Na3V(SO4)3 crystallizes in the trigonal R-3 space group. Na(1) is bonded in a 6-coordinate geometry to one O(4), two equivalent O(2), and three equivalent O(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent S(1)O4 tetrahedra. In the second V site, V(2) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent S(1)O4 tetrahedra. S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-44°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(2) and one S(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one S(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one S(1) atom.
Na3V(SO4)3 crystallizes in the trigonal R-3 space group. Na(1) is bonded in a 6-coordinate geometry to one O(4), two equivalent O(2), and three equivalent O(3) atoms. The Na(1)-O(4) bond length is 2.73 Å. There is one shorter (2.50 Å) and one longer (2.55 Å) Na(1)-O(2) bond length. There are a spread of Na(1)-O(3) bond distances ranging from 2.34-2.78 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent S(1)O4 tetrahedra. All V(1)-O(4) bond lengths are 2.06 Å. In the second V site, V(2) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent S(1)O4 tetrahedra. All V(2)-O(1) bond lengths are 2.01 Å. S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-44°. The S(1)-O(1) bond length is 1.51 Å. The S(1)-O(2) bond length is 1.46 Å. The S(1)-O(3) bond length is 1.48 Å. The S(1)-O(4) bond length is 1.52 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(2) and one S(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one S(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one S(1) atom.