Na3VO13I crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(10), one O(3), one O(4), one O(5), one O(6), and one O(9) atom. In the second Na site, Na(2) is bonded to one O(1), one O(11), one O(12), one O(13), one O(3), and one O(7) atom to form distorted NaO6 pentagonal pyramids that share  a cornercorner with one I(1)O6 octahedra and  an edgeedge with one I(1)O6 octahedra. The corner-sharing octahedral tilt angles are 60°. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(10), one O(3), one O(4), one O(5), one O(6), and one O(8) atom. V(1) is bonded in a 6-coordinate geometry to one O(4), one O(5), one O(6), one O(7), and two equivalent O(8) atoms. There are thirteen inequivalent O sites. In the first O site, O(12) is bonded in a bent 120 degrees geometry to one Na(2) and one O(2) atom. In the second O site, O(13) is bonded in a water-like geometry to one Na(2) and one O(11) atom. In the third O site, O(1) is bonded in a water-like geometry to one Na(2) and one I(1) atom. In the fourth O site, O(2) is bonded in a bent 120 degrees geometry to one O(12) and one I(1) atom. In the fifth O site, O(3) is bonded in a see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one I(1) atom. In the sixth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), and one V(1) atom. In the seventh O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), and one V(1) atom. In the eighth O site, O(6) is bonded to one Na(1), one Na(3), one V(1), and one I(1) atom to form distorted edge-sharing ONa2VI trigonal pyramids. In the ninth O site, O(7) is bonded in a trigonal planar geometry to one Na(2), one V(1), and one I(1) atom. In the tenth O site, O(8) is bonded to one Na(3), two equivalent V(1), and one I(1) atom to form distorted ONaV2I trigonal pyramids that share  an edgeedge with one O(8)NaV2I trigonal pyramid and edges with two equivalent O(6)Na2VI trigonal pyramids. In the eleventh O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one O(10) atom. In the twelfth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), and one O(9) atom. In the thirteenth O site, O(11) is bonded in a water-like geometry to one Na(2) and one O(13) atom. I(1) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form IO6 octahedra that share  a cornercorner with one Na(2)O6 pentagonal pyramid and  an edgeedge with one Na(2)O6 pentagonal pyramid.
Na3VO13I crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(10), one O(3), one O(4), one O(5), one O(6), and one O(9) atom. The Na(1)-O(10) bond length is 2.87 Å. The Na(1)-O(3) bond length is 2.49 Å. The Na(1)-O(4) bond length is 2.70 Å. The Na(1)-O(5) bond length is 2.28 Å. The Na(1)-O(6) bond length is 2.43 Å. The Na(1)-O(9) bond length is 2.75 Å. In the second Na site, Na(2) is bonded to one O(1), one O(11), one O(12), one O(13), one O(3), and one O(7) atom to form distorted NaO6 pentagonal pyramids that share  a cornercorner with one I(1)O6 octahedra and  an edgeedge with one I(1)O6 octahedra. The corner-sharing octahedral tilt angles are 60°. The Na(2)-O(1) bond length is 2.31 Å. The Na(2)-O(11) bond length is 2.77 Å. The Na(2)-O(12) bond length is 2.37 Å. The Na(2)-O(13) bond length is 2.76 Å. The Na(2)-O(3) bond length is 2.46 Å. The Na(2)-O(7) bond length is 2.34 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(10), one O(3), one O(4), one O(5), one O(6), and one O(8) atom. The Na(3)-O(10) bond length is 2.74 Å. The Na(3)-O(3) bond length is 2.55 Å. The Na(3)-O(4) bond length is 2.34 Å. The Na(3)-O(5) bond length is 2.50 Å. The Na(3)-O(6) bond length is 2.57 Å. The Na(3)-O(8) bond length is 2.34 Å. V(1) is bonded in a 6-coordinate geometry to one O(4), one O(5), one O(6), one O(7), and two equivalent O(8) atoms. The V(1)-O(4) bond length is 1.67 Å. The V(1)-O(5) bond length is 1.69 Å. The V(1)-O(6) bond length is 2.00 Å. The V(1)-O(7) bond length is 1.95 Å. There is one shorter (2.22 Å) and one longer (2.48 Å) V(1)-O(8) bond length. There are thirteen inequivalent O sites. In the first O site, O(12) is bonded in a bent 120 degrees geometry to one Na(2) and one O(2) atom. The O(12)-O(2) bond length is 1.29 Å. In the second O site, O(13) is bonded in a water-like geometry to one Na(2) and one O(11) atom. The O(13)-O(11) bond length is 1.24 Å. In the third O site, O(1) is bonded in a water-like geometry to one Na(2) and one I(1) atom. The O(1)-I(1) bond length is 1.83 Å. In the fourth O site, O(2) is bonded in a bent 120 degrees geometry to one O(12) and one I(1) atom. The O(2)-I(1) bond length is 2.31 Å. In the fifth O site, O(3) is bonded in a see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one I(1) atom. The O(3)-I(1) bond length is 1.86 Å. In the sixth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), and one V(1) atom. In the seventh O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), and one V(1) atom. In the eighth O site, O(6) is bonded to one Na(1), one Na(3), one V(1), and one I(1) atom to form distorted edge-sharing ONa2VI trigonal pyramids. The O(6)-I(1) bond length is 1.98 Å. In the ninth O site, O(7) is bonded in a trigonal planar geometry to one Na(2), one V(1), and one I(1) atom. The O(7)-I(1) bond length is 1.99 Å. In the tenth O site, O(8) is bonded to one Na(3), two equivalent V(1), and one I(1) atom to form distorted ONaV2I trigonal pyramids that share  an edgeedge with one O(8)NaV2I trigonal pyramid and edges with two equivalent O(6)Na2VI trigonal pyramids. The O(8)-I(1) bond length is 1.88 Å. In the eleventh O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one O(10) atom. The O(9)-O(10) bond length is 1.23 Å. In the twelfth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), and one O(9) atom. In the thirteenth O site, O(11) is bonded in a water-like geometry to one Na(2) and one O(13) atom. I(1) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form IO6 octahedra that share  a cornercorner with one Na(2)O6 pentagonal pyramid and  an edgeedge with one Na(2)O6 pentagonal pyramid.