The first use of a bulky barrel-shaped ligand is demonstrated in HHUD-3, with accessible porosity only feasible for a defect structure. With 35%+ missing linker defects and S-BET = 890 m(2)g(-1) (N-2), HHUD-3 features higher CH4 but lower CO2 and H-2 adsorption than UiO-66.