Ba6Ca6Cu9Hg3O25 crystallizes in the monoclinic C2/m space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one O(4); two equivalent O(1); two equivalent O(2); and three equivalent O(5,6) atoms. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one O(4); two equivalent O(2); two equivalent O(3); and three equivalent O(5,6) atoms. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to one O(9); two equivalent O(1); two equivalent O(3); two equivalent O(4); and two equivalent O(5,6) atoms. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(2), two equivalent O(7), and two equivalent O(8) atoms. In the second Ca site, Ca(2) is bonded in a body-centered cubic geometry to two equivalent O(2), two equivalent O(3), and four equivalent O(7) atoms. In the third Ca site, Ca(3) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(3), two equivalent O(7), and two equivalent O(8) atoms. There are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. In the second Cu site, Cu(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. In the third Cu site, Cu(3) is bonded in a rectangular see-saw-like geometry to two equivalent O(2) and two equivalent O(3) atoms. In the fourth Cu site, Cu(4) is bonded in a rectangular see-saw-like geometry to two equivalent O(7) and two equivalent O(8) atoms. In the fifth Cu site, Cu(5) is bonded in a square co-planar geometry to four equivalent O(7) atoms. There are two inequivalent Hg sites. In the first Hg site, Hg(1) is bonded in a linear geometry to two equivalent O(4) and two equivalent O(9) atoms. In the second Hg site, Hg(2) is bonded in a distorted T-shaped geometry to one O(9) and two equivalent O(5,6) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Ba(1), one Ba(3), one Ca(1), one Ca(3), one Cu(1), and one Cu(2) atom to form distorted OBa2Ca2Cu2 octahedra that share  a cornercorner with one O(2)Ba2Ca2Cu2 octahedra,  a cornercorner with one O(3)Ba2Ca2Cu2 octahedra,  a cornercorner with one O(9)Ba2Hg4 octahedra, corners with two equivalent O(8)Ca4Cu2 octahedra, corners with four equivalent O(7)Ca4Cu2 octahedra,  an edgeedge with one O(2)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(3)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(8)Ca4Cu2 octahedra,  a faceface with one O(2)Ba2Ca2Cu2 octahedra,  a faceface with one O(3)Ba2Ca2Cu2 octahedra, and faces with two equivalent O(1)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 2-67°. In the second O site, O(2) is bonded to one Ba(1), one Ba(2), one Ca(1), one Ca(2), one Cu(2), and one Cu(3) atom to form distorted OBa2Ca2Cu2 octahedra that share  a cornercorner with one O(1)Ba2Ca2Cu2 octahedra,  a cornercorner with one O(3)Ba2Ca2Cu2 octahedra, corners with two equivalent O(8)Ca4Cu2 octahedra, corners with four equivalent O(7)Ca4Cu2 octahedra,  an edgeedge with one O(1)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(3)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(7)Ca4Cu2 octahedra,  a faceface with one O(1)Ba2Ca2Cu2 octahedra,  a faceface with one O(3)Ba2Ca2Cu2 octahedra, and faces with two equivalent O(2)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 2-66°. In the third O site, O(3) is bonded to one Ba(2), one Ba(3), one Ca(2), one Ca(3), one Cu(1), and one Cu(3) atom to form distorted OBa2Ca2Cu2 octahedra that share  a cornercorner with one O(1)Ba2Ca2Cu2 octahedra,  a cornercorner with one O(2)Ba2Ca2Cu2 octahedra,  a cornercorner with one O(9)Ba2Hg4 octahedra, corners with two equivalent O(8)Ca4Cu2 octahedra, corners with four equivalent O(7)Ca4Cu2 octahedra,  an edgeedge with one O(1)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(2)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(7)Ca4Cu2 octahedra,  a faceface with one O(1)Ba2Ca2Cu2 octahedra,  a faceface with one O(2)Ba2Ca2Cu2 octahedra, and faces with two equivalent O(3)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 2-67°. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), two equivalent Ba(3), and one Hg(1) atom. In the fifth O site, O(5,6) is bonded in a 5-coordinate geometry to one Ba(2), one Ba(3), two equivalent Ba(1), and one Hg(2) atom. In the sixth O site, O(7) is bonded to one Ca(1), one Ca(3), two equivalent Ca(2), one Cu(4), and one Cu(5) atom to form OCa4Cu2 octahedra that share  a cornercorner with one O(7)Ca4Cu2 octahedra,  a cornercorner with one O(8)Ca4Cu2 octahedra, corners with four equivalent O(1)Ba2Ca2Cu2 octahedra, corners with four equivalent O(2)Ba2Ca2Cu2 octahedra, corners with four equivalent O(3)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(2)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(3)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(7)Ca4Cu2 octahedra,  an edgeedge with one O(8)Ca4Cu2 octahedra,  a faceface with one O(8)Ca4Cu2 octahedra, and faces with three equivalent O(7)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-67°. In the seventh O site, O(8) is bonded to two equivalent Ca(1), two equivalent Ca(3), and two equivalent Cu(4) atoms to form OCa4Cu2 octahedra that share corners with two equivalent O(7)Ca4Cu2 octahedra, corners with four equivalent O(1)Ba2Ca2Cu2 octahedra, corners with four equivalent O(2)Ba2Ca2Cu2 octahedra, corners with four equivalent O(3)Ba2Ca2Cu2 octahedra, edges with two equivalent O(1)Ba2Ca2Cu2 octahedra, edges with two equivalent O(7)Ca4Cu2 octahedra, faces with two equivalent O(7)Ca4Cu2 octahedra, and faces with two equivalent O(8)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-67°. In the eighth O site, O(9) is bonded to two equivalent Ba(3), two equivalent Hg(1), and two equivalent Hg(2) atoms to form distorted OBa2Hg4 octahedra that share corners with two equivalent O(9)Ba2Hg4 octahedra, corners with four equivalent O(1)Ba2Ca2Cu2 octahedra, and corners with four equivalent O(3)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-41°.
Ba6Ca6Cu9Hg3O25 crystallizes in the monoclinic C2/m space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one O(4); two equivalent O(1); two equivalent O(2); and three equivalent O(5,6) atoms. The Ba(1)-O(4) bond length is 2.84 Å. Both Ba(1)-O(1) bond lengths are 2.83 Å. Both Ba(1)-O(2) bond lengths are 2.84 Å. There is one shorter (2.79 Å) and two longer (2.86 Å) Ba(1)-O(5,6) bond lengths. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one O(4); two equivalent O(2); two equivalent O(3); and three equivalent O(5,6) atoms. The Ba(2)-O(4) bond length is 2.84 Å. Both Ba(2)-O(2) bond lengths are 2.84 Å. Both Ba(2)-O(3) bond lengths are 2.83 Å. There is one shorter (2.79 Å) and two longer (2.86 Å) Ba(2)-O(5,6) bond lengths. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to one O(9); two equivalent O(1); two equivalent O(3); two equivalent O(4); and two equivalent O(5,6) atoms. The Ba(3)-O(9) bond length is 2.68 Å. Both Ba(3)-O(1) bond lengths are 2.98 Å. Both Ba(3)-O(3) bond lengths are 2.98 Å. Both Ba(3)-O(4) bond lengths are 2.82 Å. Both Ba(3)-O(5,6) bond lengths are 2.87 Å. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(2), two equivalent O(7), and two equivalent O(8) atoms. Both Ca(1)-O(1) bond lengths are 2.46 Å. Both Ca(1)-O(2) bond lengths are 2.48 Å. Both Ca(1)-O(7) bond lengths are 2.54 Å. Both Ca(1)-O(8) bond lengths are 2.55 Å. In the second Ca site, Ca(2) is bonded in a body-centered cubic geometry to two equivalent O(2), two equivalent O(3), and four equivalent O(7) atoms. Both Ca(2)-O(2) bond lengths are 2.48 Å. Both Ca(2)-O(3) bond lengths are 2.46 Å. There are two shorter (2.54 Å) and two longer (2.55 Å) Ca(2)-O(7) bond lengths. In the third Ca site, Ca(3) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(3), two equivalent O(7), and two equivalent O(8) atoms. Both Ca(3)-O(1) bond lengths are 2.46 Å. Both Ca(3)-O(3) bond lengths are 2.46 Å. Both Ca(3)-O(7) bond lengths are 2.57 Å. Both Ca(3)-O(8) bond lengths are 2.57 Å. There are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Cu(1)-O(1) bond lengths are 1.94 Å. Both Cu(1)-O(3) bond lengths are 1.94 Å. In the second Cu site, Cu(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Cu(2)-O(1) bond lengths are 1.93 Å. Both Cu(2)-O(2) bond lengths are 1.95 Å. In the third Cu site, Cu(3) is bonded in a rectangular see-saw-like geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Cu(3)-O(2) bond lengths are 1.95 Å. Both Cu(3)-O(3) bond lengths are 1.93 Å. In the fourth Cu site, Cu(4) is bonded in a rectangular see-saw-like geometry to two equivalent O(7) and two equivalent O(8) atoms. Both Cu(4)-O(7) bond lengths are 1.94 Å. Both Cu(4)-O(8) bond lengths are 1.94 Å. In the fifth Cu site, Cu(5) is bonded in a square co-planar geometry to four equivalent O(7) atoms. All Cu(5)-O(7) bond lengths are 1.94 Å. There are two inequivalent Hg sites. In the first Hg site, Hg(1) is bonded in a linear geometry to two equivalent O(4) and two equivalent O(9) atoms. Both Hg(1)-O(4) bond lengths are 2.06 Å. Both Hg(1)-O(9) bond lengths are 2.75 Å. In the second Hg site, Hg(2) is bonded in a distorted T-shaped geometry to one O(9) and two equivalent O(5,6) atoms. The Hg(2)-O(9) bond length is 2.65 Å. Both Hg(2)-O(5,6) bond lengths are 2.06 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Ba(1), one Ba(3), one Ca(1), one Ca(3), one Cu(1), and one Cu(2) atom to form distorted OBa2Ca2Cu2 octahedra that share  a cornercorner with one O(2)Ba2Ca2Cu2 octahedra,  a cornercorner with one O(3)Ba2Ca2Cu2 octahedra,  a cornercorner with one O(9)Ba2Hg4 octahedra, corners with two equivalent O(8)Ca4Cu2 octahedra, corners with four equivalent O(7)Ca4Cu2 octahedra,  an edgeedge with one O(2)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(3)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(8)Ca4Cu2 octahedra,  a faceface with one O(2)Ba2Ca2Cu2 octahedra,  a faceface with one O(3)Ba2Ca2Cu2 octahedra, and faces with two equivalent O(1)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 2-67°. In the second O site, O(2) is bonded to one Ba(1), one Ba(2), one Ca(1), one Ca(2), one Cu(2), and one Cu(3) atom to form distorted OBa2Ca2Cu2 octahedra that share  a cornercorner with one O(1)Ba2Ca2Cu2 octahedra,  a cornercorner with one O(3)Ba2Ca2Cu2 octahedra, corners with two equivalent O(8)Ca4Cu2 octahedra, corners with four equivalent O(7)Ca4Cu2 octahedra,  an edgeedge with one O(1)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(3)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(7)Ca4Cu2 octahedra,  a faceface with one O(1)Ba2Ca2Cu2 octahedra,  a faceface with one O(3)Ba2Ca2Cu2 octahedra, and faces with two equivalent O(2)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 2-66°. In the third O site, O(3) is bonded to one Ba(2), one Ba(3), one Ca(2), one Ca(3), one Cu(1), and one Cu(3) atom to form distorted OBa2Ca2Cu2 octahedra that share  a cornercorner with one O(1)Ba2Ca2Cu2 octahedra,  a cornercorner with one O(2)Ba2Ca2Cu2 octahedra,  a cornercorner with one O(9)Ba2Hg4 octahedra, corners with two equivalent O(8)Ca4Cu2 octahedra, corners with four equivalent O(7)Ca4Cu2 octahedra,  an edgeedge with one O(1)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(2)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(7)Ca4Cu2 octahedra,  a faceface with one O(1)Ba2Ca2Cu2 octahedra,  a faceface with one O(2)Ba2Ca2Cu2 octahedra, and faces with two equivalent O(3)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 2-67°. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), two equivalent Ba(3), and one Hg(1) atom. In the fifth O site, O(5,6) is bonded in a 5-coordinate geometry to one Ba(2), one Ba(3), two equivalent Ba(1), and one Hg(2) atom. In the sixth O site, O(7) is bonded to one Ca(1), one Ca(3), two equivalent Ca(2), one Cu(4), and one Cu(5) atom to form OCa4Cu2 octahedra that share  a cornercorner with one O(7)Ca4Cu2 octahedra,  a cornercorner with one O(8)Ca4Cu2 octahedra, corners with four equivalent O(1)Ba2Ca2Cu2 octahedra, corners with four equivalent O(2)Ba2Ca2Cu2 octahedra, corners with four equivalent O(3)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(2)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(3)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(7)Ca4Cu2 octahedra,  an edgeedge with one O(8)Ca4Cu2 octahedra,  a faceface with one O(8)Ca4Cu2 octahedra, and faces with three equivalent O(7)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-67°. In the seventh O site, O(8) is bonded to two equivalent Ca(1), two equivalent Ca(3), and two equivalent Cu(4) atoms to form OCa4Cu2 octahedra that share corners with two equivalent O(7)Ca4Cu2 octahedra, corners with four equivalent O(1)Ba2Ca2Cu2 octahedra, corners with four equivalent O(2)Ba2Ca2Cu2 octahedra, corners with four equivalent O(3)Ba2Ca2Cu2 octahedra, edges with two equivalent O(1)Ba2Ca2Cu2 octahedra, edges with two equivalent O(7)Ca4Cu2 octahedra, faces with two equivalent O(7)Ca4Cu2 octahedra, and faces with two equivalent O(8)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-67°. In the eighth O site, O(9) is bonded to two equivalent Ba(3), two equivalent Hg(1), and two equivalent Hg(2) atoms to form distorted OBa2Hg4 octahedra that share corners with two equivalent O(9)Ba2Hg4 octahedra, corners with four equivalent O(1)Ba2Ca2Cu2 octahedra, and corners with four equivalent O(3)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-41°.