Synthesis, crystal structure, and NMR investigation of 4-amino-1,2,4-triazolium hexafluoridotitanate(IV)

• Published in: Journal of fluorine chemistry Vol. 178; pp. 68 - 72
• Main Authors: Kavun, V.Ya, Davidovich, R.L., Logvinova, V.B., Merkulov, E.B., Tkachev, V.V.
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 01.10.2015; Elsevier
• Subjects: 19F and 1H NMR spectra; 4-Amino-1,2,4-triazolium; Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Hexafluoridotitanate(IV); Ion mobility; Physical Sciences; Science & Technology; Structure; Synthesis; Hexafluoridotitanate(IV); Synthesis; Ion mobility; Structure; 4-Amino-1,2,4-triazolium; 19F and 1H NMR spectra; COMPLEX ANIONS; INTERNAL MOBILITY; X-RAY; F-19 and H-1 NMR spectra
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2015.06.027

A new hybrid organic–inorganic fluoride complex of titanium(IV) with monoprotonated cation of the heterocyclic base 4-amino-1,2,4-triazole, (C2H5N4)2TiF6, which is a representative of a new class of ionic liquids containing complex [TiF6]2− anions above 369K, has been synthesized and investigated using the methods of X-ray structural study, and 1H and 19F NMR spectroscopy. •A new hybrid organic–inorganic fluoridotitanate(IV) (C2H5N4)2TiF6 was synthesized and its structure has been determined.•Octahedral complex [TiF6]2− anions and (C2H5N4)+ cations form the structural motif.•At 355–375K, (C2H5N4)2TiF6 melts with transformation into an ionic liquid.•The character and types of ionic motions in the anionic and cationic sublattices (C2H5N4)2TiF6 were investigated. A hybrid organic–inorganic hexafluoride complex of titanium(IV) with protonated cation of the five-membered heterocyclic base 4-amino-1,2,4-triazole, (C2H5N4)2TiF6 has been synthesized for the first time and investigated by the methods of X-ray structural analysis, and 1H and 19F NMR spectroscopy. The structure of (C2H5N4)2TiF6 is formed by virtually ideal octahedral complex [TiF6]2− anions and monoprotonated (C2H5N4)+ cations linked through hydrogen bonds N–H⋯F and C–H⋯F into a three-dimensional framework. The character and types of ionic motions in anionic and cationic subsystems of the synthesized compound structure have been analyzed and discussed. At 355–375K (C2H5N4)2TiF6 melts and transforms into an ionic liquid.