Pb5(PO4)3F crystallizes in the hexagonal P6_3/m space group. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(3) atoms. In the second Pb site, Pb(2) is bonded to one O(1), four equivalent O(2), and one F(1) atom to form distorted PbO5F pentagonal pyramids that share corners with six equivalent Pb(2)O5F pentagonal pyramids, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. P(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Pb(2)O5F pentagonal pyramids and  an edgeedge with one Pb(2)O5F pentagonal pyramid. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Pb(2), two equivalent Pb(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Pb(2) and one P(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Pb(1) and one P(1) atom. F(1) is bonded in a trigonal planar geometry to three equivalent Pb(2) atoms.
Pb5(PO4)3F crystallizes in the hexagonal P6_3/m space group. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(3) atoms. All Pb(1)-O(1) bond lengths are 2.66 Å. All Pb(1)-O(3) bond lengths are 2.62 Å. In the second Pb site, Pb(2) is bonded to one O(1), four equivalent O(2), and one F(1) atom to form distorted PbO5F pentagonal pyramids that share corners with six equivalent Pb(2)O5F pentagonal pyramids, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The Pb(2)-O(1) bond length is 2.50 Å. There are two shorter (2.60 Å) and two longer (2.67 Å) Pb(2)-O(2) bond lengths. The Pb(2)-F(1) bond length is 2.49 Å. P(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Pb(2)O5F pentagonal pyramids and  an edgeedge with one Pb(2)O5F pentagonal pyramid. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.55 Å. Both P(1)-O(2) bond lengths are 1.56 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Pb(2), two equivalent Pb(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Pb(2) and one P(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Pb(1) and one P(1) atom. F(1) is bonded in a trigonal planar geometry to three equivalent Pb(2) atoms.