Reactions of a mononuclear molybdenum(V) starting material, (PyH) 5[MoOCl 4(H 2O)] 3Cl 2, with 2,2-dimethylsuccinic acid in the presence of base afforded two products, (PyH) 3[Mo 2O 4Cl 4(μ 2-dmsH)]·1/2CH 3CN ( 1) and (PyH) 4[Mo 2O 4Cl 4(μ 2-dmsH)]Cl ( 2). As revealed by the X-ray structure analysis, the half-neutralized form of the dicarboxylic acid, the dmsH ？ ion, coordinated to the well-known {Mo 2O 4} 2+ core in the syn-syn bidentate bridging manner. In both compounds, the non-ionized terminus of the ligand, the COOH function, participated in hydrogen-bonding interactions. The incorporation of the chloride counteranion in 2, prevented the formation of the common “carboxylic acid dimer” which was observed for 1. Instead, a hydrogen-bonded linkage of the COOH function with the chloride occurred.
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