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The structure of the title compound, [Li2(C8H2N2O8)(H2O)4]·H2O, is composed of dinuclear mol­ecules in which the ligand bridges two symmetry-related LiI ions, each coordinated also by two water O atoms, in an O,N,O′-manner. The Li and N atoms occupy special positions on twofold rotation axes, whereas a crystal water mol­ecule is located at the inter­section of three twofold rotation axes. The LiI cation shows a distorted trigonal–bipyramidal coordination. Two carboxyl­ate groups remain protonated and form short inter­ligand hydrogen bonds. The mol­ecules are held together by a network of hydrogen bonds in which the coordinating and solvation water mol­ecules act as donors and carboxyl­ate O atoms as acceptors, forming a three-dimensional architecture.

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The title coordination polymer, {[Li2(C8H2N2O8)(H2O)2]·2.5H2O}n, is built up from mol­ecular ribbons propagating in the c-axis direction of the ortho­rhom­bic unit cell; the ligand bridges two Li+ ions using both its N,O,O′-bonding sites and adjacent Li+ ions are bridged by pairs of water mol­ecules. The coordination geometry of the metal ion is distorted trigonal bipyramidal, with the ligand O atoms in the axial sites. Two of the carboxyl­ate groups of the ligand remain protonated and form short symmetric O—H...O hydrogen bonds. In the crystal, the ribbons inter­act via a network of O—H...O hydrogen bonds in which coordinating water mol­ecules act as donors and carboxyl­ate O atoms within adjacent ribbons act as acceptors, giving rise to a three-dimensional framework. O—H...N inter­actions are also observed. The asymmetric unit contains quarter of the ligand and the complete ligand has 2/m symmetry; the Li+ ion lies on a special position with m.. site symmetry. Both bridging water mol­ecules have m2m site symmetry and both lattice water mol­ecules have m.. site symmetry; one of the latter was modelled with a site occupancy of 0.25.
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