Solvothermal treatment of a mixture of Co(OAc)(2), NaN3, NaN(CN)(2), HF, MeCN, and H2O generated an AlB2-like metal-organic framework, namely, [{(Co3F)(3)(trta)(2)(H2O)(9)}{Co(Hbta)(3)}2] center dot 11H(2)O (1) (H(3)trta = N,N,N-tris-tetrazol-5-yl-amine; H(3)bta = N,N-bis-tetrazol-5-yl-amine), in which supedrianglar supramolecular building blocks (SBBs) {(Co3F)(3)(trta)(2)} act as 12-connected nodes of hexagonal prisms. The unprecedented ligand N,N,N-tris-tetrazol-5-yl-amine is in situ generated via metal-assisted reactions of NaN(CN)(2), MeCN, and NaN3, and a possible mechanism involves both 1,3-dipolar cycloaddition and nucleophilic addition. The F-centered CO3 triangles are bridged by trta groups to result in supertriangular {(Co3F)(3)(trta)(2)} SBBs that are further arranged in a frustrated triangular lattice. The long-range ordering temperature is reduced to 4.8 K due to strong spin frustration.