Investigation of the disorder of dibromo- and dichloromethane in their tri-ortho-thymotide clathrates using X-ray diffraction and solid-state 2H NMR spectroscopy

The tri-ortho-thymotide (TOT) clathrates of dibromo- and dichloromethane were characterized by single crystal X-ray diffraction at 200 K and solid-state H-2 NMR spectroscopy as a function of temperature. The host structure was found to be typical of other cage-type TOT clathrates. The X-ray results showed a substantial amount of disorder among the guest molecules. In both clathrates, multiple guest molecule positions could be modeled. The heavy atoms of all the guest molecule positions lie approximately in the same plane, with some out-of-plane distortion. The guest molecules were of two different types in positions symmetric about the crystallographic twofold rotation axis: type A guests, with carbon atoms well removed from the crystallographic twofold axis, and type B guests, with carbon atoms very close to the twofold axis. The H-2 NMR spectra for the guests confirmed that the disorder was dynamic. The experimental results could be accounted for by the presence of three simultaneous types of molecular motion, all fast with respect to the H-2 quadrupolar interaction: (i) twofold molecular flips about the molecular C-2 symmetry axis, (ii) exchange between the type A and type B sites in a single plane, and (iii) a two-site libration of the plane containing the heavy atoms of the A and B guest sites with a temperature-dependent amplitude.