Na2Ge2O5 crystallizes in the orthorhombic Pbcn space group. Na(1) is bonded to one O(3) and four equivalent O(2) atoms to form distorted NaO5 trigonal bipyramids that share corners with four equivalent Ge(1)O4 tetrahedra, corners with four equivalent Na(1)O5 trigonal bipyramids,  an edgeedge with one Ge(1)O4 tetrahedra, and edges with four equivalent Na(1)O5 trigonal bipyramids. Ge(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form GeO4 tetrahedra that share corners with three equivalent Ge(1)O4 tetrahedra, corners with four equivalent Na(1)O5 trigonal bipyramids, and  an edgeedge with one Na(1)O5 trigonal bipyramid. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent Ge(1) atoms. In the second O site, O(2) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one Ge(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent Ge(1) atoms.
Na2Ge2O5 crystallizes in the orthorhombic Pbcn space group. Na(1) is bonded to one O(3) and four equivalent O(2) atoms to form distorted NaO5 trigonal bipyramids that share corners with four equivalent Ge(1)O4 tetrahedra, corners with four equivalent Na(1)O5 trigonal bipyramids,  an edgeedge with one Ge(1)O4 tetrahedra, and edges with four equivalent Na(1)O5 trigonal bipyramids. The Na(1)-O(3) bond length is 2.34 Å. There are a spread of Na(1)-O(2) bond distances ranging from 2.30-2.78 Å. Ge(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form GeO4 tetrahedra that share corners with three equivalent Ge(1)O4 tetrahedra, corners with four equivalent Na(1)O5 trigonal bipyramids, and  an edgeedge with one Na(1)O5 trigonal bipyramid. The Ge(1)-O(1) bond length is 1.77 Å. The Ge(1)-O(2) bond length is 1.73 Å. There is one shorter (1.80 Å) and one longer (1.81 Å) Ge(1)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent Ge(1) atoms. In the second O site, O(2) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one Ge(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent Ge(1) atoms.