Methane Sorption and Structural Characterization of the Sorption Sites in Zn2(bdc)2(dabco) by Single Crystal X-ray Crystallography

Store it away: Methane adsorption isotherms of Zn2(bdc)2(dabco) (1) are measured up to a pressure of 35 bar. X-ray structure analysis of methane-adsorbed 1 at 90 K reveals that methane molecules occupy three independent sorption sites A, B, and C while interacting with the framework as well as each other through van der Waals interactions. Sorption isotherms of methane in Zn2(bdc)2(dabco) are measured up to a pressure of 35 bar in the temperature range between 198–296 K. The methane sorption measurements at 296 K showed an uptake of 137 cm3 cm−3 at 35 bar. The enthalpy of methane adsorption for Zn2(bdc)2(dabco) estimated by the virial equation is 13.6 kJ mol−1 at zero coverage. X-ray structure analysis of methane-adsorbed Zn2(bdc)2(dabco) by synchrotron radiation at 90 K revealed that methane molecules occupy three independent sorption sites (A, B, and C) with a stoichiometry of Zn2(bdc)2(dabco)⋅6.69CH4, which is consistent with the results of the gas sorption measurements at 198 K. In a cavity, eight symmetry-related methane sorption sites A are located near the {Zn2(CO2)4} paddle-wheel units, while four symmetry-related methane sorption sites B are near the center of the small windows along the a and b axes. Both A and B sites are half-occupied. Methane molecules occupying sites A are not only in van der Waals contact with the paddle-wheel units, but also interact with the phenyl rings of bdc ligands through partial π-HC interactions. Methane molecules in B sites interact with the side of the phenyl rings through van der Waals interaction. The site C, located at the center of the cavity, is a secondary sorption site; methane molecules occupying sites C are in van der Waals contact with those in sites A and B.