ZnBiF5 crystallizes in the triclinic P1 space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one F(10), one F(2), one F(7), one F(8), and one F(9) atom to form distorted ZnF5 trigonal bipyramids that share corners with three equivalent Bi(1)F6 octahedra and corners with three equivalent Bi(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 19-66°. In the second Zn site, Zn(2) is bonded to one F(1), one F(3), one F(4), one F(5), and one F(6) atom to form distorted ZnF5 trigonal bipyramids that share corners with three equivalent Bi(1)F6 octahedra and corners with three equivalent Bi(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 17-66°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one F(1), one F(2), one F(4), one F(5), one F(7), and one F(9) atom to form BiF6 octahedra that share corners with two equivalent Bi(2)F6 octahedra, corners with three equivalent Zn(1)F5 trigonal bipyramids, and corners with three equivalent Zn(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 49°. In the second Bi site, Bi(2) is bonded to one F(1), one F(10), one F(2), one F(3), one F(6), and one F(8) atom to form BiF6 octahedra that share corners with two equivalent Bi(1)F6 octahedra, corners with three equivalent Zn(1)F5 trigonal bipyramids, and corners with three equivalent Zn(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 49°. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Zn(2), one Bi(1), and one Bi(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Zn(1), one Bi(1), and one Bi(2) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Zn(2) and one Bi(2) atom. In the fourth F site, F(4) is bonded in a distorted linear geometry to one Zn(2) and one Bi(1) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Zn(2) and one Bi(1) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Zn(2) and one Bi(2) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one Zn(1) and one Bi(1) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Zn(1) and one Bi(2) atom. In the ninth F site, F(9) is bonded in a distorted bent 150 degrees geometry to one Zn(1) and one Bi(1) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one Zn(1) and one Bi(2) atom.
ZnBiF5 crystallizes in the triclinic P1 space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one F(10), one F(2), one F(7), one F(8), and one F(9) atom to form distorted ZnF5 trigonal bipyramids that share corners with three equivalent Bi(1)F6 octahedra and corners with three equivalent Bi(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 19-66°. The Zn(1)-F(10) bond length is 1.94 Å. The Zn(1)-F(2) bond length is 2.42 Å. The Zn(1)-F(7) bond length is 2.02 Å. The Zn(1)-F(8) bond length is 2.01 Å. The Zn(1)-F(9) bond length is 1.95 Å. In the second Zn site, Zn(2) is bonded to one F(1), one F(3), one F(4), one F(5), and one F(6) atom to form distorted ZnF5 trigonal bipyramids that share corners with three equivalent Bi(1)F6 octahedra and corners with three equivalent Bi(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 17-66°. The Zn(2)-F(1) bond length is 2.43 Å. The Zn(2)-F(3) bond length is 1.93 Å. The Zn(2)-F(4) bond length is 1.95 Å. The Zn(2)-F(5) bond length is 2.02 Å. The Zn(2)-F(6) bond length is 2.01 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one F(1), one F(2), one F(4), one F(5), one F(7), and one F(9) atom to form BiF6 octahedra that share corners with two equivalent Bi(2)F6 octahedra, corners with three equivalent Zn(1)F5 trigonal bipyramids, and corners with three equivalent Zn(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 49°. The Bi(1)-F(1) bond length is 2.34 Å. The Bi(1)-F(2) bond length is 2.37 Å. The Bi(1)-F(4) bond length is 2.26 Å. The Bi(1)-F(5) bond length is 2.24 Å. The Bi(1)-F(7) bond length is 2.28 Å. The Bi(1)-F(9) bond length is 2.25 Å. In the second Bi site, Bi(2) is bonded to one F(1), one F(10), one F(2), one F(3), one F(6), and one F(8) atom to form BiF6 octahedra that share corners with two equivalent Bi(1)F6 octahedra, corners with three equivalent Zn(1)F5 trigonal bipyramids, and corners with three equivalent Zn(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 49°. The Bi(2)-F(1) bond length is 2.36 Å. The Bi(2)-F(10) bond length is 2.27 Å. The Bi(2)-F(2) bond length is 2.36 Å. The Bi(2)-F(3) bond length is 2.27 Å. The Bi(2)-F(6) bond length is 2.25 Å. The Bi(2)-F(8) bond length is 2.26 Å. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Zn(2), one Bi(1), and one Bi(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Zn(1), one Bi(1), and one Bi(2) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Zn(2) and one Bi(2) atom. In the fourth F site, F(4) is bonded in a distorted linear geometry to one Zn(2) and one Bi(1) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Zn(2) and one Bi(1) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Zn(2) and one Bi(2) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one Zn(1) and one Bi(1) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Zn(1) and one Bi(2) atom. In the ninth F site, F(9) is bonded in a distorted bent 150 degrees geometry to one Zn(1) and one Bi(1) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one Zn(1) and one Bi(2) atom.