NaSmV4O12 crystallizes in the tetragonal P4/mmm space group. Na(1) is bonded to four equivalent O(2) and eight equivalent O(1) atoms to form NaO12 cuboctahedra that share corners with four equivalent Na(1)O12 cuboctahedra, corners with eight equivalent Sm(1)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. Sm(1) is bonded to four equivalent O(3) and eight equivalent O(1) atoms to form SmO12 cuboctahedra that share corners with four equivalent Sm(1)O12 cuboctahedra, corners with eight equivalent Na(1)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. V(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent V(1)O6 octahedra, faces with two equivalent Na(1)O12 cuboctahedra, and faces with two equivalent Sm(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-6°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to one Na(1), one Sm(1), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted linear geometry to two equivalent Na(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a distorted linear geometry to two equivalent Sm(1) and two equivalent V(1) atoms.
NaSmV4O12 crystallizes in the tetragonal P4/mmm space group. Na(1) is bonded to four equivalent O(2) and eight equivalent O(1) atoms to form NaO12 cuboctahedra that share corners with four equivalent Na(1)O12 cuboctahedra, corners with eight equivalent Sm(1)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. All Na(1)-O(2) bond lengths are 2.65 Å. All Na(1)-O(1) bond lengths are 2.72 Å. Sm(1) is bonded to four equivalent O(3) and eight equivalent O(1) atoms to form SmO12 cuboctahedra that share corners with four equivalent Sm(1)O12 cuboctahedra, corners with eight equivalent Na(1)O12 cuboctahedra, and faces with eight equivalent V(1)O6 octahedra. All Sm(1)-O(3) bond lengths are 2.65 Å. All Sm(1)-O(1) bond lengths are 2.59 Å. V(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent V(1)O6 octahedra, faces with two equivalent Na(1)O12 cuboctahedra, and faces with two equivalent Sm(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-6°. The V(1)-O(2) bond length is 1.84 Å. The V(1)-O(3) bond length is 1.92 Å. All V(1)-O(1) bond lengths are 1.88 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to one Na(1), one Sm(1), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted linear geometry to two equivalent Na(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a distorted linear geometry to two equivalent Sm(1) and two equivalent V(1) atoms.