A benchmark for non-covalent interactions in organometallic crystals

Abstract

Organometallic complexes are the basis for homogeneous catalysis, have applications in materials science and are also active pharmaceutical ingredients. The interaction between transition metal complexes in the solid state is determining their thermodynamics and bio-availability. Non-covalent interactions such as hydrogen bonding and van der Waals are stabilizing crystals of transition metal complexes. The variation of ligand field, central metal atoms and their oxidation and spin states are determinants of the magnitude of their inter-molecular interactions. A comparison of a set of 43 manually curated experimental heats of sublimation (the new XTMC43 set) and results from periodic DFT calculations shows that an agreement to within 9% can be achieved using GGA or mGGA functionals with atom-centred Gaussian-type basis functions. The need for careful assessments of consistency, calibration and reproducibility of experimental and computational data is discussed. Results regarding the new XTMC43 benchmark set are suggested to serve as a starting point for further method development, systematic screening and crystal engineering.