Figure : Ratio of G3 molecules involved in the coordination of [Li] + as a function of the mixing ratio and temperature. The dashed horizontal line marks the threshold of 20 % free G3 molecules given by Ueno and co-workers for the definition of SILs. atoms on different sulfonyl groups of the anion. Here, MD simulations of the pure lithium salt were taken into account for better distinguishing between monodentate and bidentate anions. However, it should be noted that the MD simulations of the pure salt rather represent a supercooled, glassy, and liquid-like state of the salt and not the crystalline structure at the investigated temperature. Nevertheless, the pure system works well as a reference for the two anionic characters since these merge into each other in the mixtures with G3, and the cut-off radii r c cannot be identified easily. A snapshot of monodentate and bidentate anions in the mixture with x([Li][NTf 2 ]) = 0.750 with their respective Li-N distances are presented in Figure . This supports the cut-off radii of 3.8 Å for monodentate anions and 5.0 Å for bidentate anions obtained from the site-site RDFs. The consequently obtained average numbers of monodentate and bidentate anions are depicted in Figure . However, Figure only shows the mixtures in which relevant coordination of the cations through anions is present. All mixtures are presented in the SI. Bidentate anions are neglectable in mixtures with more or equal the amount of G3 compared to the salt ion pairs. Only in the mixture with more anions than G3 molecules, significant amounts of bidentate anions are present, although the majority of anions also has a monodentate character at this mixing ratio. The predominant occurrence of monodentate anions can be explained by steri-0.400 0.450 0.500 0.750 cal hindrance. If G3 is also involved in the coordination of a cation, the space left in the first solvation sphere of the cation can only accommodate a single oxygen atom from the anion involved in the coordination.