Structural and spectroscopic characterization of DMF complexes with nitrogen, carbon monoxide, ammonia and water....

An infrared spectroscopic and MP2/6-311++G(2d,2p) study of the complexes between N,N-dimethylformamide (DMF) and nitrogen, carbon monoxide, water, ammonia trapped in solid argon matrices is reported [corrected]. The 1:1 molecular complexes have been identified in the DMF/B/Ar matrices (B=N₂, CO, H₂O, NH₃); their structures were determined by comparison of the spectra with the results of calculations. The analysis of the experimental and theoretical data indicate that the DMF-N₂, CO complexes present in the matrices are stabilized by (C=)O⋯N and (C=)O⋯C van der Waals interactions. In turn, in the DMF-H₂O, NH₃ complexes the (C=)O⋯H(OH) and (C=)O⋯H(NH₂) hydrogen bonding is present in which the carbonyl group of DMF acts as a proton acceptor. In all systems studied the C-H⋯X (X=N, C, O) bonding is a second intermolecular force stabilizing the planar complexes. Some spectral features indicate that for DMF-H₂O, DMF-NH₃ systems the nonplanar structures with the C=O⋯H interaction are also present. The study demonstrated the strong sensitivity of the CH stretching wavenumber to an involvement of the C-H and/or C=O groups of DMF in an intermolecular interaction.