SOME COMPLEX HALIDES OF VANADIUM(II) AND VANADIUM(III) - THE CRYSTAL AND MOLECULAR-STRUCTURE OF TETRAKIS(METHYLAMMONIUM) HEXACHLOROVANADATE(III) CHLORIDE

Some complex chlorides of vanadium(II), A(2)[VCl4(CH3CO2H)(2)], where A = NMeH(3), C(NH2)(3) (guanidinium) and C4H12N2 (pyrazinium), have been isolated from vanadium(II) chloride in acetic acid and characterized by magnetic and spectroscopic measurements. By controlled aerial oxidation of the vanadium(II) complexes or directly from VCl3, a series of hexachlorovanadates (III), A(4)[VCl6]Cl, has been prepared in which A = NMeH(3), NMe(2)H(2), NEtH(3), (NPrH3)-H-II and NBzH(3). A single crystal X-ray investigation has been carried out on the methylammonium salt. There are two independent VCl6 octahedra in the structure. Both are regular, with V-Cl distances in the range 2.380(2)-2.401(2) Angstrom and the internal Cl-V-Cl angles ah within 0.5 degrees of 90 degrees. The complexes [Hpy](3)[VCl6], [NBu(II)H(3)](2)[VCl5] and [NMeH(3)](4)[VBr6]Br have also been isolated. From VCl3 and the alkylammonium chloride in acetic acid or propionic acid as appropriate, the salts A(2)[VCl5(CH3CO2H)] (A = NMe(2)H(2) and NEtH(3)) and A(2)[VCl5[C2H5CO2H)] (A = (NPrH3)-H-II and NBu(II)H(3)) have been obtained.