Non-Covalent Interactions in the Biphenyl Crystal: Is the Planar Conformer a Transition State?

A combined experimental and theoretical study of the biphenyl (BP) crystal is presented. The X-ray diffraction data collected at 100 K were subjected to Hirshfeld atom and multipole refinements of the electron density, rho(r). A theoretical exploration of the potential energy surface (PES) of the crystal was also carried out. This investigation challenges the common assumption that the planar structure of BP in the phase I crystal is an average of two twisted configurations in a double-well potential. The theoretical computations provide compelling evidence that this structure corresponds to a minimum on the PES hence to a stable molecular arrangement. Consistently, the experiment showed no evidence of positional or dynamic disorder. The intramolecular hydrogen-hydrogen bonds detected are not repulsive. The topological analysis of the experimental and theoretical rho(r) reveals that both the intra- and intermolecular HH and the C-H pi contacts stabilize the BP crystal.

Automated summary

The study challenges the common assumption about the planar structure of the biphenyl crystal and provides compelling evidence from theoretical computations for its stable molecular arrangement, which is also supported by the experimental results.