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Managing Hydrogen Bonding in Clathrate Hydrates by Crystal Engineering
Author(s) -
Shin Kyuchul,
Moudrakovski Igor L.,
Ratcliffe Christopher I.,
Ripmeester John A.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201700654
Subject(s) - clathrate hydrate , methanol , chemistry , crystal engineering , hydrogen bond , hydrate , crystal structure , crystallography , molecule , organic chemistry
Methanol is one of the most common inhibitors for clathrate hydrate formation. Crystalline clathrate hydrates containing methanol were synthesized and analyzed by powder X‐ray diffraction and 13 C NMR spectroscopy. The data obtained demonstrate that methanol can be a helper guest for forming structure I, structure II, and structure H clathrate hydrates, as long as the lattice framework contains NH 4 F. The latter acts as a lattice stabilizer by providing sites for strong hydrogen bonding of the normally disruptive methanol hydroxy group. NH 4 F and methanol can be considered key materials for crystal engineering of clathrate hydrates, as the modified lattices allow preparation of hydrates of non‐traditional water‐soluble guests such as alcohols and diols. Methanol takes on the role of an unconventional helper guest. This extends clathrate chemistry to a realm where neither hydrophobic guests nor high pressures are required. This also suggests that more stable lattices can be engineered for applications such as gas storage.