ZnCN5H2F crystallizes in the monoclinic P2/m space group. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent N(4) and two equivalent F(1) atoms to form edge-sharing ZnN2F2 trigonal pyramids. Both Zn(1)-N(4) bond lengths are 2.02 Å. There is one shorter (1.95 Å) and one longer (2.09 Å) Zn(1)-F(1) bond length. In the second Zn site, Zn(2) is bonded to four equivalent N(1) and two equivalent F(2) atoms to form corner-sharing ZnN4F2 octahedra. The corner-sharing octahedral tilt angles are 72°. All Zn(2)-N(1) bond lengths are 2.14 Å. Both Zn(2)-F(2) bond lengths are 2.06 Å. In the third Zn site, Zn(3) is bonded to four equivalent N(3) and two equivalent F(2) atoms to form corner-sharing ZnN4F2 octahedra. The corner-sharing octahedral tilt angles are 72°. All Zn(3)-N(3) bond lengths are 2.17 Å. Both Zn(3)-F(2) bond lengths are 2.00 Å. C(1) is bonded in a trigonal planar geometry to one N(1), one N(4), and one N(5) atom. The C(1)-N(1) bond length is 1.33 Å. The C(1)-N(4) bond length is 1.35 Å. The C(1)-N(5) bond length is 1.35 Å. There are five inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Zn(2), one C(1), and one N(3) atom. The N(1)-N(3) bond length is 1.35 Å. In the second N site, N(2) is bonded in a water-like geometry to one N(3) and one N(4) atom. The N(2)-N(3) bond length is 1.29 Å. The N(2)-N(4) bond length is 1.36 Å. In the third N site, N(3) is bonded in a distorted trigonal planar geometry to one Zn(3), one N(1), and one N(2) atom. In the fourth N site, N(4) is bonded in a 3-coordinate geometry to one Zn(1), one C(1), and one N(2) atom. In the fifth N site, N(5) is bonded in a trigonal planar geometry to one C(1) and two equivalent H(1,2) atoms. Both N(5)-H(1,2) bond lengths are 0.86 Å. H(1,2) is bonded in a single-bond geometry to one N(5) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a water-like geometry to two equivalent Zn(1) atoms. In the second F site, F(2) is bonded in a water-like geometry to one Zn(2) and one Zn(3) atom. Linkers: 4 NC1=NN=N[N]1. Metal clusters: 1 F[Zn].F[Zn] ,2 [Zn]. The MOF has largest included sphere 3.90 A, density 2.03 g/cm3, surface area 2981.42 m2/g, accessible volume 0.15 cm3/g