Unlike the highly sensitive and relatively narrow lineshapes associated with the Li NMR spectra of the A-site, the M-site may contain one or two NMR-active nuclei, namely 121/123 Sb and 209 Bi. Although each isotope is found in high natural abundance (57% for 121 Sb (I = 5/2), 43% for 123 Sb (I = 7/2) and 100% for 209 Bi (I = 9/2)), all are half-integer quadrupole nuclear spins, and can suffer from intrinsically broad central transition lineshapes due to their sizeable quadrupole moments. This broadening can further complicate both interpretation and acquisition of their NMR spectra if their electric field gradient (EFG) is non-zero. Fortunately, the parent phases (Li3M, M = Sb or Bi) have local octahedral symmetry within the cubic crystalline phase (i.e., a zero EFG), warranting an attempt to study these sites in more detail. The non-spinning 121 Sb and 209 Bi NMR spectra (Figure ) show broad Gaussian-like resonances (Li3Sb -fwhm = 15 kHz; Li3Bi -fwhm = 14 kHz) with center-of-gravity chemical shifts ( cgs) of 496 and 1790 ppm, respec i el . As predic ed based on he cr s alline si e s mme r , no e idence of second-order quadrupole broadening nor shielding anisotropy is observed for the M site nuclei of either parent phase. Furthermore, hetero-and homonuclear dipolar coupling does not appear to contribute to the NMR linewidth as virtually no spectral differences were observed between nonspinning and MAS conditions. In contrast to these cubic crystalline systems, the 121 Sb NMR of the hexagonal Li2Sb phase has two crystallographic inequivalent Sb sites with similar chemical environments in a pentacapped trigonal prism polyhedron (Li9Sb2). Resolution of two sites is not possible, b fi ing he po der pa ern re eals a si e i h an iso = 1100 50 ppm, quadrupole coupling constant, CQ = 51.0 ± 0.7 MHz and an axial symmetry tensor ( = 0) consis en i h he reduction in local symmetry between Li3Sb and Li2Sb (see Figure ).