Na2GeO3 crystallizes in the orthorhombic Cmc2_1 space group. Na(1) is bonded to one O(1) and four equivalent O(2) atoms to form distorted NaO5 trigonal bipyramids that share corners with four equivalent Ge(1)O4 tetrahedra, corners with five 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 two equivalent O(1) and two equivalent O(2) atoms to form GeO4 tetrahedra that share corners with two equivalent Ge(1)O4 tetrahedra, corners with eight equivalent Na(1)O5 trigonal bipyramids, and edges with two equivalent Na(1)O5 trigonal bipyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and two equivalent Ge(1) atoms to form distorted ONa2Ge2 trigonal pyramids that share corners with eight equivalent O(2)Na4Ge trigonal bipyramids, corners with two equivalent O(1)Na2Ge2 trigonal pyramids, and edges with two equivalent O(2)Na4Ge trigonal bipyramids. In the second O site, O(2) is bonded to four equivalent Na(1) and one Ge(1) atom to form distorted ONa4Ge trigonal bipyramids that share corners with five equivalent O(2)Na4Ge trigonal bipyramids, corners with four equivalent O(1)Na2Ge2 trigonal pyramids, edges with four equivalent O(2)Na4Ge trigonal bipyramids, and  an edgeedge with one O(1)Na2Ge2 trigonal pyramid.
Na2GeO3 crystallizes in the orthorhombic Cmc2_1 space group. Na(1) is bonded to one O(1) and four equivalent O(2) atoms to form distorted NaO5 trigonal bipyramids that share corners with four equivalent Ge(1)O4 tetrahedra, corners with five 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(1) bond length is 2.37 Å. There are a spread of Na(1)-O(2) bond distances ranging from 2.28-2.57 Å. Ge(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form GeO4 tetrahedra that share corners with two equivalent Ge(1)O4 tetrahedra, corners with eight equivalent Na(1)O5 trigonal bipyramids, and edges with two equivalent Na(1)O5 trigonal bipyramids. There is one shorter (1.80 Å) and one longer (1.82 Å) Ge(1)-O(1) bond length. Both Ge(1)-O(2) bond lengths are 1.72 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and two equivalent Ge(1) atoms to form distorted ONa2Ge2 trigonal pyramids that share corners with eight equivalent O(2)Na4Ge trigonal bipyramids, corners with two equivalent O(1)Na2Ge2 trigonal pyramids, and edges with two equivalent O(2)Na4Ge trigonal bipyramids. In the second O site, O(2) is bonded to four equivalent Na(1) and one Ge(1) atom to form distorted ONa4Ge trigonal bipyramids that share corners with five equivalent O(2)Na4Ge trigonal bipyramids, corners with four equivalent O(1)Na2Ge2 trigonal pyramids, edges with four equivalent O(2)Na4Ge trigonal bipyramids, and  an edgeedge with one O(1)Na2Ge2 trigonal pyramid.