cg9b01081_si_001.pdf (902.98 kB)
Crystal Structure Evidence for the Directionality of Lone Pair−π interactions: Fact or Fiction?
journal contribution
posted on 2019-10-18, 12:06 authored by Chuandong Jia, Haohao Miao, Benjamin P. HayThe
location of intermolecular lone pair atom contacts with C6F5X, where X = any atom, was evaluated using the
Cambridge Structural Database (CSD). The results establish that it
is not possible to distinguish the distribution of lone pair atoms
in contact with this arene surface from an isotropic distribution
of van der Waals contacts. In other words, the CSD provides no evidence
for either the directionality or the existence of the lone pair−π
interaction with this electron-deficient arene. The current findings
are in stark contrast to prior reports that crystal structure data
provide (i) examples of lone pair−π interactions and
(ii) evidence that lone pair−π interactions are strongly
directional. Examination of the previous CSD analyses reveals that
in every case the data had been misinterpreted. The most common mistake
involves using search criteria to select subsets of contacts and then
attaching significance to these selected contacts without the context
of the entire contact distribution.