The crystal structures of minerals and inorganic compounds with OPb4 oxocentered tetrahedra are reviewed. It is shown that the OPb4 tetrahedral units may link by sharing common Pb atoms to form structural units of various shape and dimensionality. These units determine basic topology of the structures and influence their stability and properties. The high strength of the OPb4 te trahedral units involves interplay between high basicity of additional O2– anions and stereochemical activity of the 6s2 lone electron pairs on Pb2+ cations. The structural chemistry of polycations based upon OPb4 tetrahedra, in general, follows major trends previously observed for cation-centered tetrahedral units (silicates, phosphates, metal sulphides with MS4 tetrahedra, etc.). One may conclude that the basic structural correlations depend upon size and charge parameters of the ions only, irrespective of their positive or negative sign.
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