Earlier work on the interaction of V(II ) salts with pyridine and acetonitrile as solvents has been extended. The structure of the compound VPy(4)(O3SCF3)(2), 1, an intermediate in many of the preparations, has been determined by X-ray diffraction. Analogous solids with I-, Br-, Cl-, SCN-, N-3(-), PhS(-), EtS(-), and BH4- as counterions have been prepared. Attempts to prepare solids with PhO(-), HO-, MeO(-), Ph(-), CN-, AlH4-, and H- failed, but the tetrapyridine complexes were prepared by titrating a solution of 1 in pyridine with the lithium salt of each anion (in the case of H-, the anion was Et(3)BH(-)) to an end point observed at the 1:2 ratio. Comparisons in a number of cases of the absorption spectra and of the cyclovoltammetric behavior of the tetrapyridine salts in pyridine and in CH2Cl2 show the species in the two solvents to be the same and to correspond to the composition of the solids. Intercomparisons of the absorption spectra in pyridine suggest that the complexes with the aforementioned anions all have similar structures : four pyridine molecules situated equatorially-on the basis of crystal structure determinations, in a propeller arrangement--and the anions occupying axial positions. : four pyridine molecules situated equatorially-on the basis of crystal structure determinations, in a propeller arrangement--and the anions occupying axial positions.