TbMn2O5 crystallizes in the orthorhombic Pbam space group. Tb(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(1) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form MnO5 square pyramids that share corners with four equivalent Mn(2)O6 octahedra and  an edgeedge with one Mn(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 48-57°. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with four equivalent Mn(1)O5 square pyramids and edges with two equivalent Mn(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Tb(1), one Mn(1), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing OTb2Mn2 trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1) and two equivalent Mn(2) atoms. In the third O site, O(3) is bonded to two equivalent Tb(1) and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing OTb2Mn2 trigonal pyramids. In the fourth O site, O(4) is bonded to two equivalent Tb(1) and two equivalent Mn(2) atoms to form a mixture of distorted corner and edge-sharing OTb2Mn2 trigonal pyramids.
TbMn2O5 crystallizes in the orthorhombic Pbam space group. Tb(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(1) atoms. Both Tb(1)-O(3) bond lengths are 2.35 Å. There is one shorter (2.33 Å) and one longer (2.41 Å) Tb(1)-O(4) bond length. There are two shorter (2.35 Å) and two longer (2.47 Å) Tb(1)-O(1) bond lengths. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form MnO5 square pyramids that share corners with four equivalent Mn(2)O6 octahedra and  an edgeedge with one Mn(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 48-57°. The Mn(1)-O(2) bond length is 2.01 Å. Both Mn(1)-O(1) bond lengths are 1.90 Å. Both Mn(1)-O(3) bond lengths are 1.93 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with four equivalent Mn(1)O5 square pyramids and edges with two equivalent Mn(2)O6 octahedra. Both Mn(2)-O(1) bond lengths are 1.91 Å. Both Mn(2)-O(2) bond lengths are 1.87 Å. Both Mn(2)-O(4) bond lengths are 1.93 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Tb(1), one Mn(1), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing OTb2Mn2 trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1) and two equivalent Mn(2) atoms. In the third O site, O(3) is bonded to two equivalent Tb(1) and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing OTb2Mn2 trigonal pyramids. In the fourth O site, O(4) is bonded to two equivalent Tb(1) and two equivalent Mn(2) atoms to form a mixture of distorted corner and edge-sharing OTb2Mn2 trigonal pyramids.