The first observed complex of 11-crown-3 ether. X-ray crystal structure and NMR study of (benzo-11-crown-3)2·LiNCS

Abstract

The title complex crystallizes in the monoclinic P21/c space group, with a = 7.7397(8), b = 18.287(2), c = 17.4726(19) Å, β = 94.008(2)°, and Z = 4. The coordination geometry around the lithium cation is pseudooctahedral. The effects of lithium complexation on the 1H and 13C solution NMR spectra are discussed. In the solid-state 13C NMR spectrum at 300 K, very long aliphatic proton spin lattice relaxation times are observed along with broadening of the aliphatic carbon resonances. These results are attributed to the dipolar washout phenomenon, where the presence of a low amplitude motion of the same frequency as the 1H decoupler, leads to less effective removal of the 1H–13C dipolar coupling. At 330 K, there is some sharpening of the aliphatic resonances since there is less interference between the motion and the decoupling frequency.Key words: crown ether analog, lithium complex.