Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXIII. Stereochemistries and Structures of the 1 : 1 Adducts of Cu¹X (X = Cl, Br, I) With 2,2'-Bipyridine

Abstract

Syntheses and single-crystal X-ray structural characterizations (at c. 295 K) are recorded for the 1 : 1 adducts of copper(I) chloride, bromide and iodide with L = 2,2′-bipyridine. The chloride is triclinic, Pī , a 14.069(5), b 10.520(3), c 7.872(2)Ǻ, α 69.00(2), β 88.62(3), γ 70.70(2)°, Z = 4 formula units; R was 0.041 for N_o 1805 'observed' [I > 3σ(I)] reflections. The bromide is monoclinic, P2₁/c, a 8.788(3), b 13.206(6), c 9.895(3)Ǻ, β 117.90(2)°, Z = 4 formula units; R 0.036 for N_o 1007. The iodide is monoclinic, C2/c, a 17.571(3), b 8.587(7), c 16.796(3)Ǻ, β 120.17(2)°, Z = 8 formula units; R 0.041 for N_o 1038. The chloride is ionic, [CuL₂]⁺ [ ClCuCl ]^-; in the cation, Cu-N are 2.005(6)-2.039(6)Ǻ with interligand N-Cu-N 114.4(3)-132.4(2)°, while, in the anion, Cl-Cu-Cl is 177.3(1)°, with Cu-Cl 2.086(2) and 2.091(2)Ǻ. The bromide (unlike its 1,10-phenanthroline counterpart, which is ionic) is a centrosymmetric dimer , as also is the iodide. In the bromide, Cu-N are 2.083(6), 2.099(5), and Cu-Br 2.428(2), 2.463(1)Ǻ, Cu…Cu and Br…Br being 2.850(1) and 3.975(2)Ǻ respectively. In the iodide, Cu-N are 2.070(8), 2.08(1), and Cu-I, 2.583(3)Ǻ (×2), and Cu…Cu and I…I are 2.610(2) and 4.420(1)Ǻ.