Sm2ReO5 crystallizes in the tetragonal P4/n space group. Sm(1) is bonded in a 8-coordinate geometry to one O(3), one O(4), three equivalent O(1), and three equivalent O(2) atoms. There are two inequivalent Re sites. In the first Re site, Re(1) is bonded in a distorted square co-planar geometry to four equivalent O(2) atoms. In the second Re site, Re(2) is bonded in a distorted square co-planar geometry to four equivalent O(1) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Sm(1) and one Re(2) atom to form distorted OSm3Re tetrahedra that share  a cornercorner with one O(4)Sm4 tetrahedra, corners with three equivalent O(1)Sm3Re tetrahedra, corners with three equivalent O(3)Sm4 tetrahedra,  an edgeedge with one O(4)Sm4 tetrahedra, and edges with three equivalent O(1)Sm3Re tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to three equivalent Sm(1) and one Re(1) atom. In the third O site, O(3) is bonded to four equivalent Sm(1) atoms to form OSm4 tetrahedra that share corners with twelve equivalent O(1)Sm3Re tetrahedra and edges with two equivalent O(4)Sm4 tetrahedra. In the fourth O site, O(4) is bonded to four equivalent Sm(1) atoms to form OSm4 tetrahedra that share corners with four equivalent O(1)Sm3Re tetrahedra, edges with two equivalent O(3)Sm4 tetrahedra, and edges with four equivalent O(1)Sm3Re tetrahedra.
Sm2ReO5 crystallizes in the tetragonal P4/n space group. Sm(1) is bonded in a 8-coordinate geometry to one O(3), one O(4), three equivalent O(1), and three equivalent O(2) atoms. The Sm(1)-O(3) bond length is 2.29 Å. The Sm(1)-O(4) bond length is 2.30 Å. There are a spread of Sm(1)-O(1) bond distances ranging from 2.46-2.53 Å. There are a spread of Sm(1)-O(2) bond distances ranging from 2.43-2.63 Å. There are two inequivalent Re sites. In the first Re site, Re(1) is bonded in a distorted square co-planar geometry to four equivalent O(2) atoms. All Re(1)-O(2) bond lengths are 1.93 Å. In the second Re site, Re(2) is bonded in a distorted square co-planar geometry to four equivalent O(1) atoms. All Re(2)-O(1) bond lengths are 1.93 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Sm(1) and one Re(2) atom to form distorted OSm3Re tetrahedra that share  a cornercorner with one O(4)Sm4 tetrahedra, corners with three equivalent O(1)Sm3Re tetrahedra, corners with three equivalent O(3)Sm4 tetrahedra,  an edgeedge with one O(4)Sm4 tetrahedra, and edges with three equivalent O(1)Sm3Re tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to three equivalent Sm(1) and one Re(1) atom. In the third O site, O(3) is bonded to four equivalent Sm(1) atoms to form OSm4 tetrahedra that share corners with twelve equivalent O(1)Sm3Re tetrahedra and edges with two equivalent O(4)Sm4 tetrahedra. In the fourth O site, O(4) is bonded to four equivalent Sm(1) atoms to form OSm4 tetrahedra that share corners with four equivalent O(1)Sm3Re tetrahedra, edges with two equivalent O(3)Sm4 tetrahedra, and edges with four equivalent O(1)Sm3Re tetrahedra.