Syntheses, structural and spectroscopic characterization of novel zinc(II)-bis(trithiocarbimato) complexes and bis(N-methylsulfonyldithiocarbimate)-sulfide

Four zinc(II)-bis(trithiocarbimato) complexes with the general formula A2[Zn(RSO2NCS3)2] [A = Ph4P+: R = CH3 (1), 4-CH3C6H4 (2); A = Bu4N+: R = CH3 (3), 4-CH3C6H4 (4)] were obtained by the reaction of sulfur with the correspondent zinc(II)-bis(dithiocarbimato) complexes. Additionally, the compound (Ph4P)2[(CH3SO2NCS2)2S)] (5) was prepared from the potassium methylsulfonildithiocarbimate by oxidation with iodine. The compounds were characterized by elemental analyses and IR, 1H NMR and 13C NMR spectroscopies. The compounds 4 and 5 were also characterized by X-ray diffraction techniques. The compound 4 crystallizes in the centrosymmetric space group C2/c of the monoclinic system. The Zn(II) is in a distorted tetrahedral environment (ZnS4) in compound 4, and differ from the coordination mode observed in compound 1, which involves one sulfur and one nitrogen atom of each trithiocarbimate ligand. Compound 5 is the first example of a compound containing a bis(N-alkylsulfonyldithiocarbimate)-sulfide dianion and crystallises in the non-centrosymmetric space group P41212 of the tetragonal system.

Graphical abstractFour zinc(II)-bis(trithiocarbimato) complexes with the general formula A2[Zn(RSO2NCS3)2] [A = Ph4P+: R = CH3 (1), 4-CH3C6H4 (2); A = Bu4N+: R = CH3 (3), 4-CH3C6H4 (4)] and (Ph4P)2[(CH3SO2NCS2)2S)] (5) were obtained and characterized by IR, 1H NMR and 13C NMR. Compounds 4 and 5 were also characterized by X-ray diffraction techniques.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► New Zn(II)-complexes containing N-R-sulfonyltrithiocarbimato ligands were obtained. ► The compound (PPh4)2[(CH3SO2NC(S)SSS(S)CNSO2CH3)] was also obtained. ► It is the first example of a bis(N-R-sulfonyldithiocarbimate)-sulfide dianion. ► The structures of the new sulfide and one Zn(II)-complex were determined by X-ray diffraction.