Sc2Cu2O5 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing ScO6 octahedra. The corner-sharing octahedral tilt angles range from 13-61°. In the second Sc site, Sc(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing ScO6 octahedra. The corner-sharing octahedral tilt angles range from 13-61°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(4), and two equivalent O(3) atoms. In the second Cu site, Cu(2) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(4), one O(5), and two equivalent O(3) atoms. There are five inequivalent O sites. In the first O site, O(5) is bonded to one Sc(1), two equivalent Sc(2), and one Cu(2) atom to form OSc3Cu tetrahedra that share corners with two equivalent O(5)Sc3Cu tetrahedra, corners with four equivalent O(1)Sc3Cu tetrahedra, corners with three equivalent O(2)Sc2Cu2 trigonal pyramids, corners with three equivalent O(4)Sc2Cu2 trigonal pyramids, and  an edgeedge with one O(2)Sc2Cu2 trigonal pyramid. In the second O site, O(1) is bonded to one Sc(2), two equivalent Sc(1), and one Cu(1) atom to form distorted OSc3Cu tetrahedra that share corners with two equivalent O(1)Sc3Cu tetrahedra, corners with four equivalent O(5)Sc3Cu tetrahedra, corners with three equivalent O(2)Sc2Cu2 trigonal pyramids, corners with three equivalent O(4)Sc2Cu2 trigonal pyramids, and  an edgeedge with one O(4)Sc2Cu2 trigonal pyramid. In the third O site, O(2) is bonded to two equivalent Sc(2), one Cu(1), and one Cu(2) atom to form OSc2Cu2 trigonal pyramids that share corners with three equivalent O(1)Sc3Cu tetrahedra, corners with three equivalent O(5)Sc3Cu tetrahedra, corners with two equivalent O(2)Sc2Cu2 trigonal pyramids,  an edgeedge with one O(5)Sc3Cu tetrahedra, and  an edgeedge with one O(4)Sc2Cu2 trigonal pyramid. In the fourth O site, O(3) is bonded in a 6-coordinate geometry to one Sc(1), one Sc(2), two equivalent Cu(1), and two equivalent Cu(2) atoms. In the fifth O site, O(4) is bonded to two equivalent Sc(1), one Cu(1), and one Cu(2) atom to form OSc2Cu2 trigonal pyramids that share corners with three equivalent O(1)Sc3Cu tetrahedra, corners with three equivalent O(5)Sc3Cu tetrahedra, corners with two equivalent O(4)Sc2Cu2 trigonal pyramids,  an edgeedge with one O(1)Sc3Cu tetrahedra, and  an edgeedge with one O(2)Sc2Cu2 trigonal pyramid.
Sc2Cu2O5 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing ScO6 octahedra. The corner-sharing octahedral tilt angles range from 13-61°. The Sc(1)-O(3) bond length is 2.21 Å. The Sc(1)-O(5) bond length is 2.09 Å. There is one shorter (2.14 Å) and one longer (2.19 Å) Sc(1)-O(1) bond length. There is one shorter (2.12 Å) and one longer (2.14 Å) Sc(1)-O(4) bond length. In the second Sc site, Sc(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing ScO6 octahedra. The corner-sharing octahedral tilt angles range from 13-61°. The Sc(2)-O(1) bond length is 2.09 Å. The Sc(2)-O(3) bond length is 2.21 Å. Both Sc(2)-O(2) bond lengths are 2.13 Å. There is one shorter (2.16 Å) and one longer (2.17 Å) Sc(2)-O(5) bond length. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(4), and two equivalent O(3) atoms. The Cu(1)-O(1) bond length is 1.99 Å. The Cu(1)-O(2) bond length is 1.99 Å. The Cu(1)-O(4) bond length is 1.94 Å. There is one shorter (1.96 Å) and one longer (2.60 Å) Cu(1)-O(3) bond length. In the second Cu site, Cu(2) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(4), one O(5), and two equivalent O(3) atoms. The Cu(2)-O(2) bond length is 1.94 Å. The Cu(2)-O(4) bond length is 2.00 Å. The Cu(2)-O(5) bond length is 1.99 Å. There is one shorter (1.96 Å) and one longer (2.63 Å) Cu(2)-O(3) bond length. There are five inequivalent O sites. In the first O site, O(5) is bonded to one Sc(1), two equivalent Sc(2), and one Cu(2) atom to form OSc3Cu tetrahedra that share corners with two equivalent O(5)Sc3Cu tetrahedra, corners with four equivalent O(1)Sc3Cu tetrahedra, corners with three equivalent O(2)Sc2Cu2 trigonal pyramids, corners with three equivalent O(4)Sc2Cu2 trigonal pyramids, and  an edgeedge with one O(2)Sc2Cu2 trigonal pyramid. In the second O site, O(1) is bonded to one Sc(2), two equivalent Sc(1), and one Cu(1) atom to form distorted OSc3Cu tetrahedra that share corners with two equivalent O(1)Sc3Cu tetrahedra, corners with four equivalent O(5)Sc3Cu tetrahedra, corners with three equivalent O(2)Sc2Cu2 trigonal pyramids, corners with three equivalent O(4)Sc2Cu2 trigonal pyramids, and  an edgeedge with one O(4)Sc2Cu2 trigonal pyramid. In the third O site, O(2) is bonded to two equivalent Sc(2), one Cu(1), and one Cu(2) atom to form OSc2Cu2 trigonal pyramids that share corners with three equivalent O(1)Sc3Cu tetrahedra, corners with three equivalent O(5)Sc3Cu tetrahedra, corners with two equivalent O(2)Sc2Cu2 trigonal pyramids,  an edgeedge with one O(5)Sc3Cu tetrahedra, and  an edgeedge with one O(4)Sc2Cu2 trigonal pyramid. In the fourth O site, O(3) is bonded in a 6-coordinate geometry to one Sc(1), one Sc(2), two equivalent Cu(1), and two equivalent Cu(2) atoms. In the fifth O site, O(4) is bonded to two equivalent Sc(1), one Cu(1), and one Cu(2) atom to form OSc2Cu2 trigonal pyramids that share corners with three equivalent O(1)Sc3Cu tetrahedra, corners with three equivalent O(5)Sc3Cu tetrahedra, corners with two equivalent O(4)Sc2Cu2 trigonal pyramids,  an edgeedge with one O(1)Sc3Cu tetrahedra, and  an edgeedge with one O(2)Sc2Cu2 trigonal pyramid.