Halogenska veza u solima sulfonskih kiselina i halogenpiridina

master's thesis

• Title (english): Halogen bonding in salts of sulfonic acids with halopyridines
• Author: Matija Čulig
• Mentor: Dominik Cinčić (mentor)
• Mentor: Vinko Nemec (komentor)
• Committee member: Dominik Cinčić (predsjednik povjerenstva)
• Committee member: Nikola Bregović (član povjerenstva)
• Committee member: Nikola Cindro (član povjerenstva)
• Committee member: Vladimir Stilinović (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2021-02-26, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U ovom radu ispitivana je mogućnost nastajanja soli benzensulfonske kiseline i p-toluensulfonske kiseline s odabranim halogenpiridinima: 3-klorpiridinom, 3-brompiridinom, 3-jodpiridinom, 4-jodpiridinom, 2,6-diklorpiridinom, 2,6-dibrompiridinom, 3,5-diklorpiridinom, 3,5-dibrompiridinom, 5-brom-2-klorpiridinom i 5-brom-2-jodpiridinom. Priprava soli provedena je mehanokemijskom sintezom te sintezom iz otopine i suspenzije reaktanata. Dobiveni produkti okarakterizirani su difrakcijom rentgenskog zračenja na praškastom uzorku i razlikovnom pretražnom kalorimetrijom. Za devet soli čiji su jedinični kristali uspješno priređeni, metodom difrakcije rentgenskog zračenja u jediničnom kristalu određene su molekulske i kristalne strukture. Strukturnom analizom priređenih spojeva utvrđeno je da je u svim solima dominantna međumolekulska interakcija između kationa i aniona vodikova veza N–H∙∙∙O. U solima u kojima su kationi jod ili brom supstituirani piridini, ioni su još međusobno povezani halogenskom vezom X∙∙∙O (X = Br, I) koja se ostvaruje između halogenog atoma kationa i kisika sulfonske skupine aniona.

Abstract (english)

The possibility of forming benzenesulfonate and p-toluenesulfonate salts with the following halogenpyridines was studied: 3-chloropyridine, 3-bromopyridine, 3-iodopyridine, 4-iodopyridine, 2,6-dichloropyridine, 2,6-dibromopyridine, 3,5-dichloropyridine, 3,5-dibromopyridine, 5-bromo-2-chloropyridine and 5-bromo-2-iodopyridine. Salts were prepared mechanochemically, by crystallization from solution, and slurry experiments. The obtained products were characterized by powder X-ray diffraction and differential scanning calorimetry. Single crystals were obtained for nine salts, and their molecular and crystal structures were determined by single crystal X-ray diffraction. Structural analysis has shown that the dominant non-covalent interaction in all salts is the N–H∙∙∙O hydrogen bond. In seven salts that contain iodo– or bromo– substituted pyridines as cations, the ions are also interconnected by X∙∙∙O (X = Br, I) halogen bonds formed between the cation halogen atom and the sulfonate anion oxygen atom.

• Keywords: halogenpiridini; halogenska veza; vodikova veza; soli; sulfonska kiselina
• Keywords (english): halopyridines; halogen bonding; hydrogen bonding; salts; sulfonic acids
• Language: croatian
• URN:NBN: urn:nbn:hr:217:703641
• Project: Number: IP-2019-04-1868; Title: Nove građevne jedinke u supramolekulskom dizajnu složenih višekomponentnih molekulskih kristala temeljenih na halogenskim vezama; Title: New building blocks for the supramolecular design of complex multi-component molecular crystals based on halogen bonds; Acronym: HaloBond; Leader: Dominik Cinčić; Jurisdiction: Croatia; Funder: HRZZ; Funding stream: IP
• Study programme: Title: Graduate university studies in chemistry; specializations in: Research programme; Course: Research programme; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra kemije (magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2023-02-26
• Created on: 2021-03-25 13:20:13