Ferrocenylpyrazole—A versatile building block for hydrogen-bonded organometallic supramolecular assemblies

The crystal architectures of 5-ferrocenylpyrazole (1) and its metal complexes were investigated. Compound 1 can form non-solvated and chloroform-solvated crystals. In both cases, 1 forms a zigzag one-dimensional architecture via NH⋯N hydrogen bonds. The hydrogen bond exhibits a twofold disorder, which was shown to be static by solid-state 13C NMR. In the solvated crystal, the chloroform is released at 415 K, associated with melting of the crystal. The reaction of 1 with metal salts provided metal-centered ferrocenyl clusters [Zn(NO3)2(1)4] (4), [Co(NO3)2(1)4] (5), [CoCl2(1)4] (6), [Zn(NCS)2(1)2] (7), cis-[Pt(NH3)2(1)2](PF6)2 (8), and trans-[Pt(NH3)2(1)4](PF6)2 (9). In all of these complexes, 1 acts as a monodentate ligand. In 4, 5, and 7, the multinuclear units are joined via hydrogen bonds to form supramolecular chains. Two polymorphs were found for the crystals of 4. Both are composed of the same hydrogen-bonded chains, but their arrangements are different. 5-Ferrocenyl-1-tritylpyrazole (2) and 4-ferrocenyl-1-methylpyrazole (3) were also crystallographically characterized.

Graphical abstractThe crystal architectures of 5-ferrocenylpyrazole (FcPz) and its metal complexes were investigated. FcPz forms a zigzag one-dimensional architecture via NH⋯N hydrogen bonds. The reaction of FcPz with metal salts provided metal-centered ferrocenyl clusters, which are joined via hydrogen bonds to form supramolecular chains in the crystal.Figure optionsDownload full-size imageDownload as PowerPoint slide