Structure of Diferrocenyl Thioketone: From Molecule to Crystal

Ferrocenyl-functionalized thioketones have recently been recognized as useful building blocks for sulfur-containing compounds with potential applications in materials chemistry. This work is devoted to a single representative of such thioketones, namely diferrocenyl thioketone (Fc₂CS), whose structure has been determined here for the first time. Both X-ray crystallography and a wide variety of quantum-chemical methods were used to explore the structure of Fc₂CS. In addition to the X-ray structure determination, intermolecular interactions occurring in the crystal structure of Fc₂CS were examined in detail by quantum-chemical methods. These methods were also an invaluable tool in studying the molecular structure of Fc₂CS, from the gas phase to solutions and to its crystal. Intramolecular interactions governing the conformational behavior of an isolated Fc₂CS molecule were deduced from quantum-chemical analyses carried out in orbital space and real space. Our experimental and theoretical results indicate that the main structural features of an isolated Fc₂CS molecule in its lowest-energy geometry are retained both upon solvation and in the crystal. The tilt of ferrocenyl groups is only slightly affected by crystal packing forces that are dominated by dispersion. Nonetheless, a network of intermolecular interactions, such as H···H, C···H and S···H, was detected in the Fc₂CS crystal but each of them is fairly weak.