NaV3(SO7)2 crystallizes in the trigonal R32 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 distorted 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 39°. 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 51°. 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 2-coordinate 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 bent 150 degrees geometry to one Na(1) and two equivalent V(1) atoms.
NaV3(SO7)2 crystallizes in the trigonal R32 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 2.86 Å. All Na(1)-O(3) bond lengths are 2.96 Å. V(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form distorted 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 39°. Both V(1)-O(2) bond lengths are 2.00 Å. There are two shorter (1.70 Å) and two longer (2.09 Å) V(1)-O(3) bond lengths. 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 51°. The S(1)-O(1) bond length is 1.43 Å. All S(1)-O(2) bond lengths are 1.52 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 2-coordinate 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 bent 150 degrees geometry to one Na(1) and two equivalent V(1) atoms.