ZnAlC2N3H3F5 crystallizes in the orthorhombic Imma space group. Zn(1) is bonded to two equivalent N(1) and four equivalent F(2) atoms to form ZnN2F4 octahedra that share corners with four equivalent Al(1)F6 octahedra. The corner-sharing octahedral tilt angles are 36°. Both Zn(1)-N(1) bond lengths are 2.15 Å. All Zn(1)-F(2) bond lengths are 2.08 Å. Al(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and corners with four equivalent Zn(1)N2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-36°. Both Al(1)-F(1) bond lengths are 1.88 Å. All Al(1)-F(2) bond lengths are 1.80 Å. C(1) is bonded in a trigonal planar geometry to one N(1), one N(2), and one H(1) atom. The C(1)-N(1) bond length is 1.32 Å. The C(1)-N(2) bond length is 1.35 Å. The C(1)-H(1) bond length is 1.08 Å. There are two inequivalent N sites. In the first N site, N(2) is bonded in a trigonal planar geometry to two equivalent C(1) and one H(2) atom. The N(2)-H(2) bond length is 1.03 Å. In the second N site, N(1) is bonded in a 3-coordinate geometry to one Zn(1), one C(1), and one N(1) atom. The N(1)-N(1) bond length is 1.39 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one N(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent Al(1) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Zn(1) and one Al(1) atom. Linkers: 2 c1nnc[nH]1. Metal clusters: 2 [Al] ,2 [Zn]. The MOF has largest included sphere 1.18 A, density 2.85 g/cm3, surface area 2164.55 m2/g, accessible volume 0.04 cm3/g