The preparations, X-ray structures, and detailed physical characterization are presented for new complexes involving an iron(II) center, a tetraimidazole ligand (TIM), and different carboxylates. [Fe(TIM)(C6H5CH2CO2)](ClO4) (1) Crystallizes in the Pbca space group with a = 10.8947(13), b = 20.343(2), and c = 22.833(3) Angstrom, Z = 8, and V = 5060.6(11) Angstrom(3). [Fe(TIM)(CH3CO2)](ClO4) (2) crystallizes in the la space group with a = 17.117(2), b = 10.3358(12), and c = 25.658(3) Angstrom, beta = 90.301(13)degrees, Z = 8, and V = 4539.5(9) Angstrom(3). In both structures, the iron(II) is hexacoordinated to the four N-imidazole donors of the TIM ligand and the two O donors of a bidentate carboxylate. The flexibility of the carboxylate bidentate coordination, symmetrical or more or less asymmetrical, associated with the steric demand of the TIM ligand results in a remarkable versatility of the (FeN4O2)-N-II coordination geometry. The diversity in carboxylate bidentate coordination modes has allowed us to clearly show the importance of the structural and electronic effects, through IR and Mossbauer spectroscopy, of this apparently tenuous carboxylate shift. Comparison of the structural and Mossbauer properties of these complexes with the non-heme ferrous site of photosynthetic systems (i) shows that the metric parameters of site 2b, including the symmetrically chelated bidentate carboxylate, are closer to those of the non-heme ferrous site in the bacterial reaction centers of Rhodopseudomonas viridis and R. sphaeroides and (ii) suggests that the ligand environment of the non-heme ferrous center of PS 2 is close to the axially distorted octahedral symmetry resulting from an asymmetrical bidentate coordination of the -CO2 motif, as in complex 1.