Abstract: | Reaction of the zinc or magnesium formate dihydrates in formic acid under solvothermal conditions results in the formation of single crystals of the anhydrous metal(II) formates β‐Zn(OOCH)2 and β‐Mg(OOCH)2. Both structures form one‐dimensional chains of μ‐oxygen‐bridged metal atoms. Single crystal diffraction studies reveal that β‐zinc formate represents the first structure in which chains of oxygen‐bridged metal atoms are connected by alternating single, double and triple oxygen atom bridges resulting in the first observation of corner, edge and face sharing coordination octahedra within a single chain. Polycrystalline material can be obtained by dehydration reaction of zinc formate dihydrate. β‐magnesium formate is the crystalline product that is obtained by annealing the amorphous intermediate phase after dehydration of magnesium formate dihydrate. |