Hydrogen bonding Part 37. N,N,N-trimethyl-1 -adamantylammonium fluoride trihydrate and hemihydrate; evidence for covalent hydrogen bonding in the hemihydrate

Add time:08/29/2019    Source:sciencedirect.com

N,N,N-trimethyl-1-adamantylammonium fluoride forms two crystalline hydrates, a trihydrate and a hemihydrate. The IR spectrum of the trihydrate demonstrates the presence of H20 bound by strong electrostatic hydrogen bonds in a framework clathrate structure. The trihydrate can be recrystallized from acetone to yield crystals which should be suitable for diffraction studies. The IR spectrum of bound H20 in the hemihydrate is unlike that of H20 in any tetraalkylammonium salt hydrate that has been previously examined. This spectrum resembles that of the H2F−3 ion in N,N,N-trimethyl-1-adamantylammonium dihydrogen trifluoride, and a model for the hemihydrate is proposed in which a bridging H20 molecule is bound to two F− ions by unsymmetrical covalent, three-center hydrogen bonds. An ab initio calculation supports the proposed structure.

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