The structure factor (SF) and atomic radial distribution function (RDF) of liquid lead simulated at a temperature of 613 K are compared. The shortest interatomic distance obtained from SF is found to be smaller than that determined as the abscissa of the first RDF coordination peak. It is shown that a satisfactory agreement between the experimental and calculated curves in the high-angle portion of SF can only be obtained when at least two most probable shortest interatomic distances r 1 and r 2, which indicate a complex structure of the first coordination shell of the liquid metal, are taken into account.