TiZnF5 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. Ti3+ is bonded to six F1- atoms to form TiF6 octahedra that share corners with two equivalent TiF6 octahedra, corners with four equivalent ZnF7 pentagonal bipyramids, and edges with two equivalent ZnF7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 46°. There are a spread of Ti–F bond distances ranging from 1.92–2.05 Å. Zn2+ is bonded to seven F1- atoms to form distorted ZnF7 pentagonal bipyramids that share corners with four equivalent TiF6 octahedra, edges with two equivalent TiF6 octahedra, and edges with two equivalent ZnF7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 6–37°. There are a spread of Zn–F bond distances ranging from 2.00–2.53 Å. There are three inequivalent F1- sites. In the first F1- site, F1- is bonded in a distorted trigonal planar geometry to two equivalent Ti3+ and one Zn2+ atom. In the second F1- site, F1- is bonded in a linear geometry to one Ti3+ and one Zn2+ atom. In the third F1- site, F1- is bonded in a 2-coordinate geometry to one Ti3+ and two equivalent Zn2+ atoms.