Crystals of the title compound, [Co(Hdmg)z(aniline)z]Cl (Hdmg is the dimethylglyoximato mono-anion), are monoclinic, space group C2/c with a=27.44 (1), b=6.32 (1), c=17.72 (1)A.; fl= 129.7 (1) ° and Z=4. The structure has been solved by Patterson and Fourier methods and refined by block-diagonal least squares (final R=4.3 %). The nitrogen atoms of two aniline molecules coordinate to cobalt in an octahedral axial position with respect to the plane of the chelate dimethylglyoximatocobalt(IlI) system. The approach distance of the aniline nitrogen to metal is significantly greater (2.001 A.) than those involving the dimethylglyoximato nitrogen atoms in the chelation plane
23 and 600°C result from the increased metal-metal distances. In order to maintain approximately constant metal-oxygen distances, the oxygens of the unshared octahedral face move farther apart while those of the shared face move together. At the same time the distance between the parallel shared and unshared faces decreases. This distortion of the filled octahedra allows both the M(1)-M(2) and M(1)-M(3) distances to increase while keeping the metal-oxygen distances essentially constant. This is consistent with the band structure proposed by Goodenough (1971) for V2Oa. The metal-oxygen bands in this scheme lie some 4 eV below the Fermi level while metal-metal bands lie at or near this level. Temperature-induced changes in bonding in such a system would primarily effect the metal-metal interactions and, consequently, the metalmetal distances and would have little effect on the metal-oxygen interactions.This work was done in the Department of Earth and Space Sciences, State University of New York, Stony Brook, New York. We wish to thank Professor C. T. Prewitt for his assistance and the National Science Foundation (Grant No. GP-17554) and Purdue University for support of the work.
References
BROWN, G. E., SUENO, S. (~ PREWITT, C. T. (1973
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