LiBa2Eu(CuO2)4 crystallizes in the monoclinic Pm space group. Li(1) is bonded in a distorted T-shaped geometry to one O(6) and two equivalent O(1) atoms. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to two equivalent O(3), two equivalent O(5), two equivalent O(8), and four equivalent O(2) atoms. In the second Ba site, Ba(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(7) atoms. Eu(1) is bonded in a body-centered cubic geometry to two equivalent O(3), two equivalent O(4), two equivalent O(7), and two equivalent O(8) atoms. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(4) and two equivalent O(7) atoms. In the second Cu site, Cu(2) is bonded to one O(2), two equivalent O(3), and two equivalent O(8) atoms to form corner-sharing CuO5 square pyramids. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to one O(1), one O(5), and two equivalent O(6) atoms. In the fourth Cu site, Cu(4) is bonded in a square co-planar geometry to one O(2), one O(6), and two equivalent O(5) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Ba(2), and one Cu(3) atom to form distorted OBa2Li2Cu trigonal bipyramids that share corners with two equivalent O(4)Ba2Eu2Cu2 octahedra, corners with four equivalent O(7)Ba2Eu2Cu2 octahedra, corners with four equivalent O(1)Ba2Li2Cu trigonal bipyramids, and  an edgeedge with one O(4)Ba2Eu2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 8-70°. In the second O site, O(2) is bonded to four equivalent Ba(1), one Cu(2), and one Cu(4) atom to form a mixture of distorted corner and edge-sharing OBa4Cu2 octahedra. The corner-sharing octahedral tilt angles are 10°. In the third O site, O(3) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Eu(1), and two equivalent Cu(2) atoms. In the fourth O site, O(4) is bonded to two equivalent Ba(2), two equivalent Eu(1), and two equivalent Cu(1) atoms to form distorted OBa2Eu2Cu2 octahedra that share corners with two equivalent O(4)Ba2Eu2Cu2 octahedra, corners with two equivalent O(1)Ba2Li2Cu trigonal bipyramids, edges with two equivalent O(4)Ba2Eu2Cu2 octahedra,  an edgeedge with one O(1)Ba2Li2Cu trigonal bipyramid, and faces with four equivalent O(7)Ba2Eu2Cu2 octahedra. The corner-sharing octahedra are not tilted. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to two equivalent Ba(1), one Cu(3), and two equivalent Cu(4) atoms. In the sixth O site, O(6) is bonded in a square co-planar geometry to one Li(1), one Cu(4), and two equivalent Cu(3) atoms. In the seventh O site, O(7) is bonded to two equivalent Ba(2), two equivalent Eu(1), and two equivalent Cu(1) atoms to form OBa2Eu2Cu2 octahedra that share corners with two equivalent O(7)Ba2Eu2Cu2 octahedra, corners with four equivalent O(1)Ba2Li2Cu trigonal bipyramids, edges with two equivalent O(7)Ba2Eu2Cu2 octahedra, and faces with four equivalent O(4)Ba2Eu2Cu2 octahedra. The corner-sharing octahedral tilt angles are 6°. In the eighth O site, O(8) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Eu(1), and two equivalent Cu(2) atoms.
LiBa2Eu(CuO2)4 crystallizes in the monoclinic Pm space group. Li(1) is bonded in a distorted T-shaped geometry to one O(6) and two equivalent O(1) atoms. The Li(1)-O(6) bond length is 1.77 Å. There is one shorter (1.96 Å) and one longer (2.01 Å) Li(1)-O(1) bond length. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to two equivalent O(3), two equivalent O(5), two equivalent O(8), and four equivalent O(2) atoms. Both Ba(1)-O(3) bond lengths are 3.02 Å. Both Ba(1)-O(5) bond lengths are 3.00 Å. There is one shorter (2.94 Å) and one longer (3.01 Å) Ba(1)-O(8) bond length. There are two shorter (2.80 Å) and two longer (2.82 Å) Ba(1)-O(2) bond lengths. In the second Ba site, Ba(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(7) atoms. Both Ba(2)-O(1) bond lengths are 2.67 Å. Both Ba(2)-O(4) bond lengths are 2.78 Å. There is one shorter (2.62 Å) and one longer (2.70 Å) Ba(2)-O(7) bond length. Eu(1) is bonded in a body-centered cubic geometry to two equivalent O(3), two equivalent O(4), two equivalent O(7), and two equivalent O(8) atoms. Both Eu(1)-O(3) bond lengths are 2.45 Å. Both Eu(1)-O(4) bond lengths are 2.63 Å. Both Eu(1)-O(7) bond lengths are 2.66 Å. There is one shorter (2.41 Å) and one longer (2.42 Å) Eu(1)-O(8) bond length. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(4) and two equivalent O(7) atoms. There is one shorter (1.95 Å) and one longer (1.96 Å) Cu(1)-O(4) bond length. Both Cu(1)-O(7) bond lengths are 2.01 Å. In the second Cu site, Cu(2) is bonded to one O(2), two equivalent O(3), and two equivalent O(8) atoms to form corner-sharing CuO5 square pyramids. The Cu(2)-O(2) bond length is 2.32 Å. Both Cu(2)-O(3) bond lengths are 1.96 Å. Both Cu(2)-O(8) bond lengths are 2.01 Å. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to one O(1), one O(5), and two equivalent O(6) atoms. The Cu(3)-O(1) bond length is 1.96 Å. The Cu(3)-O(5) bond length is 1.91 Å. Both Cu(3)-O(6) bond lengths are 1.96 Å. In the fourth Cu site, Cu(4) is bonded in a square co-planar geometry to one O(2), one O(6), and two equivalent O(5) atoms. The Cu(4)-O(2) bond length is 1.84 Å. The Cu(4)-O(6) bond length is 1.86 Å. There is one shorter (1.95 Å) and one longer (1.96 Å) Cu(4)-O(5) bond length. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Ba(2), and one Cu(3) atom to form distorted OBa2Li2Cu trigonal bipyramids that share corners with two equivalent O(4)Ba2Eu2Cu2 octahedra, corners with four equivalent O(7)Ba2Eu2Cu2 octahedra, corners with four equivalent O(1)Ba2Li2Cu trigonal bipyramids, and  an edgeedge with one O(4)Ba2Eu2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 8-70°. In the second O site, O(2) is bonded to four equivalent Ba(1), one Cu(2), and one Cu(4) atom to form a mixture of distorted corner and edge-sharing OBa4Cu2 octahedra. The corner-sharing octahedral tilt angles are 10°. In the third O site, O(3) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Eu(1), and two equivalent Cu(2) atoms. In the fourth O site, O(4) is bonded to two equivalent Ba(2), two equivalent Eu(1), and two equivalent Cu(1) atoms to form distorted OBa2Eu2Cu2 octahedra that share corners with two equivalent O(4)Ba2Eu2Cu2 octahedra, corners with two equivalent O(1)Ba2Li2Cu trigonal bipyramids, edges with two equivalent O(4)Ba2Eu2Cu2 octahedra,  an edgeedge with one O(1)Ba2Li2Cu trigonal bipyramid, and faces with four equivalent O(7)Ba2Eu2Cu2 octahedra. The corner-sharing octahedra are not tilted. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to two equivalent Ba(1), one Cu(3), and two equivalent Cu(4) atoms. In the sixth O site, O(6) is bonded in a square co-planar geometry to one Li(1), one Cu(4), and two equivalent Cu(3) atoms. In the seventh O site, O(7) is bonded to two equivalent Ba(2), two equivalent Eu(1), and two equivalent Cu(1) atoms to form OBa2Eu2Cu2 octahedra that share corners with two equivalent O(7)Ba2Eu2Cu2 octahedra, corners with four equivalent O(1)Ba2Li2Cu trigonal bipyramids, edges with two equivalent O(7)Ba2Eu2Cu2 octahedra, and faces with four equivalent O(4)Ba2Eu2Cu2 octahedra. The corner-sharing octahedral tilt angles are 6°. In the eighth O site, O(8) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Eu(1), and two equivalent Cu(2) atoms.