Synthesis and crystal structure of copper(I) nitrate π-complex with 1-(4-methylphenyl)-5-allylsulfanyl-1H-tetrazole

Abstract

By means of the alternating-current electrochemical technique a novel copper(I) π,σ-compound [Cu 2 ( Matht ) 2 (H 2 O) 2 ](NO 3 ) 2 ( 1 ) with 1-(4-methylphenyl)-5-allylsulfanyl-1 H -tetrazole ( Matht ) was obtained in a single crystal form and structurally characterized by single crystal X-ray diffraction. 1-(4-Methylphenyl)-5-allylsulfanyl-1 H -tetrazole was prepared in several stages by known protocol, starting from 4-methylaniline. Diffraction data for 1 were collected on a Rigaku AFC7 diffractometer using Mo K a radiation ( λ = 0.71069 Å). The collected diffraction data were processed using CrysAlis RED program. The structure was solved by SIR-92 and refined by least squares method on F 2 by ShelXL. π-Complexe crystallize in the acentric space group Pna 2 1 : a = 27.2002(7), b = 9.7219(3), c = 10.9773(3) Å, V = 2902.81(14) Å 3 , Z = 4. The organometallic component of the structure of complex 1 is represented by the dimer {Cu 2 ( Matht ) 2 (H 2 O) 2 } 2+ , which is formed by chelate-bridging coordination of two organic molecules Matht to Cu + ions. The Cu(I) ion assumes a close to trigonal-pyramidal coordination environment (2N, (C=C) + O), which includes the η 2 -allyl group, the two most nucleophilic N atoms of two adjacent tetrazole nuclei and a water molecule. The water O atom occupies the apical position of the copper(I) polyhedron. The corresponding geometric index τ 4 for copper(I) is 0.81 (for Cu1) and 0.79 (for Cu2). In the structure, despite the trans-arrangement of coordinated molecules relatively to the six-membered {Cu 2 N 4 } cycle, an acentric dimer {Cu 2 ( Matht ) 2 (H 2 O) 2 } 2+ with two independent copper(I) ions is formed. The asymmetry of the latter is associated with the arrangement of one of the allylic groups (atoms C31 and C32) in two positions with a S.O.F. = 0.5. The dihedral angle between the planes of tetrazole and aryl rings equals to 50.0 o . Water molecule plays a role of bridge among the cationic organometallic nucleus and nitrate anions, connecting them by means of hydrogen bonds O−H···O into H-bonded framework. Keywords: copper(I), π-complex, allyl tetrazole, crystal structure.