title: Nitranilic acid hexahydrate, a novel benchmark system of the Zundel cation in an intrinsically asymmetric environment: spectroscopic features and hydrogen bond dynamics characterised by experimental and theoretical methods.
abstract: Nitranilic acid (2,5-dihydroxy-3,6-dinitro-2,5-cyclohexadiene-1,4-dione) as a strong dibasic acid in acidic aqueous media creates the Zundel cation, H5O2(+). The structural unit in a crystal comprises (H5O2)2(+) (2,5-dihydroxy-3,6-dinitro-1,4-benzoquinonate)(2-) dihydrate where the Zundel cation reveals no symmetry, being an ideal case for studying proton dynamics and its stability. The Zundel cation and proton transfer dynamics are studied by variable-temperature X-ray diffraction, IR and solid-state NMR spectroscopy, and various quantum chemical methods, including periodic DFT calculations, ab initio molecular dynamics simulation, and quantization of nuclear motion along three fully coupled internal coordinates. The Zundel cation features a short H-bond with the O···O distance of 2.433(2) Å with an asymmetric placement of hydrogen. The proton potential is of a single well type and, due to the non-symmetric surroundings, of asymmetric shape. The formation of the Zundel cation is facilitated by the electronegative NO2 groups. The employed spectroscopic techniques supported by calculations confirm the presence of a short H-bond with a complex proton dynamics.
authors.affiliation: Rudjer Bošković Institute, Bijenička 54, HR-10000 Zagreb, Croatia. kojic@irb.hr.
authors.forename: Krešimir
authors.initials: K
authors.lastname: Molčanov
authors.forename: Jernej
authors.initials: J
authors.lastname: Stare
authors.forename: Mikhail V
authors.initials: MV
authors.lastname: Vener
authors.forename: Biserka
authors.initials: B
authors.lastname: Kojić-Prodić
authors.forename: Gregor
authors.initials: G
authors.lastname: Mali
authors.forename: Jože
authors.initials: J
authors.lastname: Grdadolnik
authors.forename: Vlasta
authors.initials: V
authors.lastname: Mohaček-Grošev
mesh_terms: D002412:Cations / Q000737:chemistry; D053138:Cyclohexenes / Q000737:chemistry*; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D009574:Nitro Compounds / Q000737:chemistry*; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared; D013816:Thermodynamics; D014961:X-Ray Diffraction
chemical_list: D002412:Cations; D053138:Cyclohexenes; D009574:Nitro Compounds; C000591936:2,5-dihydroxy-3,6-dinitro-2,5-cyclohexadiene-1,4-dione