The complex compounds [Co(DH)(2)(Anil)(2)][BF4] and [Co(DH)(2)(PY)(2)][BF4] were synthesized from Co(BF4)(2) (.) 6H(2)O-DH2-A-alcohol-water systems (DH2 is dimethylglyoxim and A is pyridine (Py) or aniline (Anil)), and their crystal structures were determined using X-ray diffraction analysis. In octahedral Co(III) complexes, two dimethylglyoxime radicals lie in the equatorial plane and are joined via the intramolecular hydrogen bond O-(HO)-O-.... The complexes with pyridine and aniline have similar configurations but different crystal structures.