Na2SrV4O12 crystallizes in the tetragonal P4/nbm space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with eight equivalent V(1)O4 tetrahedra. Sr(1) is bonded in a 8-coordinate geometry to eight equivalent O(1) atoms. V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with four equivalent Na(1)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-70°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Sr(1), and one V(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1) and two equivalent V(1) atoms.
Na2SrV4O12 crystallizes in the tetragonal P4/nbm space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with eight equivalent V(1)O4 tetrahedra. Both Na(1)-O(2) bond lengths are 2.68 Å. All Na(1)-O(1) bond lengths are 2.45 Å. Sr(1) is bonded in a 8-coordinate geometry to eight equivalent O(1) atoms. All Sr(1)-O(1) bond lengths are 2.60 Å. V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with four equivalent Na(1)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-70°. Both V(1)-O(1) bond lengths are 1.68 Å. Both V(1)-O(2) bond lengths are 1.83 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Sr(1), and one V(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1) and two equivalent V(1) atoms.