Na5V2(PO5)3 crystallizes in the monoclinic Cm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(6), one O(8), and one O(9) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(4), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(8), two equivalent O(1), and two equivalent O(7) atoms. V(1) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form distorted VO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O5 trigonal bipyramids. In the second P site, P(2) is bonded to one O(8), one O(9), and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O5 trigonal bipyramids. There are nine inequivalent O sites. In the first O site, O(8) is bonded in a distorted tetrahedral geometry to one Na(3), two equivalent Na(1), and one P(2) atom. In the second O site, O(9) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one P(2) atom. In the third O site, O(1) is bonded in a distorted linear geometry to two equivalent Na(3) atoms. In the fourth O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one P(1) atom. In the fifth O site, O(3) is bonded in a 1-coordinate geometry to one Na(1), two equivalent Na(2), and one V(1) atom. In the sixth O site, O(4) is bonded in a 2-coordinate geometry to one Na(2), one V(1), and one P(1) atom. In the seventh O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(2), one V(1), and one P(1) atom. In the eighth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one P(1) atom. In the ninth O site, O(7) is bonded in a 3-coordinate geometry to one Na(3), one V(1), and one P(2) atom.
Na5V2(PO5)3 crystallizes in the monoclinic Cm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(6), one O(8), and one O(9) atom. The Na(1)-O(2) bond length is 2.53 Å. The Na(1)-O(3) bond length is 2.67 Å. The Na(1)-O(6) bond length is 2.46 Å. The Na(1)-O(8) bond length is 2.32 Å. The Na(1)-O(9) bond length is 2.29 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(4), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. The Na(2)-O(4) bond length is 2.73 Å. There is one shorter (2.33 Å) and one longer (2.36 Å) Na(2)-O(2) bond length. There is one shorter (2.51 Å) and one longer (2.89 Å) Na(2)-O(3) bond length. Both Na(2)-O(5) bond lengths are 2.46 Å. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(8), two equivalent O(1), and two equivalent O(7) atoms. The Na(3)-O(8) bond length is 2.26 Å. There is one shorter (2.60 Å) and one longer (2.63 Å) Na(3)-O(1) bond length. Both Na(3)-O(7) bond lengths are 2.38 Å. V(1) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form distorted VO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. The V(1)-O(3) bond length is 1.65 Å. The V(1)-O(4) bond length is 2.01 Å. The V(1)-O(5) bond length is 2.00 Å. The V(1)-O(6) bond length is 2.00 Å. The V(1)-O(7) bond length is 1.92 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O5 trigonal bipyramids. The P(1)-O(2) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.58 Å. The P(1)-O(6) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(8), one O(9), and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O5 trigonal bipyramids. The P(2)-O(8) bond length is 1.52 Å. The P(2)-O(9) bond length is 1.51 Å. Both P(2)-O(7) bond lengths are 1.60 Å. There are nine inequivalent O sites. In the first O site, O(8) is bonded in a distorted tetrahedral geometry to one Na(3), two equivalent Na(1), and one P(2) atom. In the second O site, O(9) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one P(2) atom. In the third O site, O(1) is bonded in a distorted linear geometry to two equivalent Na(3) atoms. In the fourth O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one P(1) atom. In the fifth O site, O(3) is bonded in a 1-coordinate geometry to one Na(1), two equivalent Na(2), and one V(1) atom. In the sixth O site, O(4) is bonded in a 2-coordinate geometry to one Na(2), one V(1), and one P(1) atom. In the seventh O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(2), one V(1), and one P(1) atom. In the eighth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one P(1) atom. In the ninth O site, O(7) is bonded in a 3-coordinate geometry to one Na(3), one V(1), and one P(2) atom.