The structure of 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene-silver(I) chloride, 1, has been determined to be a monomer with weak head-to-tail H...Cl interactions in the solid state. A multinuclear NMR study using a C-13(carbene) labeled derivative, 1(C-13), exhibits C-13-Ag-107,Ag-109 coupling in solution. Further, the solid state CP/MAS NMR parameters, including the principal components of the chemical shift tensors for both the C-13 and Ag-109 centers, have been determined. With the aid of DFT calculations, the orientation of the chemical shift tensors have been assigned.