BaMnP(O2F)2 crystallizes in the monoclinic P2_1/c space group. Ba(1) is bonded in a 10-coordinate geometry to one O(2), one O(3), two equivalent O(4), three equivalent O(1), one F(2), and two equivalent F(1) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent F(2) atoms to form MnO4F2 octahedra that share corners with two equivalent Mn(2)O2F4 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. In the second Mn site, Mn(2) is bonded to two equivalent O(3), two equivalent F(1), and two equivalent F(2) atoms to form MnO2F4 octahedra that share corners with two equivalent Mn(1)O4F2 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O2F4 octahedra and corners with two equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 35-56°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to three equivalent Ba(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ba(1), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Ba(1), one Mn(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Ba(1), one Mn(1), and one P(1) atom. There are two inequivalent F sites. In the first F site, F(2) is bonded in a trigonal planar geometry to one Ba(1), one Mn(1), and one Mn(2) atom. In the second F site, F(1) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one Mn(2) atom.
BaMnP(O2F)2 crystallizes in the monoclinic P2_1/c space group. Ba(1) is bonded in a 10-coordinate geometry to one O(2), one O(3), two equivalent O(4), three equivalent O(1), one F(2), and two equivalent F(1) atoms. The Ba(1)-O(2) bond length is 3.14 Å. The Ba(1)-O(3) bond length is 3.04 Å. There is one shorter (2.86 Å) and one longer (2.97 Å) Ba(1)-O(4) bond length. There are a spread of Ba(1)-O(1) bond distances ranging from 2.94-2.97 Å. The Ba(1)-F(2) bond length is 2.61 Å. There is one shorter (2.70 Å) and one longer (2.81 Å) Ba(1)-F(1) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent F(2) atoms to form MnO4F2 octahedra that share corners with two equivalent Mn(2)O2F4 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. Both Mn(1)-O(2) bond lengths are 1.93 Å. Both Mn(1)-O(4) bond lengths are 2.08 Å. Both Mn(1)-F(2) bond lengths are 2.08 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(3), two equivalent F(1), and two equivalent F(2) atoms to form MnO2F4 octahedra that share corners with two equivalent Mn(1)O4F2 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. Both Mn(2)-O(3) bond lengths are 1.98 Å. Both Mn(2)-F(1) bond lengths are 1.92 Å. Both Mn(2)-F(2) bond lengths are 2.10 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O2F4 octahedra and corners with two equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 35-56°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.58 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to three equivalent Ba(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ba(1), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Ba(1), one Mn(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Ba(1), one Mn(1), and one P(1) atom. There are two inequivalent F sites. In the first F site, F(2) is bonded in a trigonal planar geometry to one Ba(1), one Mn(1), and one Mn(2) atom. In the second F site, F(1) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one Mn(2) atom.