The hexamer duplex d(CACGCG).d(CGCGTG) produces unusual hexagonal ring shaped crystals when crystallized in the presence of cobalt hexammine chloride. Observation of the growth of these crystals over a period of about 6 days indicated that this morphology resulted from radial dissolution of the crystal from the center of the well-formed hexagonal plates. X-ray diffraction studies were carried out for crystals of four stages in the ring crystal morphology. The structure of the DNA in all four crystals was the Z type DNA double helix. The packing mode of the Z DNA duplex in all four crystal structures was that of the ¡®spermine¡¯ form. The crystal morphology changes from hexagonal plates to hexagonal rings without any apparent change in the molecular structure of the oligonucleotide or helical packing of the duplexes.