Na3SmV2O8 crystallizes in the trigonal P-3m1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a single-bond geometry to one O(1) atom. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to six equivalent O(2) atoms. Sm(1) is bonded to six equivalent O(2) atoms to form SmO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra. V(1) is bonded to one O(1) and three equivalent O(2) atoms to form VO4 tetrahedra that share corners with three equivalent Sm(1)O6 octahedra. The corner-sharing octahedral tilt angles are 17°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Na(1) and one V(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(2), one Sm(1), and one V(1) atom.
Na3SmV2O8 crystallizes in the trigonal P-3m1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a single-bond geometry to one O(1) atom. The Na(1)-O(1) bond length is 2.18 Å. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to six equivalent O(2) atoms. All Na(2)-O(2) bond lengths are 2.89 Å. Sm(1) is bonded to six equivalent O(2) atoms to form SmO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra. All Sm(1)-O(2) bond lengths are 2.30 Å. V(1) is bonded to one O(1) and three equivalent O(2) atoms to form VO4 tetrahedra that share corners with three equivalent Sm(1)O6 octahedra. The corner-sharing octahedral tilt angles are 17°. The V(1)-O(1) bond length is 1.68 Å. All V(1)-O(2) bond lengths are 1.76 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Na(1) and one V(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(2), one Sm(1), and one V(1) atom.