Na2TiGeO5 crystallizes in the tetragonal P4/nmm space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Ge(1)O4 tetrahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 57°. Ti(1) is bonded in a 5-coordinate geometry to one O(2) and four equivalent O(1) atoms. Ge(1) is bonded to four equivalent O(1) atoms to form GeO4 tetrahedra that share corners with eight equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 62°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Ti(1), and one Ge(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to four equivalent Na(1) and one Ti(1) atom.
Na2TiGeO5 crystallizes in the tetragonal P4/nmm space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Ge(1)O4 tetrahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 57°. Both Na(1)-O(2) bond lengths are 2.70 Å. All Na(1)-O(1) bond lengths are 2.33 Å. Ti(1) is bonded in a 5-coordinate geometry to one O(2) and four equivalent O(1) atoms. The Ti(1)-O(2) bond length is 1.72 Å. All Ti(1)-O(1) bond lengths are 2.01 Å. Ge(1) is bonded to four equivalent O(1) atoms to form GeO4 tetrahedra that share corners with eight equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 62°. All Ge(1)-O(1) bond lengths are 1.77 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Ti(1), and one Ge(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to four equivalent Na(1) and one Ti(1) atom.