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Non‐Covalent Interactions in the Biphenyl Crystal: Is the Planar Conformer a Transition State?
Author(s) -
LanderosRivera Bruno,
Jancik Vojtech,
MorenoEsparza Rafael,
Martínez Otero Diego,
HernándezTrujillo Jesús
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202101490
Subject(s) - intramolecular force , intermolecular force , multipole expansion , crystal (programming language) , biphenyl , crystallography , crystal structure , hydrogen bond , planar , chemistry , conformational isomerism , crystal structure prediction , chemical physics , materials science , computational chemistry , molecule , physics , stereochemistry , quantum mechanics , computer graphics (images) , organic chemistry , computer science , programming language
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, ρ(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 ρ(r) reveals that both the intra‐ and intermolecular H⋅⋅⋅H and the C−H⋅⋅⋅π contacts stabilize the BP crystal.