MgBiF5 crystallizes in the monoclinic P2_1/c space group. Mg(1) is bonded to one F(1), one F(3), one F(4), one F(5), and two equivalent F(2) atoms to form distorted MgF6 octahedra that share corners with five equivalent Bi(1)F6 octahedra,  an edgeedge with one Mg(1)F6 octahedra, and  an edgeedge with one Bi(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 10-50°. Bi(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form distorted BiF6 octahedra that share corners with two equivalent Bi(1)F6 octahedra, corners with five equivalent Mg(1)F6 octahedra, and  an edgeedge with one Mg(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 10-54°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Mg(1) and one Bi(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to two equivalent Mg(1) and one Bi(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Mg(1) and one Bi(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Mg(1) and one Bi(1) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Mg(1) and two equivalent Bi(1) atoms.
MgBiF5 crystallizes in the monoclinic P2_1/c space group. Mg(1) is bonded to one F(1), one F(3), one F(4), one F(5), and two equivalent F(2) atoms to form distorted MgF6 octahedra that share corners with five equivalent Bi(1)F6 octahedra,  an edgeedge with one Mg(1)F6 octahedra, and  an edgeedge with one Bi(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 10-50°. The Mg(1)-F(1) bond length is 1.98 Å. The Mg(1)-F(3) bond length is 1.97 Å. The Mg(1)-F(4) bond length is 1.95 Å. The Mg(1)-F(5) bond length is 2.26 Å. There is one shorter (2.04 Å) and one longer (2.10 Å) Mg(1)-F(2) bond length. Bi(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form distorted BiF6 octahedra that share corners with two equivalent Bi(1)F6 octahedra, corners with five equivalent Mg(1)F6 octahedra, and  an edgeedge with one Mg(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 10-54°. The Bi(1)-F(1) bond length is 2.23 Å. The Bi(1)-F(2) bond length is 2.33 Å. The Bi(1)-F(3) bond length is 2.21 Å. The Bi(1)-F(4) bond length is 2.25 Å. There is one shorter (2.28 Å) and one longer (2.46 Å) Bi(1)-F(5) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Mg(1) and one Bi(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to two equivalent Mg(1) and one Bi(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Mg(1) and one Bi(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Mg(1) and one Bi(1) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Mg(1) and two equivalent Bi(1) atoms.