Análise das ligações de hidrogênio em sais complexos e polímeros de coordenação do íon ditionato

• Ano de defesa: 2013
• Autor(a) principal: Duarte, Rafael
• Tipo de documento: Dissertação
• Tipo de acesso: Acesso aberto
• Idioma: por
• Instituição de defesa: Universidade Federal de Santa Maria; BR; Química; UFSM; Programa de Pós-Graduação em Química
• Palavras-chave em Português: Ditionatos; Ligação de hidrogênio; Superfície de Hirshfeld; Dithionates; Hydrogen bonds; Hirshfeld surface; CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
• Link de acesso: http://repositorio.ufsm.br/handle/1/10581

In this work six aqua complexes of the transition metals Fe2+, Co2+, Ni2+, Cu2+, Zn2+ and Cd2+ containing the dithionate ion were synthesized and characterized through metathesis reactions in aqueous solution between BaS2O6·2H2O and the sulfate of the metal. Single crystals suitable for X-ray diffraction were obtained from the filtrates of the reactions and the structures of four complex salts, hexaaquairon(2+) dithionate hydrate, [Fe(H2O)6](S2O6)·H2O 1, hexaaquacobalt(2+) dithionate, [Co(H2O)6](S2O6) 2, hexaaquanickel(2+) dithionate, [Ni(H2O)6](S2O6) 3 and hexaaquazinc(2+) dithionate [Zn(H2O)6](S2O6) 5, and of two coordination polymers, catena-poli-[trans-tetraaquacopper-μ-dithionato-κ2O,O ] ([Cu(H2O)4(S2O6)]) 4 and catena-poli-[trans-tetraaquacadmium-μ-dithionato-κ2O,O ] ([Cd(H2O)4(S2O6)]) 6, all in triclinic system, space group P1 ‾ . The products were characterized by infrared spectroscopic, thermogravimetric, single crystal X-ray diffraction and powder Xray diffraction analyses. The Hirshfeld surface and the electron density were mapped with a cutoff 0.002 e− au−3 and basis 6-31G** for 1 to 5 and basis 3-21G* to 6, both basis in the Hartree-Fock method, revealing 79% and 75% of the contacts O···H, 19% and 11% of contacts H···H and 2% and 9% of the contacts O···O, for salts and complex coordination polymers, respectively. With the Hirshfeld surface, it was also possible to determine the volume of the molecules, determining the distorted cubic packing, according to the rules of Pauling.