Na3PrV2O8 crystallizes in the trigonal P-3m1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a single-bond geometry to one O(1) atom. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to six equivalent O(2) atoms. Pr(1) is bonded to six equivalent O(2) atoms to form PrO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra. V(1) is bonded to one O(1) and three equivalent O(2) atoms to form VO4 tetrahedra that share corners with three equivalent Pr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Na(1) and one V(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(2), one Pr(1), and one V(1) atom.
Na3PrV2O8 crystallizes in the trigonal P-3m1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a single-bond geometry to one O(1) atom. The Na(1)-O(1) bond length is 2.17 Å. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to six equivalent O(2) atoms. All Na(2)-O(2) bond lengths are 2.91 Å. Pr(1) is bonded to six equivalent O(2) atoms to form PrO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra. All Pr(1)-O(2) bond lengths are 2.35 Å. V(1) is bonded to one O(1) and three equivalent O(2) atoms to form VO4 tetrahedra that share corners with three equivalent Pr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 18°. The V(1)-O(1) bond length is 1.68 Å. All V(1)-O(2) bond lengths are 1.76 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Na(1) and one V(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(2), one Pr(1), and one V(1) atom.