bonded to one O(2), one O(3), one O(7), one O(9), and two equivalent O(5) atoms to form CoO6 octahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with three equivalent Co(1)O6 octahedra, corners with two equivalent Co(4)O5 square pyramids, faces with two equivalent Ba(1)O12 cuboctahedra, and faces with two equivalent Ba(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 5-9°. The Co(2)-O(2) bond length is 2.09 Å. The Co(2)-O(3) bond length is 2.09 Å. The Co(2)-O(7) bond length is 1.80 Å. The Co(2)-O(9) bond length is 1.81 Å. Both Co(2)-O(5) bond lengths are 2.09 Å. In the third Co site, Co(3) is bonded to one O(1), one O(10), one O(3), one O(8), and two equivalent O(6) atoms to form CoO6 octahedra that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(4)O5 square pyramids, faces with two equivalent Ba(1)O12 cuboctahedra, and faces with two equivalent Ba(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-8°. The Co(3)-O(1) bond length is 1.95 Å. The Co(3)-O(10) bond length is 1.92 Å. The Co(3)-O(3) bond length is 1.93 Å. The Co(3)-O(8) bond length is 1.93 Å. Both Co(3)-O(6) bond lengths are 2.11 Å. In the fourth Co site, Co(4) is bonded to one O(2), one O(4), one O(7), and two equivalent O(6) atoms to form CoO5 square pyramids that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, faces with two equivalent Ba(1)O12 cuboctahedra, and faces with two equivalent Ba(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 2-18°. The Co(4)-O(2) bond length is 1.91 Å. The Co(4)-O(4) bond length is 1.93 Å. The Co(4)-O(7) bond length is 2.11 Å. Both Co(4)-O(6) bond lengths are 1.90 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ba(2), two equivalent La(1), one Co(1), and one Co(3) atom to form distorted OBa2La2Co2 octahedra that share  a cornercorner with one O(3)Ba2La2Co2 octahedra, corners with four equivalent O(7)Ba4Co2 octahedra,  an edgeedge with one O(1)Ba2La2Co2 octahedra,  an edgeedge with one O(3)Ba2La2Co2 octahedra, and faces with two equivalent O(8)Ba4Co2 octahedra. The corner-sharing octahedral tilt angles range from 7-63°. In the second O site, O(2) is bonded in a 6-coordinate geometry to two equivalent Ba(2), two equivalent La(1), one Co(2), and one Co(4) atom. In the third O site, O(3) is bonded to two equivalent Ba(1), two equivalent La(1), one Co(2), and one Co(3) atom to form distorted OBa2La2Co2 octahedra that share  a cornercorner with one O(1)Ba2La2Co2 octahedra, corners with two equivalent O(3)Ba2La2Co2 octahedra, corners with two equivalent O(7)Ba4Co2 octahedra, corners with two equivalent O(8)Ba4Co2 octahedra,  an edgeedge with one O(1)Ba2La2Co2 octahedra,  a faceface with one O(7)Ba4Co2 octahedra, and  a faceface with one O(8)Ba4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent La(1), one Co(1), and one Co(4) atom. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), two equivalent La(1), one Co(1), and one Co(2) atom. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), two equivalent La(1), one Co(3), and one Co(4) atom. In the seventh O site, O(7) is bonded to two equivalent Ba(1), two equivalent Ba(2), one Co(2), and one Co(4) atom to form distorted OBa4Co2 octahedra that share corners with two equivalent O(3)Ba2La2Co2 octahedra, corners with two equivalent O(7)Ba4Co2 octahedra, corners with two equivalent O(8)Ba4Co2 octahedra, corners with four equivalent O(1)Ba2La2Co2 octahedra,  an edgeedge with one O(7)Ba4Co2 octahedra, edges with three equivalent O(8)Ba4Co2 octahedra, and  a faceface with one O(3)Ba2La2Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-63°. In the eighth O site, O(8) is bonded to two equivalent Ba(1), two equivalent Ba(2), one Co(1), and one Co(3) atom to form distorted OBa4Co2 octahedra that share corners with two equivalent O(3)Ba2La2Co2 octahedra, corners with two equivalent O(7)Ba4Co2 octahedra, corners with two equivalent O(8)Ba4Co2 octahedra,  an edgeedge with one O(8)Ba4Co2 octahedra, edges with three equivalent O(7)Ba4Co2 octahedra,  a faceface with one O(3)Ba2La2Co2 octahedra, and faces with two equivalent O(1)Ba2La2Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-59°. In the ninth O site, O(9) is bonded in a distorted linear geometry to four equivalent La(1), one Co(1), and one Co(2) atom. In the tenth O site, O(10) is bonded in a distorted linear geometry to four equivalent La(1) and two equivalent Co(3) atoms.