SUPRAMOLEKULSKI PRISTUP BOJENJU: KRISTALNO PAKOVANJE AZO PIRIDONSKE BOJE

Abstract

Reakcija azo kuplovanja omogućava laku sintezu niza molekula sa različitim svojstvima, što čini azo boje najrasprostranjenijim kolorantima. Pored primene azo boja u tekstilnoj industriji, primenjuju se i kod proizvoda naprednih tehnologija. Takođe, poznata su i po svojoj izvanrednoj biološkoj aktivnosti. Prisustvo jezgra piridina značajno poboljšava obojenje i postojanost boja. Supramolekulskim pristupom objašnjavaju se intra- i inter-molekulske interakcije, što omogućava bolje razumevanje interakcija između boja i tekstilnog vlakna [1]. U ovom radu dobijen je 5'-(2-(2,6-dihlorfenil)hidrazon)-4'-metil-2',6'-diokso- 1',2',5',6'-tetrahidro-[1,3'-bipiridin]-1-ium-hlorid (slika). Struktura jedinjenja potvrđena je NMR, ATR-FTIR, UV-Vis spektroskopijama i rendgenskom strukturnom analizom. Supramolekulsko umrežavanje postignuto je vodoničnim vezama, π-interakcijama, interakcijama atoma hlora vezanih za fenilno jezgro kao i interakcijama Cl–-jona koji se nalazi u kristalnoj rešetki. Ovim interakcijama objašnjena je i sposobnost vezivanja boje za tekstilno vlakno. Kristalografski podaci: C34H26Cl6N8O4, Mr = 823,33, P–1, a = 7,3784(15), b = 10,394(2), c = 13,254(3) Å, α = 103,29(3), β = 105,71(3), γ = 106,11(3) °, V = 887,5(4) Å3, Z = 1, F(000) = 420, ρx = 1,541 g cm–3, µ(MoKα) = 0,537 mm–1. Utačnjavanje sa F2 (236 parametara) dalo je R1 = 0,0561 i S = 1,063 za 3247 primećenih refleksija sa I ≥ 2σ(I).

The reaction of azo coupling easily provides access to a wide range of different molecules with numerous material properties, therefore making azo dyes most widely used colorants. Their use is not limited only on textile dyeing as it expands on usage in advanced technology products. On the other hand, these compounds are known for their remarkable biologial activities. Inclusion of a pyridine ring into the molecular architecture leads to a better color properties. Supramolecular organization of azo dyes provides details on the molecular conformation, including intra- and inter-molecular interactions in the solid state. This information assists towards understanding of molecular properties as well as dye–fibre interactions [1]. In this work azo coupling reaction was employed to obtain 5'-(2-(2,6- dichlorophenyl)hydrazono)-4'-methyl-2',6'-dioxo-1',2',5',6'-tetrahydro-[1,3'-bipyridin]-1- ium chloride (Figure). The molecular structure was confirmed by 1H, 13C NMR, ATR- FTIR, UV-Vis spectroscopies and by single-crystal X-Ray diffraction. Various hydrogen bonds, π-stacking interactions and interactions involving chlorine substituents, as well as the chloride ion are responsible for supramolecular organization. Furthermore these interactions were used to explain dye- fiber afinities. Crystal data: C34H26Cl6N8O4, Mr = 823.33, P–1, a = 7.3784(15), b = 10.394(2), c = 13.254(3) Å, α = 103.29(3), β = 105.71(3), γ = 106.11(3) °, V = 887.5(4) Å3, Z = 1, F(000) = 420, ρx = 1.541 g cm–3, µ(MoKα) = 0.537 mm–1. The refinement on F2 (236 parameters) yielded R1 = 0.0561 and S = 1.063 for 3247 observed reflections with I ≥ 2σ(I).