Na3B2PO5F4 crystallizes in the orthorhombic Ama2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent F(2) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(4), and two equivalent F(2) atoms. In the third Na site, Na(3) is bonded to two equivalent O(3), two equivalent O(4), two equivalent F(1), and two equivalent F(2) atoms to form distorted NaO4F4 hexagonal bipyramids that share corners with two equivalent Na(3)O4F4 hexagonal bipyramids, corners with two equivalent B(1)O2F2 tetrahedra, edges with two equivalent B(2)O2F2 tetrahedra, and edges with two equivalent P(1)O4 tetrahedra. There are two inequivalent B sites. In the first B site, B(1) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form BO2F2 tetrahedra that share corners with two equivalent Na(3)O4F4 hexagonal bipyramids,  a cornercorner with one B(2)O2F2 tetrahedra, and  a cornercorner with one P(1)O4 tetrahedra. In the second B site, B(2) is bonded to one O(1), one O(3), and two equivalent F(2) atoms to form BO2F2 tetrahedra that share  a cornercorner with one B(1)O2F2 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, and edges with two equivalent Na(3)O4F4 hexagonal bipyramids. P(1) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form PO4 tetrahedra that share  a cornercorner with one B(1)O2F2 tetrahedra,  a cornercorner with one B(2)O2F2 tetrahedra, and edges with two equivalent Na(3)O4F4 hexagonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to two equivalent Na(1), one B(1), and one B(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(2), one B(1), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(3), one B(2), and one P(1) atom. In the fourth O site, O(4) is bonded to one Na(1), one Na(2), one Na(3), and one P(1) atom to form a mixture of distorted corner and edge-sharing ONa3P tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to one Na(3) and one B(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), one Na(3), and one B(2) atom.
Na3B2PO5F4 crystallizes in the orthorhombic Ama2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent F(2) atoms. Both Na(1)-O(1) bond lengths are 2.60 Å. Both Na(1)-O(4) bond lengths are 2.29 Å. Both Na(1)-F(2) bond lengths are 2.51 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(4), and two equivalent F(2) atoms. Both Na(2)-O(2) bond lengths are 2.57 Å. Both Na(2)-O(4) bond lengths are 2.44 Å. Both Na(2)-F(2) bond lengths are 2.41 Å. In the third Na site, Na(3) is bonded to two equivalent O(3), two equivalent O(4), two equivalent F(1), and two equivalent F(2) atoms to form distorted NaO4F4 hexagonal bipyramids that share corners with two equivalent Na(3)O4F4 hexagonal bipyramids, corners with two equivalent B(1)O2F2 tetrahedra, edges with two equivalent B(2)O2F2 tetrahedra, and edges with two equivalent P(1)O4 tetrahedra. Both Na(3)-O(3) bond lengths are 2.49 Å. Both Na(3)-O(4) bond lengths are 2.53 Å. Both Na(3)-F(1) bond lengths are 2.37 Å. Both Na(3)-F(2) bond lengths are 2.72 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form BO2F2 tetrahedra that share corners with two equivalent Na(3)O4F4 hexagonal bipyramids,  a cornercorner with one B(2)O2F2 tetrahedra, and  a cornercorner with one P(1)O4 tetrahedra. The B(1)-O(1) bond length is 1.43 Å. The B(1)-O(2) bond length is 1.49 Å. Both B(1)-F(1) bond lengths are 1.45 Å. In the second B site, B(2) is bonded to one O(1), one O(3), and two equivalent F(2) atoms to form BO2F2 tetrahedra that share  a cornercorner with one B(1)O2F2 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, and edges with two equivalent Na(3)O4F4 hexagonal bipyramids. The B(2)-O(1) bond length is 1.41 Å. The B(2)-O(3) bond length is 1.47 Å. Both B(2)-F(2) bond lengths are 1.46 Å. P(1) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form PO4 tetrahedra that share  a cornercorner with one B(1)O2F2 tetrahedra,  a cornercorner with one B(2)O2F2 tetrahedra, and edges with two equivalent Na(3)O4F4 hexagonal bipyramids. The P(1)-O(2) bond length is 1.60 Å. The P(1)-O(3) bond length is 1.61 Å. Both P(1)-O(4) bond lengths are 1.51 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to two equivalent Na(1), one B(1), and one B(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(2), one B(1), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(3), one B(2), and one P(1) atom. In the fourth O site, O(4) is bonded to one Na(1), one Na(2), one Na(3), and one P(1) atom to form a mixture of distorted corner and edge-sharing ONa3P tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to one Na(3) and one B(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), one Na(3), and one B(2) atom.