Three isomers in a (hydrogen L-Cysteinato)-thallium(I): Crystal structure, spectroscopic and thermal properties

Golovnev, Nicolay N.; Molokeev, Maxim S.; Lesnikov, Maxim K. Polyhedron. DOI: 10.1016/j.poly.2019.114141

The isolation of thallium(I) complexes [Tl2(HCys)2]n (1) and [Tl4(HCys)4]n (2) {H2Cys = l-Cysteine} from aqueous solution by means of crystallization is reported herein. Polar crystals of 1 and 2 were crystallized in P21 and P212121 space groups respectively. Elemental analysis, XRD, IR, UV–Vis, TG-DSC and a single crystal X-ray diffraction were applied for characterizing the compounds. Linkage isomers 1 and 2 have 1D and 2D coordination polymeric structures respectively. The lone pair electrons of thallium(I) in 12 are stereo-chemically active. In 1, each of two independent Tl+ ions is coordinated by three HCys ions forming TlS3O irregular polyhedron that is linked to each other by vertexes in an infinite chain. In 2, four independent Tl+ ions are coordinated by HCys ions through S and O atoms, forming Tl1S3O2, Tl2S4, Tl3S3, Tl4S3 irregular polyhedrons. The crystallographic independent HCys ions are linked to the metal ion differently, two are μ3-S,S,S-, one is μ4-O,S,S,S-, and one is μ4-O,O',S,S,S-coordinated ligands. The amine group of compounds 1 and 2 is in the form of an ammonium ion (–NH3+). The structures of 1–2 are stabilized by NH⋯O hydrogen bonds, thallophilic Tl⋯Tl and anagostic Tl⋯HC interactions. The spectroscopic and thermal properties of compounds were analyzed.