The Syntheses, Structures, and Laser Raman and Infrared Spectra of Co(NH3)(6)CuCl5, [Co(NH3)(5)OH2] CuCl5, Co(NH3)(6)CdCl5, Co(NIH3)(6)ZnCl5, and Co(NH3)(6)ZnCl4(NO3)

The new compounds Co(NH3),CdCl5, Co(NH4)ZnCl5, and Co(NH3)6ZnCl(4)(NO3) have been synthesized, and their infrared and laser Raman spectra have been measured, along with that of Co(NH3)(6)CuCL5, in an effort to draw conclusions regarding their structures. The differences observed in the spectra of the isomorphic cadmium and copper salts indicate that the CdCl58- ion exists as a trigonal-bipyramidal species in which the axial Cd-Cl bonds are equivalent in length or longer than the equatorial ones. This inference was verified by an X-ray diffraction study, which shows that r(Cd-Cl-ax.) = 2.527 (5) A and r(Cd-Cl-eq) = 2.564 (5) angstrom. The observed equivalence in the Cd-Cl-ax. bonds implies that the axial compression in the CuCl53-, ion is a manifestation of the electronic structure of the Cu(II) ion, rather than crystalline effects. The spectra of the zinc-containing compounds indicate that the tetrachlorozincate(II) ion is the anionic species in these salts, although both this moiety and the Co(NH3)(5)(3+) ions appear to be considerably distorted from their ideal symmetries, probably due to hydrogen-bonding effects.