On basis of IR-spectroscopy [1] the structure of [CoCl2(DH)(DH2)] (DH2 = dimethylglyoxime) [2] is considered as dichloroacid compound, in which one hydrogen bond is assumed to be disrupted. Subsequently [2], with mono-o-methylester of diacetyldioxime the compound [CoBr2(DMe)(DHMe)] was obtained from methanol solution of CoBr2 and DHMe, to which some drops of H2O2 were added. In the structure of this compound the four nitrogen atoms and cobalt formed the planar fragment. Intramolecular hydrogen bonds in the complex are somewhat shorter than in dimethylglyoximates of cobalt(III). The absence of a second intramolecular hydrogen bond leads to deformation of the square. We obtained the crystals of [CoBr2(DH)(DH2)].2H2O from alcohol solutions of CoBr2 and DH2 with the acidification of up to pH ~ 2. The X-ray diffraction study established the formation of dibromo-complex with composition [CoBr2(DH)(DH2)].2H2O, unit cell parameters are a = 7.017(1), b = 7.869(2), c = 14.371(3) Å, b = 97.31(3)°, space group P21/c, R = 0.035, isostructural to [CoCl2(DH)(DH2)] [2]. The R divergence is 0.118 in [2] and the water molecule was not detected. formula The crystal structure of [CoBr2(DH)(DH2)].2H2O and packing in the crystal. In the reported complex the coordination of the cobalt ion can be described as an octahedral. Co(III) is surrounded in the equatorial plane by one a-dioxime residue and one neutral dioxime ligand. The apical coordination sites are occupied by Br¯anions. The Co–N bond lengths in coordination polyhedron of the complex are 1.897(3) and 1.891(3) Å, Co–Br 2.3760(9) Å. Crystal packing of centrosymmetric complexes and water molecules suggest formation of cooperative system of hydrogen bridges O(oxime) –H ... O (W) –H ... O (W) –H ... O(oxime), having a “flip-flop” model. The report also deals with: i) the justification of the structural formula of the complex and location of H atom in such type of structure; ii) specificity of intramolecular H-bonds interaction; iii) intermolecular H-bonds in the crystal with participation of water molecules including weak O...O contacts, O(W)–H...Br and C–H...Br hydrogen-bonds.