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The rational selection of ligands is vitally important in the construction of new organic–inorganic hybrid three‐dimensional perovskite complexes. As part of an exploration of perovskite‐type materials, two new Na–I compounds based on the piperazine ligand, namely poly[piperazinediium [tri‐μ‐iodido‐sodium]], {(C4H12N2)[NaI3]}n, 1, and catena‐poly[tris(piperazinediium) [[triiodidosodium]‐μ‐iodido] triiodide monohydrate], {(C4H12N2)3[NaI4]I3·H2O}n, 2, have been synthesized by adjusting the stoichiometric ratio of sodium iodide and piperazine, and were characterized by single‐crystal X‐ray diffraction. In the crystal structures of 1 and 2, each NaI cation is linked to six I atoms, but the compounds show completely different configurations. In 1, the structure includes a perovskite‐like array of vertex‐sharing NaI6 octahedra stretching along the direction of the three axes, and each piperazinediium dication is enclosed in the NaI3 perovskite cage. However, in 2, each NaI atom bridges a single I atom to form a one‐dimensional linear chain, and complex intermolecular hydrogen bonds connect these one‐dimensional chains into a three‐dimensional supramolecular network. [ABSTRACT FROM AUTHOR]

The rational selection of ligands is vitally important in the construction of new organic-inorganic hybrid three-dimensional perovskite complexes. As part of an exploration of perovskite-type materials, two new Na-I compounds based on the piperazine ligand, namely poly[piperazinediium [tri-μ-iodido-sodium]], {(C 4 H 12 N 2 )[NaI 3 ]} n , 1, and catena-poly[tris(piperazinediium) [[triiodidosodium]-μ-iodido] triiodide monohydrate], {(C 4 H 12 N 2 ) 3 [NaI 4 ]I 3 ·H 2 O} n , 2, have been synthesized by adjusting the stoichiometric ratio of sodium iodide and piperazine, and were characterized by single-crystal X-ray diffraction. In the crystal structures of 1 and 2, each Na I cation is linked to six I atoms, but the compounds show completely different configurations. In 1, the structure includes a perovskite-like array of vertex-sharing NaI 6 octahedra stretching along the direction of the three axes, and each piperazinediium dication is enclosed in the NaI 3 perovskite cage. However, in 2, each Na I atom bridges a single I atom to form a one-dimensional linear chain, and complex intermolecular hydrogen bonds connect these one-dimensional chains into a three-dimensional supramolecular network., (open access.)

The title compound, [Cu(C7H3NO4)(C5H6N2)(C3H7NO] n , is an amino-function-alized chiral metal-organic framework with (10,3)-a topology. It has been constructed via the assembly of the achiral triconnected pyridine-3,5-di-carboxyl-ate (3,5-PDC) building block and a triconnected Cu(II) atom. Each Cu(II) ion is coordinated by two O atoms and one N atom, respectively, of three crystallographically independent 3,5-PDC ligands. The square-pyramidal (CuN2O3) coordination geometry of the Cu(II) ion is completed by an N atom of a terminal 4-amino-pyridine (4-APY) ligand and the O atom of a terminal N,N-di-methyl-formamide (DMF) ligand to give a triconnected 'T'-shaped secondary building unit, which becomes trigonal in the resulting (10,3)-a topology. In the three-dimensional structure, weak N-H⋯O hydrogen bonds are observed in which the donor N-H groups are provided by the 4-APY ligands and the acceptor O atoms are provided by the non-coordinating carboxylate O atoms of the 3,5-PDC ligands.