Na5Nd4Ge4O16F crystallizes in the tetragonal I-4 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to four equivalent O(1) and two equivalent F(1) atoms. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(3), one O(4), and three equivalent O(2) atoms. Nd(1) is bonded in a 8-coordinate geometry to one O(2), two equivalent O(1), two equivalent O(3), two equivalent O(4), and one F(1) atom. Ge(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. There are four inequivalent O sites. In the first O site, O(3) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Nd(1), and one Ge(1) atom. In the second O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Nd(1), and one Ge(1) atom. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Nd(1), and one Ge(1) atom. In the fourth O site, O(2) is bonded to three equivalent Na(2), one Nd(1), and one Ge(1) atom to form distorted ONa3NdGe square pyramids that share  a cornercorner with one F(1)Na2Nd4 octahedra and edges with three equivalent O(2)Na3NdGe square pyramids. The corner-sharing octahedral tilt angles are 34°. F(1) is bonded to two equivalent Na(1) and four equivalent Nd(1) atoms to form FNa2Nd4 octahedra that share corners with two equivalent F(1)Na2Nd4 octahedra and corners with four equivalent O(2)Na3NdGe square pyramids. The corner-sharing octahedra are not tilted.
Na5Nd4Ge4O16F crystallizes in the tetragonal I-4 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to four equivalent O(1) and two equivalent F(1) atoms. All Na(1)-O(1) bond lengths are 2.61 Å. Both Na(1)-F(1) bond lengths are 2.87 Å. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(3), one O(4), and three equivalent O(2) atoms. The Na(2)-O(3) bond length is 2.75 Å. The Na(2)-O(4) bond length is 2.44 Å. There are a spread of Na(2)-O(2) bond distances ranging from 2.40-2.62 Å. Nd(1) is bonded in a 8-coordinate geometry to one O(2), two equivalent O(1), two equivalent O(3), two equivalent O(4), and one F(1) atom. The Nd(1)-O(2) bond length is 2.56 Å. There is one shorter (2.43 Å) and one longer (2.46 Å) Nd(1)-O(1) bond length. There is one shorter (2.35 Å) and one longer (2.44 Å) Nd(1)-O(3) bond length. There is one shorter (2.47 Å) and one longer (2.63 Å) Nd(1)-O(4) bond length. The Nd(1)-F(1) bond length is 2.63 Å. Ge(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Ge(1)-O(1) bond length is 1.77 Å. The Ge(1)-O(2) bond length is 1.77 Å. The Ge(1)-O(3) bond length is 1.78 Å. The Ge(1)-O(4) bond length is 1.79 Å. There are four inequivalent O sites. In the first O site, O(3) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Nd(1), and one Ge(1) atom. In the second O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Nd(1), and one Ge(1) atom. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Nd(1), and one Ge(1) atom. In the fourth O site, O(2) is bonded to three equivalent Na(2), one Nd(1), and one Ge(1) atom to form distorted ONa3NdGe square pyramids that share  a cornercorner with one F(1)Na2Nd4 octahedra and edges with three equivalent O(2)Na3NdGe square pyramids. The corner-sharing octahedral tilt angles are 34°. F(1) is bonded to two equivalent Na(1) and four equivalent Nd(1) atoms to form FNa2Nd4 octahedra that share corners with two equivalent F(1)Na2Nd4 octahedra and corners with four equivalent O(2)Na3NdGe square pyramids. The corner-sharing octahedra are not tilted.