The involvement of Cd(II) in toxic manifestations and pathological aberrations in lower and higher organisms entails interactions with low and high molecular mass biological targets. To understand the relevant chemistry in aqueous media, we have launched pH-dependent synthetic efforts targeting Cd(II) with the physiological ligand citric acid. Reactions of Cd(II) with citric acid upon the addition of NaOH at pH 2.5 and pyridine at pH 3 and the addition of ammonia at pH similar to 7 led to the new complexes [Cd-3(C6H5O7)(2)(H2O)(5)](H2O)-H-. (1) and (NH4)[Cd(C6H5O7)(H2O)](H2O)-H-. (2), respectively. Complexes 1 and 2 were characterized by elemental analysis, spectroscopy (FT-IR and NMR), and X-ray crystallography, Complex 1 crystallizes in the monoclinic space group P2(1)/n, with a = 18-035(6) angstrom, b = 10.279(4) angstrom, c = 12.565(4) angstrom, beta = 109.02(1)degrees, V = 2202(2) angstrom(3), and Z = 4. Complex 2 crystallizes in the monoclinic space group P2(1), with a = 9.686(4) angstrom, b = 8.484(4) angstrom, c = 7.035(3) angstrom, beta = 110.28(1)degrees, V = 542.3(4) angstrom(3), and Z = 2. Complex 1 is a trinuclear assembly with the citrate ligand securing a stable metallacyclic ring around one Cd(II), with the terminal carboxylates spanning into the coordination sphere of two nearby Cd(II) ions. Complex 2 contains mononuclear units of Cd(II) bound by citrate in an overall coordination number of 8. In both 1 and 2, the participating citrates exhibit three different modes of coordination, thus projecting a distinct yet variable aqueous structural chemistry of Cd(II) with physiological substrates. The pH-dependent chemistry and its apparent structural diversity validate past solution speciation studies, projecting the existence of mononuclear species such as the one in the anion of 2. The spectroscopic and structural properties of 2 emphasize the significance of the information emerging from synthetic studies that otherwise would not have been revealed through conventional solution studies, while concurrently shedding light onto the linkage of the requisite chemistry with the potential biological toxicity of Cd(II).