Sm2V2O7 crystallizes in the cubic Fd-3m space group. Sm(1) is bonded to two equivalent O(2) and six equivalent O(1) atoms to form distorted SmO8 hexagonal bipyramids that share edges with six equivalent Sm(1)O8 hexagonal bipyramids and edges with six equivalent V(1)O6 octahedra. V(1) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent V(1)O6 octahedra and edges with six equivalent Sm(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Sm(1) and two equivalent V(1) atoms to form distorted OSm2V2 tetrahedra that share corners with two equivalent O(2)Sm4 tetrahedra, corners with twelve equivalent O(1)Sm2V2 tetrahedra,  an edgeedge with one O(2)Sm4 tetrahedra, and edges with four equivalent O(1)Sm2V2 tetrahedra. In the second O site, O(2) is bonded to four equivalent Sm(1) atoms to form OSm4 tetrahedra that share corners with four equivalent O(2)Sm4 tetrahedra, corners with twelve equivalent O(1)Sm2V2 tetrahedra, and edges with six equivalent O(1)Sm2V2 tetrahedra.
Sm2V2O7 crystallizes in the cubic Fd-3m space group. Sm(1) is bonded to two equivalent O(2) and six equivalent O(1) atoms to form distorted SmO8 hexagonal bipyramids that share edges with six equivalent Sm(1)O8 hexagonal bipyramids and edges with six equivalent V(1)O6 octahedra. Both Sm(1)-O(2) bond lengths are 2.22 Å. All Sm(1)-O(1) bond lengths are 2.53 Å. V(1) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent V(1)O6 octahedra and edges with six equivalent Sm(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. All V(1)-O(1) bond lengths are 1.98 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Sm(1) and two equivalent V(1) atoms to form distorted OSm2V2 tetrahedra that share corners with two equivalent O(2)Sm4 tetrahedra, corners with twelve equivalent O(1)Sm2V2 tetrahedra,  an edgeedge with one O(2)Sm4 tetrahedra, and edges with four equivalent O(1)Sm2V2 tetrahedra. In the second O site, O(2) is bonded to four equivalent Sm(1) atoms to form OSm4 tetrahedra that share corners with four equivalent O(2)Sm4 tetrahedra, corners with twelve equivalent O(1)Sm2V2 tetrahedra, and edges with six equivalent O(1)Sm2V2 tetrahedra.