Effect of heteroatoms in the inorganic–organic layered perovskite-type hybrids [(ZCnH2nNH3)2PbI4], n = 2, 3, 4, 5, 6; Z = OH, Br and I; and [(H3NC2H4S2C2H4NH3)PbI4]

Ten inorganic–organic hybrids have been synthesized and characterized by single crystal X-ray diffraction experiments. The inorganic component is based on lead(II) iodide units and four different types of alkylammonium cations. The structural motif adopted by the inorganic component has 2-D layers of corner-sharing PbI6 octahedra, which are closely related to the K2NiF4 and RbAlF4 structure types. This motif is observed in hybrids containing alkylammonium cations (ZCnH2nNH3) that contain three different heteroatoms: [(HOC2H4NH3)2PbI4] and [(HOC3H6NH3)2PbI4], [(BrC2H4NH3)2PbI4] and [(ICnH2nNH3)2PbI4] (n = 2–6). Additionally the hybrids [(H3NC2H4S2C2H4NH3)PbI4] and [(NH3C2H4S2C2H4NH3)2PbI5·I] crystallized from a single solution and have two distinct inorganic motifs, the former has 2-D layers of corner-sharing octahedra and the latter has 1-D chains of corner-sharing octahedra. The identity of the heteroatom and the chain length have an effect on the overall packing exhibited by the hybrid structures.