By means of large-angle X-ray scattering zinc(II) and mercury(II) ions in N,N-dimethylthioformamide solution are found to coordinate to four N,N-dimethylthioformamide molecules with Zn-S and Hg-S bond distances of 2.362(5) and 2.527(6) Angstrom, respectively. The intermediate divalent ion in group 12, cadmium, is solvated by six N,N-dimethylthioformamide molecules with a Cd-S bond distance of 2.69(1) Angstrom. Raman and far-infrared spectra have been recorded and assigned for the solvated ions both in solution and in the solid state. The character of the bands to the metal ion is discussed in order to explain the lower coordination numbers of the zinc and mercury-(II) ions.