Synthesis and Crystal Structure of the Heterovalent Copper(I,II) π-Complex Cu7Br6.48Cl1.52 ⋅ 2C3N3(OC3H5)3

Abstract

Single crystals of the heterovalent CuI,CuII π,σ-complex Cu7Br6.48Cl1.52 ⋅ 2C3N3(OC3H5)3 are synthesized by the ac electrochemical method from an ethanol solution containing 2,4,6-triallyloxy-1,3,5-triazine, CuCl2 ⋅ 2H2O, and CuBr2. The unit cell parameters of the crystals are: space group \(P\bar 1\), a = 8.271(3) A, b = 11.391(3) A, c = 11.821(3) A, α = 67.43(1)°, β = 84.41(2)°, γ = 85.14(2)°, V = 1022(1) A3, and R(F) = 0.0714. The copper and halogen atoms form unique moieties Cu6X6 linked by bridging fragments [Cu2+ (C3N3(OC3H5)3)2]X2 into infinite chains. Each inorganic moiety Cu6X6 is linked with four 2,4,6-triallyl- oxy-1,3,5-triazine molecules. The ligand molecule is coordinated to one CuII atom through the nitrogen atom of the triazine cycle and to two CuI atoms through the C=C bonds of two allyl groups. The Br content equal to 0.57 in the X(4) position linking the CuI and CuII atoms differs markedly from a value of 0.85–0.91 for the X(1), X(2), and X(3) positions linked only with the Cu(I) atoms.