The previously predicted ability of the methyl group of nitromethane to form hydrogen bonding with halides is now confirmed experimentally based on X-ray data of novel nitromethane solvates followed by theoretical ab initio calculations at the MP2 level of theory. The cationic (1,3,5-triazapentadiene)PtII complexes [Pt{HN
C(NC5H10)N(Ph)C(NH2)
NPh}2](Cl)2, [1](Hal)2 (Hal = Cl, Br, I), and [Pt{HN
C(NC4H8O)N(Ph)C(NH2)
NPh}2](Cl)2, [2](Cl)2, were crystallized from MeNO2-containing systems providing nitromethane solvates studied by X-ray diffraction. In the crystal structure of [1][(Hal)2(MeNO2)2] (Hal = Cl, Br, I) and [2][(Cl)2(MeNO2)2], the solvated MeNO2 molecules occupy vacant spaces between lasagna-type layers and connect to the Hal− ion through a weak hydrogen bridge via the H atom of the methyl thus forming, by means of the Hal−⋯HCH2NO2 contact, the halide–nitromethane cluster “filling”. The quantum-chemical calculations demonstrated that the short distance between the Hal− anion and the hydrogen atom of nitromethane in clusters [1][(Hal)2(MeNO2)2] and [2][(Cl)2(MeNO2)2] is not just a consequence of the packing effect but a result of the moderately strong hydrogen bonding.
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