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The crystal structure of Li2Na2NiP6O18·12H2O is characterized by the presence of six-membered P6O186− phosphate ring anions (inter­nal symmetry -1) having a chair conformation and three different cations, viz. Li+, Na+ and Ni2+, to counterbalance the anionic charge. All atoms are in general positions except for nickel, which lies on a special position with site symmetry 2. Lithium has a tetra­hedral environment (LiO4), and sodium and nickel have octa­hedral environments [NaO6 and Ni(H2O)6, respectively]. The P6O18 rings are linked via corner sharing by NaO6 octa­hedra and LiO4 tetra­hedra to form a three-dimensional framework presenting tunnels running along [010] in which the six-coordinated Ni2+ cations are located. The structure is stabilized by a network of O—H...O hydrogen bonds.
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