NaV3H6(SO7)2 crystallizes in the trigonal R-3m space group. Na(1) is bonded to six equivalent O(2) and six equivalent O(3) atoms to form NaO12 cuboctahedra that share corners with six equivalent S(1)O4 tetrahedra and faces with six equivalent V(1)O6 octahedra. V(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with two equivalent S(1)O4 tetrahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 48°. H(1) is bonded in a single-bond geometry to one O(3) atom. S(1) is bonded to one O(1) and three equivalent O(2) atoms to form SO4 tetrahedra that share corners with three equivalent Na(1)O12 cuboctahedra and corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one S(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(1), one V(1), and one S(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(1), two equivalent V(1), and one H(1) atom.
NaV3H6(SO7)2 crystallizes in the trigonal R-3m space group. Na(1) is bonded to six equivalent O(2) and six equivalent O(3) atoms to form NaO12 cuboctahedra that share corners with six equivalent S(1)O4 tetrahedra and faces with six equivalent V(1)O6 octahedra. All Na(1)-O(2) bond lengths are 3.01 Å. All Na(1)-O(3) bond lengths are 2.78 Å. V(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with two equivalent S(1)O4 tetrahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 48°. Both V(1)-O(2) bond lengths are 2.09 Å. All V(1)-O(3) bond lengths are 2.03 Å. H(1) is bonded in a single-bond geometry to one O(3) atom. The H(1)-O(3) bond length is 0.99 Å. S(1) is bonded to one O(1) and three equivalent O(2) atoms to form SO4 tetrahedra that share corners with three equivalent Na(1)O12 cuboctahedra and corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. The S(1)-O(1) bond length is 1.48 Å. All S(1)-O(2) bond lengths are 1.49 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one S(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(1), one V(1), and one S(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(1), two equivalent V(1), and one H(1) atom.