Na4GeO4 crystallizes in the triclinic P-1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form distorted NaO5 square pyramids that share corners with three equivalent Na(2)O5 square pyramids, corners with two equivalent Na(4)O4 tetrahedra, corners with three equivalent Ge(1)O4 tetrahedra,  a cornercorner with one Na(3)O4 trigonal pyramid, edges with two equivalent Na(1)O5 square pyramids, edges with three equivalent Na(2)O5 square pyramids,  an edgeedge with one Ge(1)O4 tetrahedra, and edges with two equivalent Na(3)O4 trigonal pyramids. In the second Na site, Na(2) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form NaO5 square pyramids that share corners with three equivalent Na(1)O5 square pyramids,  a cornercorner with one Ge(1)O4 tetrahedra, corners with two equivalent Na(4)O4 tetrahedra, corners with three equivalent Na(3)O4 trigonal pyramids, edges with two equivalent Na(2)O5 square pyramids, edges with three equivalent Na(1)O5 square pyramids, edges with two equivalent Ge(1)O4 tetrahedra, and  an edgeedge with one Na(3)O4 trigonal pyramid. In the third Na site, Na(3) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted NaO4 trigonal pyramids that share  a cornercorner with one Na(1)O5 square pyramid, corners with three equivalent Na(2)O5 square pyramids, corners with four equivalent Na(4)O4 tetrahedra, corners with four equivalent Ge(1)O4 tetrahedra,  an edgeedge with one Na(2)O5 square pyramid, and edges with two equivalent Na(1)O5 square pyramids. In the fourth Na site, Na(4) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(1)O5 square pyramids, corners with two equivalent Na(2)O5 square pyramids, corners with four equivalent Ge(1)O4 tetrahedra, corners with four equivalent Na(3)O4 trigonal pyramids, and edges with two equivalent Na(4)O4 tetrahedra. Ge(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form GeO4 tetrahedra that share  a cornercorner with one Na(2)O5 square pyramid, corners with three equivalent Na(1)O5 square pyramids, corners with four equivalent Na(4)O4 tetrahedra, corners with four equivalent Na(3)O4 trigonal pyramids,  an edgeedge with one Na(1)O5 square pyramid, and edges with two equivalent Na(2)O5 square pyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing ONa5Ge octahedra. The corner-sharing octahedral tilt angles range from 11-27°. In the second O site, O(2) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Ge(1) atom to form a mixture of edge and corner-sharing ONa5Ge octahedra. The corner-sharing octahedral tilt angles range from 11-27°. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), two equivalent Na(4), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing ONa5Ge octahedra. The corner-sharing octahedral tilt angles range from 13-15°. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), two equivalent Na(4), and one Ge(1) atom.
Na4GeO4 crystallizes in the triclinic P-1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form distorted NaO5 square pyramids that share corners with three equivalent Na(2)O5 square pyramids, corners with two equivalent Na(4)O4 tetrahedra, corners with three equivalent Ge(1)O4 tetrahedra,  a cornercorner with one Na(3)O4 trigonal pyramid, edges with two equivalent Na(1)O5 square pyramids, edges with three equivalent Na(2)O5 square pyramids,  an edgeedge with one Ge(1)O4 tetrahedra, and edges with two equivalent Na(3)O4 trigonal pyramids. The Na(1)-O(3) bond length is 2.46 Å. There is one shorter (2.36 Å) and one longer (2.37 Å) Na(1)-O(1) bond length. There is one shorter (2.32 Å) and one longer (2.37 Å) Na(1)-O(2) bond length. In the second Na site, Na(2) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form NaO5 square pyramids that share corners with three equivalent Na(1)O5 square pyramids,  a cornercorner with one Ge(1)O4 tetrahedra, corners with two equivalent Na(4)O4 tetrahedra, corners with three equivalent Na(3)O4 trigonal pyramids, edges with two equivalent Na(2)O5 square pyramids, edges with three equivalent Na(1)O5 square pyramids, edges with two equivalent Ge(1)O4 tetrahedra, and  an edgeedge with one Na(3)O4 trigonal pyramid. The Na(2)-O(3) bond length is 2.34 Å. There is one shorter (2.40 Å) and one longer (2.48 Å) Na(2)-O(1) bond length. There is one shorter (2.34 Å) and one longer (2.37 Å) Na(2)-O(2) bond length. In the third Na site, Na(3) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted NaO4 trigonal pyramids that share  a cornercorner with one Na(1)O5 square pyramid, corners with three equivalent Na(2)O5 square pyramids, corners with four equivalent Na(4)O4 tetrahedra, corners with four equivalent Ge(1)O4 tetrahedra,  an edgeedge with one Na(2)O5 square pyramid, and edges with two equivalent Na(1)O5 square pyramids. The Na(3)-O(1) bond length is 2.33 Å. The Na(3)-O(2) bond length is 2.34 Å. The Na(3)-O(3) bond length is 2.33 Å. The Na(3)-O(4) bond length is 2.31 Å. In the fourth Na site, Na(4) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(1)O5 square pyramids, corners with two equivalent Na(2)O5 square pyramids, corners with four equivalent Ge(1)O4 tetrahedra, corners with four equivalent Na(3)O4 trigonal pyramids, and edges with two equivalent Na(4)O4 tetrahedra. Both Na(4)-O(3) bond lengths are 2.31 Å. There is one shorter (2.27 Å) and one longer (2.29 Å) Na(4)-O(4) bond length. Ge(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form GeO4 tetrahedra that share  a cornercorner with one Na(2)O5 square pyramid, corners with three equivalent Na(1)O5 square pyramids, corners with four equivalent Na(4)O4 tetrahedra, corners with four equivalent Na(3)O4 trigonal pyramids,  an edgeedge with one Na(1)O5 square pyramid, and edges with two equivalent Na(2)O5 square pyramids. The Ge(1)-O(1) bond length is 1.78 Å. The Ge(1)-O(2) bond length is 1.78 Å. The Ge(1)-O(3) bond length is 1.78 Å. The Ge(1)-O(4) bond length is 1.76 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing ONa5Ge octahedra. The corner-sharing octahedral tilt angles range from 11-27°. In the second O site, O(2) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Ge(1) atom to form a mixture of edge and corner-sharing ONa5Ge octahedra. The corner-sharing octahedral tilt angles range from 11-27°. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), two equivalent Na(4), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing ONa5Ge octahedra. The corner-sharing octahedral tilt angles range from 13-15°. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), two equivalent Na(4), and one Ge(1) atom.