In continuation of a systematic study of bis(citrate)germanates, we synthesized a number of heterometallic germanium(IV) and 3d metal complexes based in citric acid (H(4)Cit) with the molecular formula [M(H2O)(6)][Ge(HCit)(2)] center dot nH(2)O, where M = Fe, n = 4 (I); Co, n = 2 (II); Ni, n = 2 (III); Cu, n = 1 (IV); Zn, n = 3 (V). The complexes were characterized by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. The X-ray diffraction analysis of compound I was performed. Crystals are monoclinic, a = 10.091(4) angstrom, b = 11.126(4) angstrom, c = 10.996(4) angstrom, beta = 100.966(6)degrees, V = 1212.1(8) angstrom(3), Z = 4, space group P2(1)/n, R1 = 0.0561 for 2266 reflections with I > 2 sigma(I). Compound I is composed of centrosymmetric octahedral complexes-[Ge(HCit)(2)](2-) anions and [Fe(H2O)(6)](2+) cations-and crystallization water molecules. Structural units in compound I are combined by a hydrogen bond system.