Crystalline sodium metasilicate, Na2SiO3, has been investigated by Si-29, Na-23, and O-17 MAS NMR spectroscopy. The O-17 quadrupolar coupling parameters have been measured for the bridging oxygen (BO) and nonbridging oxygen (NBO) sites. Ab initio calculations have also been performed for clusters modeling these oxygen sites, as well as other sites in crystalline silicates of known structure. On the bases of ab initio calculations, parametrized equations are discussed which describe trends in the BO O-17 quadrupolar coupling parameters. The agreement between these parametrized equations and reported values for a variety of crystalline environments is shown to be quite good. The ab initio calculated NBO O-17 quadrupolar coupling parameters are also in agreement with measured results for Na2SiO3 and analogous crystalline alkali silicates such as alpha -Na2Si2O5 and Li2Si2O5.