Na5Ca4(PO4)4F 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 7-coordinate geometry to one O(2), one O(3), one O(4), and four equivalent O(1) atoms. In the second Na site, Na(2) is bonded in a 10-coordinate geometry to four equivalent O(2), four equivalent O(4), and two equivalent F(1) atoms. Ca(1) is bonded in a 8-coordinate geometry to one O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), and one F(1) atom. P(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(1) is bonded in a 1-coordinate geometry to four equivalent Na(1), one Ca(1), and one P(1) atom. In the second O site, O(2) is bonded in a 1-coordinate geometry to one Na(1), one Na(2), two equivalent Ca(1), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Ca(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), two equivalent Ca(1), and one P(1) atom. F(1) is bonded to two equivalent Na(2) and four equivalent Ca(1) atoms to form corner-sharing FNa2Ca4 octahedra. The corner-sharing octahedra are not tilted.
Na5Ca4(PO4)4F 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 7-coordinate geometry to one O(2), one O(3), one O(4), and four equivalent O(1) atoms. The Na(1)-O(2) bond length is 2.56 Å. The Na(1)-O(3) bond length is 2.38 Å. The Na(1)-O(4) bond length is 2.79 Å. There are a spread of Na(1)-O(1) bond distances ranging from 2.49-2.91 Å. In the second Na site, Na(2) is bonded in a 10-coordinate geometry to four equivalent O(2), four equivalent O(4), and two equivalent F(1) atoms. All Na(2)-O(2) bond lengths are 2.92 Å. All Na(2)-O(4) bond lengths are 2.62 Å. Both Na(2)-F(1) bond lengths are 2.74 Å. Ca(1) is bonded in a 8-coordinate geometry to one O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), and one F(1) atom. The Ca(1)-O(1) bond length is 2.57 Å. There is one shorter (2.35 Å) and one longer (2.44 Å) Ca(1)-O(2) bond length. There is one shorter (2.41 Å) and one longer (2.70 Å) Ca(1)-O(3) bond length. There is one shorter (2.39 Å) and one longer (2.44 Å) Ca(1)-O(4) bond length. The Ca(1)-F(1) bond length is 2.48 Å. P(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.55 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to four equivalent Na(1), one Ca(1), and one P(1) atom. In the second O site, O(2) is bonded in a 1-coordinate geometry to one Na(1), one Na(2), two equivalent Ca(1), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Ca(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), two equivalent Ca(1), and one P(1) atom. F(1) is bonded to two equivalent Na(2) and four equivalent Ca(1) atoms to form corner-sharing FNa2Ca4 octahedra. The corner-sharing octahedra are not tilted.