NiZnF5 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are two inequivalent Ni3+ sites. In the first Ni3+ site, Ni3+ is bonded to six F1- atoms to form NiF6 octahedra that share corners with two equivalent NiF6 octahedra, corners with four ZnF7 pentagonal bipyramids, and edges with two ZnF7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 39–40°. There are a spread of Ni–F bond distances ranging from 1.82–2.02 Å. In the second Ni3+ site, Ni3+ is bonded to six F1- atoms to form NiF6 octahedra that share corners with two equivalent NiF6 octahedra, corners with four ZnF7 pentagonal bipyramids, and edges with two ZnF7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 39–40°. There are a spread of Ni–F bond distances ranging from 1.82–2.02 Å. There are two inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to seven F1- atoms to form distorted ZnF7 pentagonal bipyramids that share corners with four NiF6 octahedra, edges with two NiF6 octahedra, and edges with two equivalent ZnF7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 3–37°. There are a spread of Zn–F bond distances ranging from 1.96–2.48 Å. In the second Zn2+ site, Zn2+ is bonded to seven F1- atoms to form distorted ZnF7 pentagonal bipyramids that share corners with four NiF6 octahedra, edges with two NiF6 octahedra, and edges with two equivalent ZnF7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 1–37°. There are a spread of Zn–F bond distances ranging from 1.96–2.47 Å. There are ten inequivalent F1- sites. In the first F1- site, F1- is bonded in a distorted trigonal planar geometry to two Ni3+ and one Zn2+ atom. In the second F1- site, F1- is bonded in a distorted trigonal planar geometry to two Ni3+ and one Zn2+ atom. In the third F1- site, F1- is bonded in a linear geometry to one Ni3+ and one Zn2+ atom. In the fourth F1- site, F1- is bonded in a linear geometry to one Ni3+ and one Zn2+ atom. In the fifth F1- site, F1- is bonded in a 2-coordinate geometry to one Ni3+ and two Zn2+ atoms. In the sixth F1- site, F1- is bonded in a 2-coordinate geometry to one Ni3+ and two Zn2+ atoms. In the seventh F1- site, F1- is bonded in a 2-coordinate geometry to one Ni3+ and two Zn2+ atoms. In the eighth F1- site, F1- is bonded in a 2-coordinate geometry to one Ni3+ and two Zn2+ atoms. In the ninth F1- site, F1- is bonded in a linear geometry to one Ni3+ and one Zn2+ atom. In the tenth F1- site, F1- is bonded in a linear geometry to one Ni3+ and one Zn2+ atom.