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Using high-throughput instrumentation to screen conditions, the reaction between FeCl2 and H3BTT·2HCl (BTT3− = 1,3,5-benzenetristetrazolate) in a mixture of DMF and DMSO was found to afford Fe3[(Fe4Cl)3(BTT)8]2·22DMF·32DMSO·11H2O. This compound adopts a porous three-dimensional framework structure consisting of square [Fe4Cl]7+ units linked via triangular BTT3− bridging ligands to give an anionic 3,8-net. Mössbauer spectroscopy carried out on a DMF-solvated version of the material indicated the framework to contain high-spin Fe2+ with a distribution of local environments and confirmed the presence of extra-framework iron cations. Upon soaking the compound in methanol and heating at 135 °C for 24 h under dynamic vacuum, most of the solvent is removed to yield Fe3[(Fe4Cl)3(BTT)8(MeOH)4]2 (Fe-BTT), a microporous solid with a BET surface area of 2010 m2 g−1 and open Fe2 …