title: Lasagna-type arrays with halide-nitromethane cluster filling. The first recognition of the Hal(-)···HCH2NO2 (Hal = Cl, Br, I) hydrogen bonding.
abstract: 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)Pt(II) complexes [Pt{HN=C(NC(5)H(10))N(Ph)C(NH(2))=NPh}(2)](Cl)(2), [1](Hal)(2) (Hal = Cl, Br, I), and [Pt{HN=C(NC(4)H(8)O)N(Ph)C(NH(2))=NPh}(2)](Cl)(2), [2](Cl)(2), were crystallized from MeNO(2)-containing systems providing nitromethane solvates studied by X-ray diffraction. In the crystal structure of [1][(Hal)(2)(MeNO(2))(2)] (Hal = Cl, Br, I) and [2][(Cl)(2)(MeNO(2))(2)], the solvated MeNO(2) 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(-)···HCH(2)NO(2) 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)(MeNO(2))(2)] and [2][(Cl)(2)(MeNO(2))(2)] is not just a consequence of the packing effect but a result of the moderately strong hydrogen bonding.
authors.affiliation: Department of Chemistry, St. Petersburg State University, 198504 Stary Petergof, Russian Federation.
authors.forename: Pavel V
authors.initials: PV
authors.lastname: Gushchin
authors.forename: Maxim L
authors.initials: ML
authors.lastname: Kuznetsov
authors.forename: Qian
authors.initials: Q
authors.lastname: Wang
authors.forename: Andrey A
authors.initials: AA
authors.lastname: Karasik
authors.forename: Matti
authors.initials: M
authors.lastname: Haukka
authors.forename: Galina L
authors.initials: GL
authors.lastname: Starova
authors.forename: Vadim Yu
authors.initials: VY
authors.lastname: Kukushkin