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In the title compound, {(C4H12N2)2[Li2(P6O18)]·4H2O}n, the phosphate ring anion, located around an inversion center, adopts a chair conformation. Adjacent P6O18 rings are linked via corner-sharing by LiO4 tetra­hedra, generating anionic porous {[Li2(P6O18)]4−}n layers parallel to (101). The piperazine-1,4-diium cations occupy the pores and develop hydrogen bonds with the inorganic framework. An extensive network of N—H...O and O—H...O hydrogen-bonding inter­actions link the components into a three-dimensional network and additional stabilization is provided by weak C—H...O hydrogen bonds.

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In the title salt, (C12H20N2)[CuCl4], the CuII atom occupies a general position in a flattened tetra­hedral environment by Cl ligands, characterized by Cl—Cu—Cl angles of 134.04 (3) and 137.18 (4)°. The six-membered piperazinediium ring adopts a chair conformation. The organic cation and inorganic anion inter­act through N—H...Cl and C—H...Cl hydrogen bonds, forming a three-dimensional network.

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In the title compound, 2C12H20N22+·2H3O+·P6O186−·2H2O, a protonated water mol­ecule bridges the centrosymmetrical anionic P6O18 ring via O—H...O hydrogen bonds. The centrosymmetric hydrogen-bonded rings formed by four oxonium cations and four phosphate anions can be described by an R48(36) graph-set motif. The ring motifs are connected by hydrogen bonds into inorganic layers perpendicular to [100]. The 1-(2,3-di­methyl­phen­yl)piperazine-1,4-diium cations are located between the layers, compensating their negative charge and establishing N—H...O hydrogen bonds with the O atoms of the anionic framework.
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