A Mn-based rod metal-organic framework (MOF), ROD-6, with a new lrk net is synthesized. It represents an unusual type of MOF topology containing both a 1-periodic secondary building unit (rod SBU) and a polytopic linker (here 1,3,6,8-tetrakis(p-benzoic acid)pyrene), and also exhibits high stability (up to 485 °C) and unusual CO2 uptake behaviour and selectivity despite the lack of strong interacting sites, demonstrated by the low and increasing heat of adsorption.