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 be en isolated from vanadium(II) chloride in acetic acid and characterize d by magnetic and spectroscopic measurements. By controlled aerial oxi dation of the vanadium(II) complexes or directly from VCl3, a series o f 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 c rystal 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) Angstr om 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 chl oride 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.