SmBi3(Ru2O7)2 crystallizes in the trigonal R-3m space group. Sm(1) is bonded to two equivalent O(3) and six equivalent O(2) atoms to form distorted SmO8 hexagonal bipyramids that share edges with six equivalent Bi(1)O8 hexagonal bipyramids and edges with six equivalent Ru(2)O6 octahedra. There are two inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to six equivalent O(1) atoms to form RuO6 octahedra that share corners with six equivalent Ru(2)O6 octahedra and edges with six equivalent Bi(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. In the second Ru site, Ru(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form RuO6 octahedra that share corners with two equivalent Ru(1)O6 octahedra, corners with four equivalent Ru(2)O6 octahedra, edges with two equivalent Sm(1)O8 hexagonal bipyramids, and edges with four equivalent Bi(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. Bi(1) is bonded to two equivalent O(2), two equivalent O(3), and four equivalent O(1) atoms to form distorted BiO8 hexagonal bipyramids that share edges with two equivalent Sm(1)O8 hexagonal bipyramids, edges with four equivalent Bi(1)O8 hexagonal bipyramids, edges with two equivalent Ru(1)O6 octahedra, and edges with four equivalent Ru(2)O6 octahedra. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Sm(1) and three equivalent Bi(1) atoms to form OSmBi3 tetrahedra that share corners with four equivalent O(3)SmBi3 tetrahedra, corners with six equivalent O(1)Bi2Ru2 tetrahedra, corners with six equivalent O(2)SmBiRu2 tetrahedra, edges with three equivalent O(1)Bi2Ru2 tetrahedra, and edges with three equivalent O(2)SmBiRu2 tetrahedra. In the second O site, O(1) is bonded to one Ru(1), one Ru(2), and two equivalent Bi(1) atoms to form distorted OBi2Ru2 tetrahedra that share corners with two equivalent O(3)SmBi3 tetrahedra, corners with four equivalent O(2)SmBiRu2 tetrahedra, corners with eight equivalent O(1)Bi2Ru2 tetrahedra,  an edgeedge with one O(3)SmBi3 tetrahedra, edges with two equivalent O(1)Bi2Ru2 tetrahedra, and edges with two equivalent O(2)SmBiRu2 tetrahedra. In the third O site, O(2) is bonded to one Sm(1), two equivalent Ru(2), and one Bi(1) atom to form distorted OSmBiRu2 tetrahedra that share corners with two equivalent O(3)SmBi3 tetrahedra, corners with four equivalent O(1)Bi2Ru2 tetrahedra, corners with eight equivalent O(2)SmBiRu2 tetrahedra,  an edgeedge with one O(3)SmBi3 tetrahedra, edges with two equivalent O(1)Bi2Ru2 tetrahedra, and edges with two equivalent O(2)SmBiRu2 tetrahedra.
SmBi3(Ru2O7)2 crystallizes in the trigonal R-3m space group. Sm(1) is bonded to two equivalent O(3) and six equivalent O(2) atoms to form distorted SmO8 hexagonal bipyramids that share edges with six equivalent Bi(1)O8 hexagonal bipyramids and edges with six equivalent Ru(2)O6 octahedra. Both Sm(1)-O(3) bond lengths are 2.23 Å. All Sm(1)-O(2) bond lengths are 2.56 Å. There are two inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to six equivalent O(1) atoms to form RuO6 octahedra that share corners with six equivalent Ru(2)O6 octahedra and edges with six equivalent Bi(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. All Ru(1)-O(1) bond lengths are 2.01 Å. In the second Ru site, Ru(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form RuO6 octahedra that share corners with two equivalent Ru(1)O6 octahedra, corners with four equivalent Ru(2)O6 octahedra, edges with two equivalent Sm(1)O8 hexagonal bipyramids, and edges with four equivalent Bi(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. Both Ru(2)-O(1) bond lengths are 2.03 Å. All Ru(2)-O(2) bond lengths are 2.01 Å. Bi(1) is bonded to two equivalent O(2), two equivalent O(3), and four equivalent O(1) atoms to form distorted BiO8 hexagonal bipyramids that share edges with two equivalent Sm(1)O8 hexagonal bipyramids, edges with four equivalent Bi(1)O8 hexagonal bipyramids, edges with two equivalent Ru(1)O6 octahedra, and edges with four equivalent Ru(2)O6 octahedra. Both Bi(1)-O(2) bond lengths are 2.56 Å. Both Bi(1)-O(3) bond lengths are 2.26 Å. All Bi(1)-O(1) bond lengths are 2.55 Å. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Sm(1) and three equivalent Bi(1) atoms to form OSmBi3 tetrahedra that share corners with four equivalent O(3)SmBi3 tetrahedra, corners with six equivalent O(1)Bi2Ru2 tetrahedra, corners with six equivalent O(2)SmBiRu2 tetrahedra, edges with three equivalent O(1)Bi2Ru2 tetrahedra, and edges with three equivalent O(2)SmBiRu2 tetrahedra. In the second O site, O(1) is bonded to one Ru(1), one Ru(2), and two equivalent Bi(1) atoms to form distorted OBi2Ru2 tetrahedra that share corners with two equivalent O(3)SmBi3 tetrahedra, corners with four equivalent O(2)SmBiRu2 tetrahedra, corners with eight equivalent O(1)Bi2Ru2 tetrahedra,  an edgeedge with one O(3)SmBi3 tetrahedra, edges with two equivalent O(1)Bi2Ru2 tetrahedra, and edges with two equivalent O(2)SmBiRu2 tetrahedra. In the third O site, O(2) is bonded to one Sm(1), two equivalent Ru(2), and one Bi(1) atom to form distorted OSmBiRu2 tetrahedra that share corners with two equivalent O(3)SmBi3 tetrahedra, corners with four equivalent O(1)Bi2Ru2 tetrahedra, corners with eight equivalent O(2)SmBiRu2 tetrahedra,  an edgeedge with one O(3)SmBi3 tetrahedra, edges with two equivalent O(1)Bi2Ru2 tetrahedra, and edges with two equivalent O(2)SmBiRu2 tetrahedra.