Metal-organic frameworks featuring open metal coordination sites have been widely studied for the separation of gas mixtures. For CO2/N2 separations, these materials have shown considerable promise. Herein, we report the characterization of a subset of the well-known PCN-250 class of frameworks upon CO2 adsorption via powder neutron diffraction methods. Noteably, in contrast to previously reported data, they display only moderate CO2 adsorption enthalpies, based on metal cation-CO2 interactions. Further, we show charge balance in these materials is likely achieved via ligand vacancies rather than the presence of μ3-OH groups in the trimetallic cluster that comprises them.