Syntheses and structure characterization of seven inorganic-organic hybrids based on N-Brønsted bases and perhalometallates

Seven organic-inorganic hybrids [(H2L1)3(Bi2Br9)(BiBr6)(H2O)] (1) (L1 = N,N,N′,N′-tetramethylethylenediamine), [(HL2)3(SbCl5)] · Cl (2) (L2 = 4-chlorobenzylamine), [(HL3)3(SbCl4)] · Cl2 (3) (L3 = 2,6-dimethylaniline), [(HL3)2(ZnCl4)] · 2H2O (4), [(HL4)4(Bi2Br10)] (5) (L4 = 2-methylquinoline), [(HL4)2(SbCl5)] (6) and [(H2L5)2(SbCl5)2] · H2O (7) (L5 = bis(N-imidazolyl)methane) were prepared and characterized by IR, XRD, EA and TG analysis. XRD analysis told that all complexes were built from non-covalent bonds between the cations and the perhalometallates anions. The lattice H2O also played crucial role in structure extension in the respective hybrids.Extensive intermolecular interactions have been used in the self-assembly of diverse motifs, ranging from strong X-H···Y (X = O, N; Y = Br, Cl, O) H-bonds to weak CH-M (M = Cl, Br), CH2-M (M = Cl, Br), CH3-M (M = O, Cl, Br), CH3-CH3/CH3-CH/CH2-CH/CH-CH, Cl-Cl, CH3-π and π-π associations. Among them, 3 D architectures are found in 1–2 and 4–7, but only 2 D motif is appeared in 3. The arrangements of the anions and cations in the solid mode are ruled not only by the size and symmetry of the cations, but also by the non-covalent bonds in the crystals.