BaMnF5 crystallizes in the orthorhombic P2_12_12_1 space group. Ba(1) is bonded to one F(5), two equivalent F(1), three equivalent F(2), three equivalent F(3), and three equivalent F(4) atoms to form distorted BaF12 cuboctahedra that share corners with four equivalent Ba(1)F12 cuboctahedra, corners with two equivalent Mn(1)F6 octahedra, edges with four equivalent Ba(1)F12 cuboctahedra,  an edgeedge with one Mn(1)F6 octahedra, faces with two equivalent Ba(1)F12 cuboctahedra, and faces with three equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. Mn(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form MnF6 octahedra that share corners with two equivalent Ba(1)F12 cuboctahedra, corners with two equivalent Mn(1)F6 octahedra,  an edgeedge with one Ba(1)F12 cuboctahedra, and faces with three equivalent Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 43°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one Mn(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to three equivalent Ba(1) and one Mn(1) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to three equivalent Ba(1) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a single-bond geometry to three equivalent Ba(1) and one Mn(1) atom. In the fifth F site, F(5) is bonded in a 2-coordinate geometry to one Ba(1) and two equivalent Mn(1) atoms.
BaMnF5 crystallizes in the orthorhombic P2_12_12_1 space group. Ba(1) is bonded to one F(5), two equivalent F(1), three equivalent F(2), three equivalent F(3), and three equivalent F(4) atoms to form distorted BaF12 cuboctahedra that share corners with four equivalent Ba(1)F12 cuboctahedra, corners with two equivalent Mn(1)F6 octahedra, edges with four equivalent Ba(1)F12 cuboctahedra,  an edgeedge with one Mn(1)F6 octahedra, faces with two equivalent Ba(1)F12 cuboctahedra, and faces with three equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. The Ba(1)-F(5) bond length is 2.85 Å. There is one shorter (2.78 Å) and one longer (2.82 Å) Ba(1)-F(1) bond length. There are a spread of Ba(1)-F(2) bond distances ranging from 2.65-2.95 Å. There are a spread of Ba(1)-F(3) bond distances ranging from 2.78-3.01 Å. There are a spread of Ba(1)-F(4) bond distances ranging from 2.87-3.05 Å. Mn(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form MnF6 octahedra that share corners with two equivalent Ba(1)F12 cuboctahedra, corners with two equivalent Mn(1)F6 octahedra,  an edgeedge with one Ba(1)F12 cuboctahedra, and faces with three equivalent Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 43°. The Mn(1)-F(1) bond length is 1.84 Å. The Mn(1)-F(2) bond length is 2.05 Å. The Mn(1)-F(3) bond length is 1.87 Å. The Mn(1)-F(4) bond length is 1.87 Å. There is one shorter (1.87 Å) and one longer (2.14 Å) Mn(1)-F(5) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one Mn(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to three equivalent Ba(1) and one Mn(1) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to three equivalent Ba(1) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a single-bond geometry to three equivalent Ba(1) and one Mn(1) atom. In the fifth F site, F(5) is bonded in a 2-coordinate geometry to one Ba(1) and two equivalent Mn(1) atoms.