BaCrF5 crystallizes in the orthorhombic P2_12_12_1 space group. Ba(1) is bonded in a 12-coordinate geometry to one F(5), two equivalent F(1), three equivalent F(2), three equivalent F(3), and three equivalent F(4) atoms. Cr(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form corner-sharing CrF6 octahedra. The corner-sharing octahedral tilt angles are 46°. 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 Cr(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to three equivalent Ba(1) and one Cr(1) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to three equivalent Ba(1) and one Cr(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to three equivalent Ba(1) and one Cr(1) atom. In the fifth F site, F(5) is bonded in a 2-coordinate geometry to one Ba(1) and two equivalent Cr(1) atoms.
BaCrF5 crystallizes in the orthorhombic P2_12_12_1 space group. Ba(1) is bonded in a 12-coordinate geometry to one F(5), two equivalent F(1), three equivalent F(2), three equivalent F(3), and three equivalent F(4) atoms. The Ba(1)-F(5) bond length is 2.94 Å. There is one shorter (2.71 Å) and one longer (2.73 Å) Ba(1)-F(1) bond length. There are a spread of Ba(1)-F(2) bond distances ranging from 2.69-3.09 Å. There are a spread of Ba(1)-F(3) bond distances ranging from 2.74-3.00 Å. There are a spread of Ba(1)-F(4) bond distances ranging from 2.86-2.99 Å. Cr(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form corner-sharing CrF6 octahedra. The corner-sharing octahedral tilt angles are 46°. The Cr(1)-F(1) bond length is 1.89 Å. The Cr(1)-F(2) bond length is 1.90 Å. The Cr(1)-F(3) bond length is 1.91 Å. The Cr(1)-F(4) bond length is 1.89 Å. There is one shorter (1.95 Å) and one longer (1.96 Å) Cr(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 Cr(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to three equivalent Ba(1) and one Cr(1) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to three equivalent Ba(1) and one Cr(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to three equivalent Ba(1) and one Cr(1) atom. In the fifth F site, F(5) is bonded in a 2-coordinate geometry to one Ba(1) and two equivalent Cr(1) atoms.