Unconventional hydrates with differently
bound water molecules
and related mazy intermolecular interaction networks need systematic
investigation. The assembly rules, interaction analysis, and dehydration
behavior can be dramatically more complicated when compared with those
of common hydrates. In this work, creatine phosphate sodium (CPS)
was selected as a model compound representing unconventional hydrates.
The packing mode and the role of water molecules related to the dehydration
mechanism were explored by the combination of experimental (diffraction,
thermal, microscopy) and quantum chemistry computational (interplay
visualization, binding energy calculation) methods. It was observed
that in the structure of CPS heptahydrate and heminonahydrate, channel,
isolated-site, and ion-associated water molecules exist simultaneously,
constructing the framework via the coordination bond
and hydrogen bond. The binding energy of some ion-coordinated water
molecules is lower than that of hydrogen-bonded ones while that of
some isolated-site water molecules is lower when compared with that
of channel ones, which is counterintuitive. Moreover, the diverse
types and locations of water molecules, complicated H2O···H2O interactions, and the trade-off between CPS···H2O and H2O···H2O lead
to multistage, variable, and binding-energy-independent dehydration
behavior. This work sheds light on the novel structure and variable
dehydration mechanism of complicated hydrate systems and inspires
the particularity and further investigation of unconventional hydrates.