The reaction of three equivalents of 5-(2,4-dihydroxyphenyl)-1H-tetrazole (H3dhptz) with iron(III) perchlorate in the presence of potassium hydroxide afforded the metallascorpionate framework. By simple recrystallization, an interesting coordination polymer, [K4.5Fe(dhptz)1.5(Hdhptz)1.5DMF7(H2O)3.5]n, was obtained. It possesses two potassium ions with either κ3-O or κ3-N binding modes, resulting in an array of K–Fe–K metal ions and a short Fe–K distance (3.427Å). One scorpionate ligand possesses 4.5 potassium ions at six different positions in the solid state by means of the bridging oxygen atoms of the DMF solvent. Further coordination modes between the potassium ions and water/DMF provide a one-dimensional (1-D) metallascorpionate array and allow the formation of a 3-D hexagonal coordination network.