Ba4NbP4(O9F)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one O(2), one O(5), one O(6), one O(8), one O(9), two equivalent O(7), and one F(1) atom. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(1), one O(3), one O(5), one O(7), one O(8), one O(9), two equivalent O(6), and one F(1) atom. Nb(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form NbO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 41°. In the second P site, P(2) is bonded to one O(2), one O(4), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 39°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Ba(2) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ba(1), one Nb(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ba(2), one Nb(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ba(1), one Ba(2), and one Nb(1) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one Ba(1), two equivalent Ba(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one P(2) atom. F(1) is bonded in a bent 120 degrees geometry to one Ba(1) and one Ba(2) atom.
Ba4NbP4(O9F)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one O(2), one O(5), one O(6), one O(8), one O(9), two equivalent O(7), and one F(1) atom. The Ba(1)-O(2) bond length is 2.87 Å. The Ba(1)-O(5) bond length is 2.77 Å. The Ba(1)-O(6) bond length is 3.00 Å. The Ba(1)-O(8) bond length is 2.91 Å. The Ba(1)-O(9) bond length is 2.94 Å. There is one shorter (2.80 Å) and one longer (3.00 Å) Ba(1)-O(7) bond length. The Ba(1)-F(1) bond length is 2.54 Å. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(1), one O(3), one O(5), one O(7), one O(8), one O(9), two equivalent O(6), and one F(1) atom. The Ba(2)-O(1) bond length is 3.00 Å. The Ba(2)-O(3) bond length is 3.17 Å. The Ba(2)-O(5) bond length is 2.86 Å. The Ba(2)-O(7) bond length is 2.97 Å. The Ba(2)-O(8) bond length is 2.77 Å. The Ba(2)-O(9) bond length is 2.67 Å. There is one shorter (3.08 Å) and one longer (3.12 Å) Ba(2)-O(6) bond length. The Ba(2)-F(1) bond length is 2.59 Å. Nb(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form NbO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. Both Nb(1)-O(2) bond lengths are 2.04 Å. Both Nb(1)-O(3) bond lengths are 2.10 Å. Both Nb(1)-O(5) bond lengths are 1.90 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 41°. The P(1)-O(1) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.58 Å. The P(1)-O(6) bond length is 1.54 Å. The P(1)-O(8) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(2), one O(4), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 39°. The P(2)-O(2) bond length is 1.59 Å. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(9) bond length is 1.53 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Ba(2) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ba(1), one Nb(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ba(2), one Nb(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ba(1), one Ba(2), and one Nb(1) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one Ba(1), two equivalent Ba(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one P(2) atom. F(1) is bonded in a bent 120 degrees geometry to one Ba(1) and one Ba(2) atom.