The analysis of heavy-metal solids with NMR spectroscopy provides a means of investigating the electronic environment through the dependence of the chemical shift on structure. We have investigated the relation of the Pb-207 NMR isotropic chemical shift, span, and skew of a series of solid Pb(II) compounds to lattice parameters. Complementary relativistic spin-orbit density functional calculations on clusters such as PbI64- that model the local environment in the dihalides show a dependence of NMR properties on the local structure in good agreement with experimental results.