Sm2MoO6 crystallizes in the monoclinic C2/c space group. There are three inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 8-coordinate geometry to one O(1), one O(5), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. In the second Sm site, Sm(2) is bonded in a distorted body-centered cubic geometry to two equivalent O(1), two equivalent O(5), and four equivalent O(4) atoms. In the third Sm site, Sm(3) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(5), and four equivalent O(6) atoms. Mo(1) is bonded in a distorted trigonal bipyramidal geometry to one O(1), one O(2), one O(3), one O(5), and one O(6) atom. There are six inequivalent O sites. In the first O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Sm(1) and one Mo(1) atom. In the second O site, O(4) is bonded to two equivalent Sm(1) and two equivalent Sm(2) atoms to form OSm4 tetrahedra that share corners with two equivalent O(4)Sm4 tetrahedra, corners with four equivalent O(5)Sm3Mo tetrahedra,  an edgeedge with one O(5)Sm3Mo tetrahedra, and edges with three equivalent O(4)Sm4 tetrahedra. In the third O site, O(5) is bonded to one Sm(1), one Sm(2), one Sm(3), and one Mo(1) atom to form OSm3Mo tetrahedra that share corners with two equivalent O(5)Sm3Mo tetrahedra, corners with four equivalent O(4)Sm4 tetrahedra, and  an edgeedge with one O(4)Sm4 tetrahedra. In the fourth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Sm(3) and one Mo(1) atom. In the fifth O site, O(1) is bonded in a 4-coordinate geometry to one Sm(1), one Sm(2), one Sm(3), and one Mo(1) atom. In the sixth O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Sm(1) and one Mo(1) atom.
Sm2MoO6 crystallizes in the monoclinic C2/c space group. There are three inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 8-coordinate geometry to one O(1), one O(5), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. The Sm(1)-O(1) bond length is 2.72 Å. The Sm(1)-O(5) bond length is 2.33 Å. There is one shorter (2.45 Å) and one longer (2.50 Å) Sm(1)-O(2) bond length. There is one shorter (2.49 Å) and one longer (2.62 Å) Sm(1)-O(3) bond length. There is one shorter (2.23 Å) and one longer (2.31 Å) Sm(1)-O(4) bond length. In the second Sm site, Sm(2) is bonded in a distorted body-centered cubic geometry to two equivalent O(1), two equivalent O(5), and four equivalent O(4) atoms. Both Sm(2)-O(1) bond lengths are 2.80 Å. Both Sm(2)-O(5) bond lengths are 2.36 Å. There are two shorter (2.28 Å) and two longer (2.43 Å) Sm(2)-O(4) bond lengths. In the third Sm site, Sm(3) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(5), and four equivalent O(6) atoms. Both Sm(3)-O(1) bond lengths are 2.50 Å. Both Sm(3)-O(5) bond lengths are 2.26 Å. There are two shorter (2.44 Å) and two longer (2.54 Å) Sm(3)-O(6) bond lengths. Mo(1) is bonded in a distorted trigonal bipyramidal geometry to one O(1), one O(2), one O(3), one O(5), and one O(6) atom. The Mo(1)-O(1) bond length is 1.81 Å. The Mo(1)-O(2) bond length is 1.82 Å. The Mo(1)-O(3) bond length is 1.79 Å. The Mo(1)-O(5) bond length is 2.21 Å. The Mo(1)-O(6) bond length is 1.79 Å. There are six inequivalent O sites. In the first O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Sm(1) and one Mo(1) atom. In the second O site, O(4) is bonded to two equivalent Sm(1) and two equivalent Sm(2) atoms to form OSm4 tetrahedra that share corners with two equivalent O(4)Sm4 tetrahedra, corners with four equivalent O(5)Sm3Mo tetrahedra,  an edgeedge with one O(5)Sm3Mo tetrahedra, and edges with three equivalent O(4)Sm4 tetrahedra. In the third O site, O(5) is bonded to one Sm(1), one Sm(2), one Sm(3), and one Mo(1) atom to form OSm3Mo tetrahedra that share corners with two equivalent O(5)Sm3Mo tetrahedra, corners with four equivalent O(4)Sm4 tetrahedra, and  an edgeedge with one O(4)Sm4 tetrahedra. In the fourth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Sm(3) and one Mo(1) atom. In the fifth O site, O(1) is bonded in a 4-coordinate geometry to one Sm(1), one Sm(2), one Sm(3), and one Mo(1) atom. In the sixth O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Sm(1) and one Mo(1) atom.