The proton signals at the 2'- and 6'-positions of the aromatic side arms of a silver(I) complex with a chiral tetra-armed cyclen ((S)-L2) are assigned by comparison with H-1 NMR spectra and X-ray structure of Ag+ complexes with three analogues of (S)-L2: (S)-L2(3D )having one benzyl group and three deuterium-substituted benzyl groups, (S)-L2(2D) having two benzyl groups and two deuterium-substituted benzyl groups, and (S)-L2(F) having three benzyl groups and one 4'-fluorobenzyl group. An interaction factor is defined by using the X-ray structures. The chemical shift values of the proton signals in the aromatic side arms can be explained by using the interaction factors that are defined by the dihedral angles, the angles between two mean planes, and the CH center dot center dot center dot pi distances from the X-ray data of the (S)-L2/Ag+ complex.