Crystal Structures of Three Organically Modified Metal Halides
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Under the hydro(solvo)thermal conditions, the reactions of metal halides with organic N-heterocyclic molecules produced three new organically modified metal halides [tmbp][Cu2Br4] (tmbp2+ = N,N,N′,N′-tetramethyl-4,4′-bipiperidinium) 1, [H2(dmbpp)][Pb2I6] (dmbpp = dimethyl-1,3-bis(4-piperidyl)propane) 2 and [PbI2(bpp)] 3 (bpp = 1,3-bis(4-pyridyl)propane). It is noteworthy that tmbp2+ in compound 1 originated from the in situ alkylation of bp with CH3OH (bp = 4,4′-bipiperidine). The mechanism study indicates that H+ and Br− play a key role in the alkylation reaction. X-ray single-crystal diffraction analysis revealed that (i) compounds 1 and 2 are the organically templated halometallates. Both possess the 1D chain structures. The 1D chain of compound 1 can be regarded as a linear arrangement of CuBr4 tetrahedra by sharing the edges, whereas that of compound 2 can be considered as an endless extension of PbI6 octahedra by sharing the faces; (ii) compound 3 is the 1:1 adduct of PbI2 and bpp. The PbI2 chain shows a linear shape. Bpp serves as the connector, propagating the PbI2 chains into a 2D layer network of compound 3.
KeywordsHalometallate Templating agent In situ N-alkylation
This research was supported by the National Natural Science Foundation of China (No. 21271083).
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