Exploring secondary bonding in p-block chemistry – an experimental study of [GeX2{o-C6H4(PMe2)2}] using variable pressure single crystal X-ray diffraction

Secondary bonding interactions play a major role in governing the overall structures adopted. The low energy contributions from these weak interactions make structure prediction very difficult, hence there is a need for experimental techniques that contribute to understanding the interplay between different types of secondary bonding. Variable pressure single crystal X-ray diffraction studies on the homologous series, [GeX2{o-C6H4(PMe2)(2)}], X = Cl 1, Br 2, I 3, show that probing the different interfaces between layers of structural building blocks, rather than conventional molecular units, provides very valuable insights. 1 and 3 undergo a smooth compression as the pressure is increased, whereas a phase transition occurs for 2 at a pressure between 29 and 41 kbar. This is associated with an abrupt change in the beta angle (from 111.33(2)degrees to 92.24(8)degrees). The structural consequences are most evident in the aromatic. aromatic layer interface. Below the phase transition there is an edge-to-face C-H center dot center dot center dot pi arrangement (like 1), with the angle between the planes of adjacent rings of similar to 75 degrees, whereas above the transition this interface has transformed to an offset-parallel face-to-face pi-pi stacking interaction (like 3). The GeX2 center dot center dot center dot X2Ge interface undergoes a concomitant, but smoother compression with increasing pressure. 2 also has the highest void volume at ambient pressure (11.9%), and as expected the phase transition results in a structure with much more efficient packing. This, the first such study involving p-block coordination complexes, reveals the subtlety and complexity of the interplay between the different forms of weak, secondary (supramolecular) interactions present. The results indicate that this type of experimental study can provide valuable additional information to help guide crystal structure prediction by computational methods, an important and very challenging target.