The coordination or ion pairing of the hydrogen-bonded anions H(CF3CO2)(2)(-) and H(CH3SO3)(2)(-) to NEt4+, Li+ Cu+, and/or CU2+ was investigated. The structure of {Cu-2(H(CH3SO3)(2))(4)}(n) consists of centrosymmetric dimeric moieties that contain two homoconjugated. (CH3SO2O-H ... OSO2CH3)(-) anions per CU2+ ion, forming typical Jahn-Teller tetragonally elongated CuO6 coordination spheres. The oxygen atoms involved in the nearly linear O-H ... O hydrogen bonds (O ... O similar to 2.62 Angstrom) are not coordinated to the Cu2+ ions. The structure of Cu-2(CO)(2)(H(CF3-CO2)(2))(2) consists of pseudo-C-2-symmetric dimers that contain one homoconjugated (CF3COO-H ... OCOCF3)(-) anion per Cut ion, forming highly distorted tetrahedral Cu(CO)O-3 coordination spheres. Three of the four oxygen atoms in each hydrogen-bonded H(CF3CO2)(2)(-) anion are coordinated to the Cu+ ions, including one of the oxygen atoms in each O-H ... O hydrogen bond (O ... O similar to 2.62 Angstrom). Infrared spectra (v(CO) values) of Cu(CO)(CF3CO)(2) or Cu(CO)(CH3SO3) dissolved in acetonitrile or benzene, with and without added CF3COOH or CH3SO3H, respectively, demonstrate that HA(2)(-) anions involving carboxylates or sulfonates are more weakly coordinating than the parent anions RCO2- and RSO3-. Direct current conductivities of THF solutions of Li(CF3CO2) containing varying concentrations of added CF3COOH further demonstrate that Li+ and NEt4+ ion pair much more weakly with H(CF3CO2)(2)(-) than with CF3CO2-.