To investigate the local environments of residual Li ions, Li NMR spectroscopy was performed on the "collapsed" oxysulfide (Sample 1: Sr2MnO2Cu0.35Li0.13S2) and its lithiated derivatives. Before lithiation, the collapsed oxysulphide featured multiple peaks (Fig. ) consistent with the complexity of the diffraction results, while both electrochemically and chemically lithiated samples exhibited much simpler spectra with lower frequency resonances (Fig. ). Large hyperfine shifts result from transfer of unpaired electron spin density from paramagnetic Mn 2+/3+ ions to lithium s orbitals. Our analysis of Li spectra of Sr2MnO2LixS2 and structural homologues estimated that each Mn 2+ -S-Li interaction resulted in a shift of 101 ppm 32 while a Mn 3+ -S-Li interaction gave a larger shift of 165 ppm due to greater Mn 3+ -S covalency. Since each Li is surrounded by four neighbouring Mn in the parent-type structure (Fig. ), and hyperfine shifts are additive, four Mn 2+ -S-Li interactions should result in a hyperfine shift of ~404 ppm, increasing to 468 or 532 ppm when one or two of the Mn ions are oxidised the 3+ state. These predicted values can be used to assign and rationalise the spectra of the lithiated phases and the lowest frequency resonances seen in Fig. for the "collapsed" phase. Higher frequency resonances in the spectrum of the "collapsed" phase (Fig. ), could be rationalized by taking in account the Mn-(S2) 2-coordination in the intergrowth structures (Fig. ). Weaker, longer Mn-S bonds are expected for Mn-(S2) 2-compared with Mn-S 2-bonds, due to the lower charge of the [S2] 2-ion and its higher energy π* antibonding orbitals that overlap directly with the Mn t2g orbitals. So a Mn ion asymmetrically bound to one S 2-and one (S2) 2-anion, will form a stronger covalent bond to the single S 2-ion than when it is bound symmetrically to two S 2-ions and we deduce that an asymmetric Li-S 2--Mn 2+ -(S2) 2-bond pathway gives rise to a larger shift of approximately 165 ppm, compared with 101 ppm for the Li-S 2--Mn 2+ -S 2-pathway. Fig. shows how the presence of intergrowth structures (Fig. ) accounts for the multiple higher frequency resonances in Fig. . A 1:1 intergrowth with more Li-S 2--Mn 2+ -(S2) 2-bond pathways result in higher shifts than 1:2 intergrowth structures, and Mn 3+ gives higher shifts than Mn 2+ .