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Solid‐state multinuclear magnetic resonance and X‐ray crystallographic investigation of the phosphorus…iodine halogen bond in a bis(dicyclohexylphenylphosphine)(1,6‐diiodoperfluorohexane) cocrystal
Author(s) -
Zheng Dan Ni,
Szell Patrick M. J.,
Khiri Safaa,
Ovens Jeffrey S.,
Bryce David L.
Publication year - 2022
Publication title -
acta crystallographica section b
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.604
H-Index - 33
ISSN - 2052-5206
DOI - 10.1107/s2052520622004322
Subject(s) - cocrystal , halogen , halogen bond , crystallography , chemistry , acceptor , nuclear magnetic resonance spectroscopy , molecule , magic angle spinning , chemical shift , solid state nuclear magnetic resonance , crystal structure , hydrogen bond , stereochemistry , nuclear magnetic resonance , organic chemistry , physics , alkyl , condensed matter physics
Halogen bonding to phosphorus atoms remains uncommon, with relatively few examples reported in the literature. Here, the preparation and investigation of the cocrystal bis(dicyclohexylphenylphosphine)(1,6‐diiodoperfluorohexane) by X‐ray crystallography and solid‐state multinuclear magnetic resonance spectroscopy is described. The crystal structure features two crystallographically unique C—I…P halogen bonds [ d I…P = 3.090 (5) Å, 3.264 (5) Å] and crystallographic disorder of one of the 1,6‐diiodoperfluorohexane molecules. The first of these is the shortest and most linear I…P halogen bond reported to date. 13 C, 19 F, and 31 P magic angle spinning solid‐state NMR spectra are reported. A 31 P chemical shift change of −7.0 p.p.m. in the cocrystal relative to pure dicyclohexylphenylphosphine, consistent with halogen bond formation, is noted. This work establishes iodoperfluoroalkanes as viable halogen bond donors when paired with phosphorus acceptors, and also shows that dicyclohexylphenylphosphine can act as a practical halogen bond acceptor.