Organic matrix-induced formation of a discrete cyclic [Cl2(H2O)2]2− cluster. (17th July 2017)

• Record Type: Journal Article
• Authors: Safin, Damir A.; Babashkina, Maria G.; Robeyns, Koen; Garcia, Yann
• Is Part Of: New journal of chemistry. Volume 41:Number 16(2017)
• Page Start: 8263
• Page End: 8269
• Publication Date: 2017-07-17
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/c7nj00700k
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : Reaction of 6-NH2 -Py-2-NHC(S)NHP(S)(OiPr)2 with DMFA·2HCl leads to the co-crystallization product of 2, 6-di(4 H -1, 2, 4-triazol-4-yl)pyridine and 2, 6-diaminopyridinium chloride monohydrate (1 ) and N -(diisopropoxythiophosphoryl)- N ′-(6-(4 H -1, 2, 4-triazol-4-yl))pyridin-2-ylthiocarbamide (2 ). Abstract : Reaction of N -thiophosphorylated thiourea 6-NH2 -Py-2-NHC(S)NHP(S)(OiPr)2 (L ) with N, N '-dimethylformamide azine dihydrochloride (DMFA·2HCl) leads to the formation of a co-crystallization product of 2, 6-di(4 H -1, 2, 4-triazol-4-yl)pyridine and 2, 6-diaminopyridinium chloride monohydrate (1 ) as well as bis-triazole N -(diisopropoxythiophosphoryl)- N' -(6-(4 H -1, 2, 4-triazol-4-yl))pyridin-2-ylthiocarbamide (2 ), which can be separated by fractional precipitation. The crystal structure analysis of1 shows the formation of a tetrameric cyclic secondary building unit (SBU) because of the formation of intermolecular hydrogen bonds by bis-triazole molecules and dipyridinium cations. The cavity of the cyclic tetramer is occupied by a rhombohedral cyclic [Cl2 (H2 O)2 ] 2− cluster. The SBU is further connected to neighboring SBUs by a number of intermolecular hydrogen bonds, forming a 3D structure. Hirshfeld surface analysis showed that the structure of the [Cl2 (H2 O)2 ] 2− cluster is almost fully characterized by highly favourable Cl⋯H and O⋯H intermolecular contacts as well as by less favourable H⋯H contacts. The former two contacts are also highly favourable in the structures of 2, 6-di(4 H -1, 2, 4-triazol-4-yl)pyridine and 2, 6-diaminopyridinium, although their contribution on the molecular surface is remarkably impoverished. The dominant and favourable contacts, however, on the Hirshfeld surface area of these two organic species are H⋯H, H⋯N and H⋯C. The isolated thiourea2 is considered as a promising coordination chemistry precursor due to a number of different possible coordination sites.