Na2V2O5 is Chalcostibite-like structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(3), one O(5), and two equivalent O(1) atoms to form distorted NaO5 trigonal bipyramids that share corners with two equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, corners with two equivalent Na(2)O4 trigonal pyramids,  an edgeedge with one V(2)O4 tetrahedra,  an edgeedge with one Na(1)O5 trigonal bipyramid, and  an edgeedge with one Na(2)O4 trigonal pyramid. In the second Na site, Na(2) is bonded to one O(1), one O(4), and two equivalent O(2) atoms to form NaO4 trigonal pyramids that share  a cornercorner with one V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, corners with two equivalent Na(1)O5 trigonal bipyramids,  an edgeedge with one Na(1)O5 trigonal bipyramid, and  an edgeedge with one Na(2)O4 trigonal pyramid. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(5), and two equivalent O(4) atoms to form VO4 tetrahedra that share  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent Na(1)O5 trigonal bipyramids, and corners with four equivalent Na(2)O4 trigonal pyramids. In the second V site, V(2) is bonded to one O(1), one O(5), and two equivalent O(3) atoms to form VO4 tetrahedra that share  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with three equivalent Na(1)O5 trigonal bipyramids,  a cornercorner with one Na(2)O4 trigonal pyramid, and  an edgeedge with one Na(1)O5 trigonal bipyramid. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one V(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one V(1) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(1) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(2) and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Na(1), one V(1), and one V(2) atom.
Na2V2O5 is Chalcostibite-like structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(3), one O(5), and two equivalent O(1) atoms to form distorted NaO5 trigonal bipyramids that share corners with two equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, corners with two equivalent Na(2)O4 trigonal pyramids,  an edgeedge with one V(2)O4 tetrahedra,  an edgeedge with one Na(1)O5 trigonal bipyramid, and  an edgeedge with one Na(2)O4 trigonal pyramid. The Na(1)-O(2) bond length is 2.44 Å. The Na(1)-O(3) bond length is 2.38 Å. The Na(1)-O(5) bond length is 2.36 Å. There is one shorter (2.37 Å) and one longer (2.76 Å) Na(1)-O(1) bond length. In the second Na site, Na(2) is bonded to one O(1), one O(4), and two equivalent O(2) atoms to form NaO4 trigonal pyramids that share  a cornercorner with one V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, corners with two equivalent Na(1)O5 trigonal bipyramids,  an edgeedge with one Na(1)O5 trigonal bipyramid, and  an edgeedge with one Na(2)O4 trigonal pyramid. The Na(2)-O(1) bond length is 2.36 Å. The Na(2)-O(4) bond length is 2.37 Å. There is one shorter (2.36 Å) and one longer (2.46 Å) Na(2)-O(2) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(5), and two equivalent O(4) atoms to form VO4 tetrahedra that share  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent Na(1)O5 trigonal bipyramids, and corners with four equivalent Na(2)O4 trigonal pyramids. The V(1)-O(2) bond length is 1.75 Å. The V(1)-O(5) bond length is 1.85 Å. There is one shorter (1.85 Å) and one longer (1.88 Å) V(1)-O(4) bond length. In the second V site, V(2) is bonded to one O(1), one O(5), and two equivalent O(3) atoms to form VO4 tetrahedra that share  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with three equivalent Na(1)O5 trigonal bipyramids,  a cornercorner with one Na(2)O4 trigonal pyramid, and  an edgeedge with one Na(1)O5 trigonal bipyramid. The V(2)-O(1) bond length is 1.72 Å. The V(2)-O(5) bond length is 1.86 Å. There is one shorter (1.82 Å) and one longer (1.87 Å) V(2)-O(3) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one V(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one V(1) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(1) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(2) and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Na(1), one V(1), and one V(2) atom.