Previously, it was shown that by reacting GeCl4 with 2-hydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde nycotinoyl-, isonycotinoylhydrazones (-, - H2Ls and -, - H2Lnf, respectively) in methanol complexes [Ge(Ls∙HCl)2] and [Ge(Inf∙HCl)2] are formed. O, N, O-coordination of protonated by Npy enol form of the ligand (Fig. 1) with compensation charge of chloride ion is realized in them. In this study established that the introduction of FeCl3 in systems «H2Ls (H2Lnf) – GeCl4 – CH3OH» complexes [Ge(Ls∙HCl)(Ls∙H)][FeCl4] ∙ CH3OH, -(I), - (II), [Ge(Lnf∙HCl)(Lnf∙H)][FeCl4] ∙ CH3OH, - (III), - (IV) are formed. Form Ge K-edge XANES region of X-ray absorption spectra, which determined by 1s4p dipole electronic transition, corresponds to a maximum of C and indicates a highly-octahedral configuration of germanium ions in the I-IV (Fig. 2). The main peak (r = 1.46-1.48 Å) in MTF EXAFS GeK-edges for the I-IV corresponds to the scattering of waves on the six nearest atoms N and O ligands coordination unit {GeO4N2}. Mossbauer spectrum IV (Fig. 3) – doublet with parameters (Qs = 0.336 ± 0.006 mm/s and Is = 0.325 ± 0.003 mm/s) is typical for [FeCl4]- and corresponds to the realization in the anion charge Fe3+ with S = 5/2 and coordination number (Fe) = 4. The quantities eff (5.87 - 5.89 BM) for the I-IV at 25 ◦C confirm high-spin 3d5 configuration with a tetrahedral coordination enviropment of Fe (III). Taking into account the data of IR spectra in the I-IV ion [FeCl4]- compensates for the protonated form of only one of ligand in the composition of cations Ge (IV), the second ligand linked with germanium in hydrochloride form; the coordinating unit {GeO4N2} (Fig. 1) is retained.figureFig. 1. Structure [Ge(-Lnf∙H)2]2+ in composition of [Ge(-Lnf∙HСl)2]Fig. 2. XANES GeK-edge for I-IVFig. 3. Mossbauer spectrum of IV at T = 13 K.