Quantum Chemical Dissection of the Shortest P=O⋅⋅⋅I Halogen Bond: The Decisive Role of Crystal Packing Effects.
A supramolecular arrangement comprising a bridged triarylphoshine oxide and an aryl iodide is reported, featuring the shortest ever reported P=O⋅⋅⋅I halogen bond of 2.683(5) Å in the solid state. X-ray crystallographic analysis together with modern quantum chemical methods were enlisted to dissect the individual contributions that compelled this exceptionally short halogen bond, pointing out the decisive role of crystal packing effects.
Department of Chemistry and Pharmacy, Chair of Organic Chemistry I, University of Erlangen-Nürnberg, Henkestrasse 42, 91054, Erlangen, Germany.
Tobias A
TA
Schaub
Mulliken Center for Theoretical Chemistry, Institute for Physical and Theoretical Chemistry, Universität Bonn, Beringstrasse 4, 53115, Bonn, Germany.
Rebecca
R
Sure
Department of Chemistry and Pharmacy, Chair of Organic Chemistry I, University of Erlangen-Nürnberg, Henkestrasse 42, 91054, Erlangen, Germany.
Frank
F
Hampel
Mulliken Center for Theoretical Chemistry, Institute for Physical and Theoretical Chemistry, Universität Bonn, Beringstrasse 4, 53115, Bonn, Germany.
Stefan
S
Grimme
Department of Chemistry and Pharmacy, Chair of Organic Chemistry I, University of Erlangen-Nürnberg, Henkestrasse 42, 91054, Erlangen, Germany.
Milan
http://orcid.org/0000-0002-4960-4636
M
Kivala
X-ray diffraction; density functional calculations; halogen bonding; phosphorus heterocycles; supramolecular chemistry