SYNTHESIS AND CRYSTAL STRUCTURE OF p,σ-COMPLEX [Cu3(C17H15N3S)2Br3]∙CH3CN BASED ON 3,4-DIPHENYL-5-THIOALLYL-1,2,4-TRIAZOLE

Yu. Slyvka, O. Pavlyuk, A. Batyuk


DOI: http://dx.doi.org/10.30970/vch.6601.069

Abstract


Novel p,σ-complex Cu3(Dthatr)2Br3]∙CH3CN (1) has been synthesized by the alternating-current electrochemical technique from acetonitrile solution of CuBr2 and 3,4-diphenyl-5-thioallyl-1,2,4-triazole (Dthatr). The structure of compound 1 has been studied by single crystal X-ray diffraction method. The collected diffraction data were processed using CrysAlis RED program. The structure was solved by ShelXT program and refined by least squares method on F2 by ShelXL program with the following graphical user interface of OLEX2. Compound 1 crystallizes in the centrosymmetric space group P21/с a = 12.1402(4), b = 13.2207(5), c = 24.7408(7) Å, β = 103.853(3), V = 3855.4(2) Å3, Z = 4. Asymmetric unit of the cell contains two crystallographically independent organic molecules and three copper(I) atoms. The Dthatr molecule acts as chelate-bridging ligand, forming acentric organometallic dimers {Cu2(Dthatr)2}2+ with two seven-membered and one six-membered rings. The Cu1 and Cu2 atoms together with π-coordinated to them two allylic groups are disordered over two sites with an occupancy ratio of 0.800(6) and 0.200(6), and 0.802(6) and 0.198(6), respectively. Cu1A and Cu1B have a trigonal-pyramidal coordination environment, the basal plane of which is occupied by two triazole N atoms and by C=C bond. The apical position of the pyramid is occupied by the Br atom of the planar CuBr32– anion. This anion, similar to FeCl42– (in [Cu2(Pathatr)2ZnCl4]∙2CH3CN) and ZnCl42– (in [Cu2(Pathatr)2FeCl4]∙2CH3CN), bridges two π-coordinated central atoms of the acentric dimer into island units {Cu3(Dthatr)2Br3}. Cu1A and Cu1B atoms also have a similar trigonal-pyramidal coordination environment, but their apical vertices are occupied by halogen atoms of neighboring units {Cu3(Dthatr)2Br3}. Such flexibility of the organometallic unit causes the connection of the {Cu3(Dthatr)2}2+ cations and CuBr32– anions into chains.

 

Keywords: copper(I), π-complex, allyl derivative of triazole, crystal structure.

 


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