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 4-coordinate geometry to one O(11), one O(12), one O(3), and one O(9) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(13), one O(2), one O(3), and one O(7) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(10), one O(3), one O(4), one O(5), one O(6), and two equivalent O(8) atoms. 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 water-like geometry to one Na(1) and one Na(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 water-like geometry to one Na(2) and one I(1) atom. In the fifth O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), and one I(1) atom to form a mixture of edge and corner-sharing ONa3I tetrahedra. In the sixth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Na(3) and one V(1) atom. In the seventh O site, O(5) is bonded in a distorted single-bond geometry to one Na(3) and one V(1) atom. In the eighth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Na(3), one V(1), and one I(1) atom. In the ninth O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one V(1), and one I(1) atom. In the tenth O site, O(8) is bonded to two equivalent Na(3), two equivalent V(1), and one I(1) atom to form distorted ONa2V2I trigonal bipyramids that share  a cornercorner with one O(3)Na3I tetrahedra,  an edgeedge with one O(3)Na3I tetrahedra, and edges with two equivalent O(8)Na2V2I trigonal bipyramids. In the eleventh O site, O(9) is bonded in a linear geometry to one Na(1) and one O(10) atom. In the twelfth O site, O(10) is bonded in a distorted single-bond geometry to one Na(3) and one O(9) atom. In the thirteenth O site, O(11) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one O(13) atom. I(1) is bonded in an octahedral geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom.
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 4-coordinate geometry to one O(11), one O(12), one O(3), and one O(9) atom. The Na(1)-O(11) bond length is 2.64 Å. The Na(1)-O(12) bond length is 2.45 Å. The Na(1)-O(3) bond length is 2.32 Å. The Na(1)-O(9) bond length is 2.71 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(13), one O(2), one O(3), and one O(7) atom. The Na(2)-O(1) bond length is 2.39 Å. The Na(2)-O(11) bond length is 2.66 Å. The Na(2)-O(12) bond length is 2.58 Å. The Na(2)-O(13) bond length is 2.81 Å. The Na(2)-O(2) bond length is 2.42 Å. The Na(2)-O(3) bond length is 2.45 Å. The Na(2)-O(7) bond length is 2.32 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(10), one O(3), one O(4), one O(5), one O(6), and two equivalent O(8) atoms. The Na(3)-O(10) bond length is 2.99 Å. The Na(3)-O(3) bond length is 2.36 Å. The Na(3)-O(4) bond length is 2.31 Å. The Na(3)-O(5) bond length is 2.70 Å. The Na(3)-O(6) bond length is 2.42 Å. There is one shorter (2.38 Å) and one longer (2.91 Å) Na(3)-O(8) bond length. 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 1.73 Å. The V(1)-O(5) bond length is 1.69 Å. The V(1)-O(6) bond length is 1.92 Å. The V(1)-O(7) bond length is 1.90 Å. There is one shorter (2.14 Å) and one longer (2.43 Å) V(1)-O(8) bond length. There are thirteen inequivalent O sites. In the first O site, O(12) is bonded in a water-like geometry to one Na(1) and one Na(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. The O(13)-O(11) bond length is 1.23 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 water-like geometry to one Na(2) and one I(1) atom. The O(2)-I(1) bond length is 1.90 Å. In the fifth O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), and one I(1) atom to form a mixture of edge and corner-sharing ONa3I tetrahedra. The O(3)-I(1) bond length is 1.87 Å. In the sixth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Na(3) and one V(1) atom. In the seventh O site, O(5) is bonded in a distorted single-bond geometry to one Na(3) and one V(1) atom. In the eighth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Na(3), one V(1), and one I(1) atom. The O(6)-I(1) bond length is 1.99 Å. In the ninth O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one V(1), and one I(1) atom. The O(7)-I(1) bond length is 1.98 Å. In the tenth O site, O(8) is bonded to two equivalent Na(3), two equivalent V(1), and one I(1) atom to form distorted ONa2V2I trigonal bipyramids that share  a cornercorner with one O(3)Na3I tetrahedra,  an edgeedge with one O(3)Na3I tetrahedra, and edges with two equivalent O(8)Na2V2I trigonal bipyramids. The O(8)-I(1) bond length is 1.97 Å. In the eleventh O site, O(9) is bonded in a linear geometry to one Na(1) and one O(10) atom. The O(9)-O(10) bond length is 1.21 Å. In the twelfth O site, O(10) is bonded in a distorted single-bond geometry to one Na(3) and one O(9) atom. In the thirteenth O site, O(11) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one O(13) atom. I(1) is bonded in an octahedral geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom.