Pb5As3O12F 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(2) atoms. In the second Pb site, Pb(2) is bonded to one O(2), four equivalent O(3), 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 As(1)O4 tetrahedra, and  an edgeedge with one As(1)O4 tetrahedra. As(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form AsO4 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 two equivalent Pb(1) and one As(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Pb(2), two equivalent Pb(1), and one As(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Pb(2) and one As(1) atom. F(1) is bonded in a trigonal planar geometry to three equivalent Pb(2) atoms.
Pb5As3O12F 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(2) atoms. All Pb(1)-O(1) bond lengths are 2.59 Å. All Pb(1)-O(2) bond lengths are 2.71 Å. In the second Pb site, Pb(2) is bonded to one O(2), four equivalent O(3), 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 As(1)O4 tetrahedra, and  an edgeedge with one As(1)O4 tetrahedra. The Pb(2)-O(2) bond length is 2.53 Å. All Pb(2)-O(3) bond lengths are 2.63 Å. The Pb(2)-F(1) bond length is 2.52 Å. As(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form AsO4 tetrahedra that share corners with three equivalent Pb(2)O5F pentagonal pyramids and  an edgeedge with one Pb(2)O5F pentagonal pyramid. The As(1)-O(1) bond length is 1.73 Å. The As(1)-O(2) bond length is 1.74 Å. Both As(1)-O(3) bond lengths are 1.73 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to two equivalent Pb(1) and one As(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Pb(2), two equivalent Pb(1), and one As(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Pb(2) and one As(1) atom. F(1) is bonded in a trigonal planar geometry to three equivalent Pb(2) atoms.