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The crystallization of a reactive zincophosphate gel (which may contain Co(II) component) in the presence of sodium cations at ambient temperature and pressure yielded products (abbreviated ZnPO-HEX or CoZnPO-HEX) with a novel anionic open framework topology. The Co(II) ions isomorphously replace zinc(II) in this zincophosphate lattice up to 30%. The hopeite phase appears as a precursor in the crystallization of these new products. The single crystal structure determination of CoZnPO-HEX reveals that the structure belongs to the hexagonal P6₁ space group with unit cell parameters a = 10.447(3) and c = 15.049(5)Å. The structure consists of a three-dimensional tetrahedral framework containing one-dimensional six-ring channels. An infinite helix built up of sodium cations and water molecules has been found inside the channel. The helix plays an important structural role because a complete dehydration of the materials is the cause for the transformation of the hexagonal structure to an unknown crystalline phase. © 1995.