The compounds [FeII(DfgH)2L2] (where DfgH –monoanion of α-benzildioxime, L – pyridine, and it derivatives) are usually obtained in alcohol-DMF medium in the presence CH3COONa. The synthesis of analogous compounds with L= 3-, 4-CH(=O)-Py under similar conditions leads to the formation of octahedral complexes, containing in the axial positions the products of addition reaction of the alcohol to the carbonyl group of aldehyde as illustrated: Py-CH(=O) + HO-R → Py-CH(-OH)(-OR). Four compounds with the general formula [Fe(DfgH)2{CH(-OH)(-OR)- Py}2] (1-4), which differ by R and by the position of substituent in Py, were synthesized and investigated. As a result 1 has the substiuent at the Py in position 3 and R = CH3, and in 2-4 the substituent is in position 4 and R=CH3 (2), C2H5 (3), C3H7 (4). In the IR spectra of 1-4 are missing the bands in the region ~1700 cm-1 characteristic for C=O group. While they show the associated bands ν(OH) (3198-3134 cm-1 ), ν(C-H)(-O-CH3) (2870-2826 cm-1 ), ν(C-H)(CHO) (2728-2706 cm-1 ), νas(C-O-R) (1266-1258 cm-1 ) and νs(C-O-R) (1048-1038 cm-1 ), ν(C-OH) (1084-1069 cm-1 ). The structures of compounds 1-4 were determined using X-ray diffraction method (Fig.1-4)figureFig.1. Molecular structure of compound 1Fig.2. Molecular structure of compound 2Fig.3. Molecular structure of compound 3Fig.4. Molecular structure of compound 41-4 are molecular coordination compounds. It is discussed the influence of position and nature of L on the stabilized form of the addition product of alcohols to aldehydes and the molecular packing in the crystals.