Synthesis and Modular Structural Architectures of Mineralogically Inspired Novel Complex Pb Oxyhalides

Three novel Pb oxyhalides, Pb3[O10Pb20]­(GeO4)4Cl10 (1), [O16Pb22]­[OPb]­(OH)­I10(I,Br)­(H2O) (2), and Pb5.5Si0.5O6Cl (3), have been prepared by high-temperature solid-state reactions (1 and 3) and hydrothermal method (2). The structure of 1 is based upon novel [O10Pb20]20+ layers of edge- and corner-sharing oxocentered OPb4 tetrahedra with cavities occupied by the GeO4 tetrahedral anions. The interlayer space contains low-occupied Pb sites and Cl– anions. The structure of 2 contains unique [O16Pb22]­[12+] layers of edge-sharing OPb4 tetrahedra with X– ions (X = I, Br) in and in between the layers. The structure of 3 is the first example of the Pb oxyhalide with the 3:1 ratio between the O–Pb and X sheets (X = halide). The unprecedented structure topologies and architectures observed in the title compounds are closely related to those observed in rare natural Pb oxyhalides that have no synthetic analogues to date.