Architecture of framework copper(I) halide π-complexes with N-allyl-N,N,N′,N′-tetramethyl-ethylenediaminium and N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium: Synthesis and crystal structure of [{C2H4N2(H+)×(CH3)4(C3H5)} Cu4Cl6] and [{C2H4N2(CH3)4(C3H5)2}0.5Cu2Cl1.67Br1.33]

• Published in: Journal of structural chemistry Vol. 53; no. 1; pp. 119 - 124
• Main Authors: Monchak, M. M., Goreshnik, E. A., Mys’kiv, M. G.
• Format: Journal Article
• Language: English
• Published: Dordrecht SP MAIK Nauka/Interperiodica 01.02.2012
• Subjects: Atomic; Atomic/Molecular Structure and Spectra; Chemistry; Chemistry and Materials Science; Inorganic Chemistry; Molecular; Optical and Plasma Physics; Physical Chemistry; Solid State Physics; allyl derivatives of N,N,N′,N′-tetramethylethylenediamine; copper halide fragments; crystal structure; π-complexes; copper(I)
• DOI: 10.1134/S0022476612010155
• ISSN: 0022-4766

N,N,N′,N′-tetramethylethylenediamine is obtained by the reaction of ethylenediamine with formaldehyde and formic acid (the Eschweiler-Clarke reaction) and then alkylated with allyl chloride (or bromide) in a ratio of 1:1 or 1:2 to obtain N-allyl-N,N,N′,N′-tetramethylethylenediaminium and N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium bromide respectively. [{C 2 H 4 N 2 (H + )(CH 3 ) 4 (C 3 H 5 )}Cu 4 Cl 6 ] ( 1 ) and [{C 2 H 4 N 2 (CH 3 ) 4 (C 3 H 5 )2} 0.5 Cu 2 Cl 1.67 Br 1.33 ] ( 2 ) π -complexes are obtained from alcohol solutions containing an ethylenediamine derivative and copper(II) chloride by ac-electrochemical synthesis on copper wire electrodes. An XRD study of the complexes is carried out. The crystals are monoclinic; 1 : P 2 1 / n space group, a = 9.0081(6) Å, b = 12.5608(7) Å, c = 16.8610(10) Å, β = 102.061(3)°, V = 1865.7(2) Å 3 , Z = 4; 2 : C 2/ c space group, a = 14.462(2) Å, b = 12.519(1) Å, c = 12.762(2) Å, β = 107.861(5)°, V = 2199.1(4) Å 3 , Z = 8. The structure of 1 consists of infinite copper halide networks with four crystallographically independent copper atoms, one of which coordinates the double bond of the allyl group of the ligand. The [C 2 H 4 N 2 (H)(CH 3 ) 4 (C 3 H 5 )] 2+ cations are attached above and below the plane of the network. The individual fragments are bonded via an extensive system of (N)H…Cl and (C)H…Cl hydrogen bonds. The structure of 2 contains a three-dimensional copper halide framework whose cavities contain the [C 2 H 4 N 2 (CH 3 ) 4 (C 3 H 5 ) 2 ] 2+ cations that are π -coordinated with copper(I) atoms. In both structures, the Cu(I) atom that coordinates the C=C bond has a trigonal-pyramidal coordination environment consisting of the double C=C bond of the corresponding ligand and three halogen atoms. The other Cu(I) atoms have a tetrahedral environment consisting solely of halogen atoms. The Cu-(C=C) distance is 1.958(1) Å, (1) and 1.974(1) Å (2) .