Ba4Nd5Cu9O22 crystallizes in the monoclinic P2/m space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one O(10), one O(11), one O(4), one O(6), two equivalent O(3), two equivalent O(7), and two equivalent O(9) atoms. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to one O(10), one O(11), one O(5), one O(6), two equivalent O(2), two equivalent O(8), and two equivalent O(9) atoms. There are three inequivalent Nd sites. In the first Nd site, Nd(1) is bonded in a body-centered cubic geometry to one O(5), one O(6), two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. In the second Nd site, Nd(2) is bonded in a body-centered cubic geometry to two equivalent O(5), two equivalent O(6), and four equivalent O(2) atoms. In the third Nd site, Nd(3) is bonded to one O(4), one O(5), two equivalent O(1), two equivalent O(10), two equivalent O(12), two equivalent O(7), and two equivalent O(8) atoms to form distorted NdO12 cuboctahedra that share corners with two equivalent Nd(3)O12 cuboctahedra, faces with three equivalent Nd(3)O12 cuboctahedra, faces with two equivalent Cu(1)O5 square pyramids, faces with two equivalent Cu(2)O5 square pyramids, and faces with four equivalent Cu(4)O5 square pyramids. There are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(3), one O(7), and two equivalent O(4) atoms to form CuO5 square pyramids that share  a cornercorner with one Cu(2)O5 square pyramid,  a cornercorner with one Cu(3)O5 square pyramid,  a cornercorner with one Cu(4)O5 square pyramid, corners with two equivalent Cu(1)O5 square pyramids, and faces with two equivalent Nd(3)O12 cuboctahedra. In the second Cu site, Cu(2) is bonded to one O(1), one O(2), one O(8), and two equivalent O(5) atoms to form CuO5 square pyramids that share  a cornercorner with one Cu(1)O5 square pyramid,  a cornercorner with one Cu(3)O5 square pyramid,  a cornercorner with one Cu(4)O5 square pyramid, corners with two equivalent Cu(2)O5 square pyramids, and faces with two equivalent Nd(3)O12 cuboctahedra. In the third Cu site, Cu(3) is bonded to one O(2), one O(3), one O(9), and two equivalent O(6) atoms to form corner-sharing CuO5 square pyramids. In the fourth Cu site, Cu(4) is bonded to one O(12), one O(7), one O(8), and two equivalent O(10) atoms to form CuO5 square pyramids that share  a cornercorner with one Cu(1)O5 square pyramid,  a cornercorner with one Cu(2)O5 square pyramid, corners with three equivalent Cu(4)O5 square pyramids, and faces with four equivalent Nd(3)O12 cuboctahedra. In the fifth Cu site, Cu(5) is bonded in a square co-planar geometry to two equivalent O(11) and two equivalent O(9) atoms. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Nd(1), two equivalent Nd(3), one Cu(1), and one Cu(2) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to two equivalent Ba(2), two equivalent Nd(2), one Cu(2), and one Cu(3) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Nd(1), one Cu(1), and one Cu(3) atom. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Ba(1), one Nd(3), two equivalent Nd(1), and two equivalent Cu(1) atoms. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Ba(2), one Nd(1), one Nd(2), one Nd(3), and two equivalent Cu(2) atoms. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Nd(1), one Nd(2), and two equivalent Cu(3) atoms. In the seventh O site, O(7) is bonded to two equivalent Ba(1), two equivalent Nd(3), one Cu(1), and one Cu(4) atom to form distorted OBa2Nd2Cu2 octahedra that share corners with two equivalent O(10)Ba2Nd2Cu2 octahedra, corners with two equivalent O(11)Ba4Cu2 octahedra, corners with two equivalent O(9)Ba4Cu2 octahedra, corners with two equivalent O(12)Nd4Cu2 octahedra, corners with three equivalent O(8)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(8)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(9)Ba4Cu2 octahedra, edges with two equivalent O(7)Ba2Nd2Cu2 octahedra,  a faceface with one O(12)Nd4Cu2 octahedra, and faces with two equivalent O(10)Ba2Nd2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 6-64°. In the eighth O site, O(8) is bonded to two equivalent Ba(2), two equivalent Nd(3), one Cu(2), and one Cu(4) atom to form distorted OBa2Nd2Cu2 octahedra that share corners with two equivalent O(10)Ba2Nd2Cu2 octahedra, corners with two equivalent O(11)Ba4Cu2 octahedra, corners with two equivalent O(9)Ba4Cu2 octahedra, corners with two equivalent O(12)Nd4Cu2 octahedra, corners with three equivalent O(7)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(7)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(9)Ba4Cu2 octahedra, edges with two equivalent O(8)Ba2Nd2Cu2 octahedra,  a faceface with one O(12)Nd4Cu2 octahedra, and faces with two equivalent O(10)Ba2Nd2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 6-64°. In the ninth O site, O(9) is bonded to two equivalent Ba(1), two equivalent Ba(2), one Cu(3), and one Cu(5) atom to form distorted OBa4Cu2 octahedra that share  a cornercorner with one O(9)Ba4Cu2 octahedra, corners with two equivalent O(7)Ba2Nd2Cu2 octahedra, corners with two equivalent O(8)Ba2Nd2Cu2 octahedra, corners with four equivalent O(10)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(7)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(8)Ba2Nd2Cu2 octahedra, edges with two equivalent O(9)Ba4Cu2 octahedra, and faces with two equivalent O(11)Ba4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-65°. In the tenth O site, O(10) is bonded to one Ba(1), one Ba(2), two equivalent Nd(3), and two equivalent Cu(4) atoms to form distorted OBa2Nd2Cu2 octahedra that share corners with two equivalent O(10)Ba2Nd2Cu2 octahedra, corners with two equivalent O(7)Ba2Nd2Cu2 octahedra, corners with two equivalent O(8)Ba2Nd2Cu2 octahedra, corners with four equivalent O(9)Ba4Cu2 octahedra,  an edgeedge with one O(10)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(11)Ba4Cu2 octahedra, faces with two equivalent O(7)Ba2Nd2Cu2 octahedra, faces with two equivalent O(8)Ba2Nd2Cu2 octahedra, and faces with two equivalent O(12)Nd4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 5-65°. In the eleventh O site, O(11) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Cu(5) atoms to form distorted OBa4Cu2 octahedra that share corners with two equivalent O(11)Ba4Cu2 octahedra, corners with four equivalent O(7)Ba2Nd2Cu2 octahedra, corners with four equivalent O(8)Ba2Nd2Cu2 octahedra, edges with two equivalent O(10)Ba2Nd2Cu2 octahedra, and faces with four equivalent O(9)Ba4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-64°. In the twelfth O site, O(12) is bonded to four equivalent Nd(3) and two equivalent Cu(4) atoms to form distorted ONd4Cu2 octahedra that share corners with four equivalent O(7)Ba2Nd2Cu2 octahedra, corners with four equivalent O(8)Ba2Nd2Cu2 octahedra, edges with two equivalent O(12)Nd4Cu2 octahedra, faces with two equivalent O(7)Ba2Nd2Cu2 octahedra, faces with two equivalent O(8)Ba2Nd2Cu2 octahedra, and faces with four equivalent O(10)Ba2Nd2Cu2 octahedra. The corner-sharing octahedral tilt angles are 55°.
Ba4Nd5Cu9O22 crystallizes in the monoclinic P2/m space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one O(10), one O(11), one O(4), one O(6), two equivalent O(3), two equivalent O(7), and two equivalent O(9) atoms. The Ba(1)-O(10) bond length is 2.99 Å. The Ba(1)-O(11) bond length is 2.89 Å. The Ba(1)-O(4) bond length is 2.92 Å. The Ba(1)-O(6) bond length is 2.93 Å. Both Ba(1)-O(3) bond lengths are 2.96 Å. Both Ba(1)-O(7) bond lengths are 2.90 Å. Both Ba(1)-O(9) bond lengths are 2.75 Å. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to one O(10), one O(11), one O(5), one O(6), two equivalent O(2), two equivalent O(8), and two equivalent O(9) atoms. The Ba(2)-O(10) bond length is 2.98 Å. The Ba(2)-O(11) bond length is 2.87 Å. The Ba(2)-O(5) bond length is 2.94 Å. The Ba(2)-O(6) bond length is 2.96 Å. Both Ba(2)-O(2) bond lengths are 2.93 Å. Both Ba(2)-O(8) bond lengths are 2.90 Å. Both Ba(2)-O(9) bond lengths are 2.76 Å. There are three inequivalent Nd sites. In the first Nd site, Nd(1) is bonded in a body-centered cubic geometry to one O(5), one O(6), two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. The Nd(1)-O(5) bond length is 2.45 Å. The Nd(1)-O(6) bond length is 2.49 Å. Both Nd(1)-O(1) bond lengths are 2.49 Å. Both Nd(1)-O(3) bond lengths are 2.49 Å. There is one shorter (2.44 Å) and one longer (2.54 Å) Nd(1)-O(4) bond length. In the second Nd site, Nd(2) is bonded in a body-centered cubic geometry to two equivalent O(5), two equivalent O(6), and four equivalent O(2) atoms. Both Nd(2)-O(5) bond lengths are 2.51 Å. Both Nd(2)-O(6) bond lengths are 2.45 Å. All Nd(2)-O(2) bond lengths are 2.48 Å. In the third Nd site, Nd(3) is bonded to one O(4), one O(5), two equivalent O(1), two equivalent O(10), two equivalent O(12), two equivalent O(7), and two equivalent O(8) atoms to form distorted NdO12 cuboctahedra that share corners with two equivalent Nd(3)O12 cuboctahedra, faces with three equivalent Nd(3)O12 cuboctahedra, faces with two equivalent Cu(1)O5 square pyramids, faces with two equivalent Cu(2)O5 square pyramids, and faces with four equivalent Cu(4)O5 square pyramids. The Nd(3)-O(4) bond length is 3.17 Å. The Nd(3)-O(5) bond length is 3.16 Å. Both Nd(3)-O(1) bond lengths are 3.13 Å. There is one shorter (2.56 Å) and one longer (2.57 Å) Nd(3)-O(10) bond length. Both Nd(3)-O(12) bond lengths are 2.65 Å. Both Nd(3)-O(7) bond lengths are 2.66 Å. Both Nd(3)-O(8) bond lengths are 2.66 Å. There are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(3), one O(7), and two equivalent O(4) atoms to form CuO5 square pyramids that share  a cornercorner with one Cu(2)O5 square pyramid,  a cornercorner with one Cu(3)O5 square pyramid,  a cornercorner with one Cu(4)O5 square pyramid, corners with two equivalent Cu(1)O5 square pyramids, and faces with two equivalent Nd(3)O12 cuboctahedra. The Cu(1)-O(1) bond length is 1.95 Å. The Cu(1)-O(3) bond length is 1.98 Å. The Cu(1)-O(7) bond length is 2.13 Å. Both Cu(1)-O(4) bond lengths are 1.97 Å. In the second Cu site, Cu(2) is bonded to one O(1), one O(2), one O(8), and two equivalent O(5) atoms to form CuO5 square pyramids that share  a cornercorner with one Cu(1)O5 square pyramid,  a cornercorner with one Cu(3)O5 square pyramid,  a cornercorner with one Cu(4)O5 square pyramid, corners with two equivalent Cu(2)O5 square pyramids, and faces with two equivalent Nd(3)O12 cuboctahedra. The Cu(2)-O(1) bond length is 1.95 Å. The Cu(2)-O(2) bond length is 1.99 Å. The Cu(2)-O(8) bond length is 2.12 Å. Both Cu(2)-O(5) bond lengths are 1.97 Å. In the third Cu site, Cu(3) is bonded to one O(2), one O(3), one O(9), and two equivalent O(6) atoms to form corner-sharing CuO5 square pyramids. The Cu(3)-O(2) bond length is 1.97 Å. The Cu(3)-O(3) bond length is 1.97 Å. The Cu(3)-O(9) bond length is 2.23 Å. Both Cu(3)-O(6) bond lengths are 1.97 Å. In the fourth Cu site, Cu(4) is bonded to one O(12), one O(7), one O(8), and two equivalent O(10) atoms to form CuO5 square pyramids that share  a cornercorner with one Cu(1)O5 square pyramid,  a cornercorner with one Cu(2)O5 square pyramid, corners with three equivalent Cu(4)O5 square pyramids, and faces with four equivalent Nd(3)O12 cuboctahedra. The Cu(4)-O(12) bond length is 1.93 Å. The Cu(4)-O(7) bond length is 1.92 Å. The Cu(4)-O(8) bond length is 1.92 Å. Both Cu(4)-O(10) bond lengths are 1.96 Å. In the fifth Cu site, Cu(5) is bonded in a square co-planar geometry to two equivalent O(11) and two equivalent O(9) atoms. Both Cu(5)-O(11) bond lengths are 1.95 Å. Both Cu(5)-O(9) bond lengths are 1.87 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Nd(1), two equivalent Nd(3), one Cu(1), and one Cu(2) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to two equivalent Ba(2), two equivalent Nd(2), one Cu(2), and one Cu(3) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Nd(1), one Cu(1), and one Cu(3) atom. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Ba(1), one Nd(3), two equivalent Nd(1), and two equivalent Cu(1) atoms. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Ba(2), one Nd(1), one Nd(2), one Nd(3), and two equivalent Cu(2) atoms. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Nd(1), one Nd(2), and two equivalent Cu(3) atoms. In the seventh O site, O(7) is bonded to two equivalent Ba(1), two equivalent Nd(3), one Cu(1), and one Cu(4) atom to form distorted OBa2Nd2Cu2 octahedra that share corners with two equivalent O(10)Ba2Nd2Cu2 octahedra, corners with two equivalent O(11)Ba4Cu2 octahedra, corners with two equivalent O(9)Ba4Cu2 octahedra, corners with two equivalent O(12)Nd4Cu2 octahedra, corners with three equivalent O(8)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(8)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(9)Ba4Cu2 octahedra, edges with two equivalent O(7)Ba2Nd2Cu2 octahedra,  a faceface with one O(12)Nd4Cu2 octahedra, and faces with two equivalent O(10)Ba2Nd2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 6-64°. In the eighth O site, O(8) is bonded to two equivalent Ba(2), two equivalent Nd(3), one Cu(2), and one Cu(4) atom to form distorted OBa2Nd2Cu2 octahedra that share corners with two equivalent O(10)Ba2Nd2Cu2 octahedra, corners with two equivalent O(11)Ba4Cu2 octahedra, corners with two equivalent O(9)Ba4Cu2 octahedra, corners with two equivalent O(12)Nd4Cu2 octahedra, corners with three equivalent O(7)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(7)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(9)Ba4Cu2 octahedra, edges with two equivalent O(8)Ba2Nd2Cu2 octahedra,  a faceface with one O(12)Nd4Cu2 octahedra, and faces with two equivalent O(10)Ba2Nd2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 6-64°. In the ninth O site, O(9) is bonded to two equivalent Ba(1), two equivalent Ba(2), one Cu(3), and one Cu(5) atom to form distorted OBa4Cu2 octahedra that share  a cornercorner with one O(9)Ba4Cu2 octahedra, corners with two equivalent O(7)Ba2Nd2Cu2 octahedra, corners with two equivalent O(8)Ba2Nd2Cu2 octahedra, corners with four equivalent O(10)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(7)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(8)Ba2Nd2Cu2 octahedra, edges with two equivalent O(9)Ba4Cu2 octahedra, and faces with two equivalent O(11)Ba4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-65°. In the tenth O site, O(10) is bonded to one Ba(1), one Ba(2), two equivalent Nd(3), and two equivalent Cu(4) atoms to form distorted OBa2Nd2Cu2 octahedra that share corners with two equivalent O(10)Ba2Nd2Cu2 octahedra, corners with two equivalent O(7)Ba2Nd2Cu2 octahedra, corners with two equivalent O(8)Ba2Nd2Cu2 octahedra, corners with four equivalent O(9)Ba4Cu2 octahedra,  an edgeedge with one O(10)Ba2Nd2Cu2 octahedra,  an edgeedge with one O(11)Ba4Cu2 octahedra, faces with two equivalent O(7)Ba2Nd2Cu2 octahedra, faces with two equivalent O(8)Ba2Nd2Cu2 octahedra, and faces with two equivalent O(12)Nd4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 5-65°. In the eleventh O site, O(11) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Cu(5) atoms to form distorted OBa4Cu2 octahedra that share corners with two equivalent O(11)Ba4Cu2 octahedra, corners with four equivalent O(7)Ba2Nd2Cu2 octahedra, corners with four equivalent O(8)Ba2Nd2Cu2 octahedra, edges with two equivalent O(10)Ba2Nd2Cu2 octahedra, and faces with four equivalent O(9)Ba4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-64°. In the twelfth O site, O(12) is bonded to four equivalent Nd(3) and two equivalent Cu(4) atoms to form distorted ONd4Cu2 octahedra that share corners with four equivalent O(7)Ba2Nd2Cu2 octahedra, corners with four equivalent O(8)Ba2Nd2Cu2 octahedra, edges with two equivalent O(12)Nd4Cu2 octahedra, faces with two equivalent O(7)Ba2Nd2Cu2 octahedra, faces with two equivalent O(8)Ba2Nd2Cu2 octahedra, and faces with four equivalent O(10)Ba2Nd2Cu2 octahedra. The corner-sharing octahedral tilt angles are 55°.