Monocrystals of a new classical dioximate of general fo1mula [Fe(DfgH)2 L2], L = 3-pyridine hemiacetal, were obtained by interaction of the iron(II) chloride with a-benzyldioxime and 3- pyridinaldehyde (a ratio 1 :2:2) in ethanol -_dimethylfo1mamide medium at presence of acetate of sodium. Obviously, during the synthesis of the complex in ethanol and in presence of iron(II) ions 3-pyridine aldehyde transfo1m into 1-ethoxy-1-hydroxy-3(pyridyl)methane according to the scheme: Py-CH(=O) + HO-C2Hs - Py-CH(OH)-O-C2Hs (L). The stmcture of the crystal was dete1mined by single X-Ray diffractions. Compound c1ystallizes in the 01thorhombic space group Pbca, a = 20.233(1), b = 9.2697(6), c = 21.393(2) A, V = 4012.3(5) A, Z = 4, D(calc)= 1.392 Mg!m3, C441Li4Fe1N6O8, R= 0.0763. In the molecular centrosymmetric complexes each Fe(II) cation binds four N atoms of two monodeprotonated Dfgff residues that reside in the equatorial plane of the coordination octahedron of metal and two N atoms of the heterocycles of two neutral L ligands in axial positions. The Fe-N distances in the coordination core range within 1.910(4) - 2.013(4) A. In the coordination environment of iron, two monodeprotonated oxime residues are linked by the intramolecular O(2)-ff 0(1)* hydrogen bonds (Fig. 1), resulting in the alternation of the fivemembered chelate rings and the six-membered hydrogen-bonded rings. The complexes are united in the crystal through O(3)-ff ·O(l)* inte1molecular hydrogen bonds in chains, were -OH group of L acts as donor and the oxime O acts as acceptor of proton. In IR spectra except of abso1ption bands of oscillation frequencies coITesponding coordinated benzyldioxime, are observed abso1ption bands of the apical ligand derived from 3-pyridine aldehyde in situ. In the IR spectra are missing the bands in the region ~1700 cm-1 that is characteristic for C=O group. While they show the associated bands v(O-H) at 3152 cm-1, v(C­H)o.c2H5 at 2825 cm-1, v(C-H)CHo at 2744.7 cm-1, Vas(C-0-R) at 1260 cm-1 and Va(C-0-R) at 1047 cm-1 (v.s.), v (C-OH) at 1084.6; 1057 cm-1. Gamma resonance spectilllll of the complex at 300 and 7K is a doublet with peaks of approximately equal intensity (Fig. 2). Decrease of the temperature from 300 to 7K does not change the shape of the specti11m. Parameters, mm/s: 300K: IS= 0,49, QS = 1,71; 7K: IS= 0,58, QS = 1, 64 are typical for low-spin (S = 0) compounds of the iron (II).