Lewis-base adducts of Group 1B metal(I) compounds. Part 18. Stereo-chemistries and structures of the 1 : 1 neutral complexes of Cu I X with 1,10-phenanthroline (X = I) or 2,9-dimethyl-1,10-phenanthroline (X = I, Br, or Cl)

Abstract

Single-crystal X-ray structure determinations have been carried out at 295 K on the compounds [Cul(phen)]·5MeOH (1)(phen = 1,1 0-phenanthroline), [Cul(dmphen)](2), [CuBr(dmphen)](3), and [CuCl(dmphen)](4)(dmphen = 2,9-dimethyl-1,10-phenanthroline). Crystals of (1) are monoclinic, P2₁/n, a= 10.659(3), b= 23.585(9), c= 10.487(3)Å, β= 91.34(2)°, Z= 8; for N₀= 2 457 independent ‘observed’ diffractometer reflections, R= 0.034. Crystals of (2) are monoclinic, C2/_c,a= 19.025(6), b= 8.489(3), c= 17.376(5)Å, β= 108.27(2)°, Z= 8; N₀= 1 582, R= 0.035. Crystals of (3) are isomorphous with (2), a= 18.497(6), b= 8.398(2), c= 17.419(5)Å, β= 110.14(2)°; N₀= 1 786, R= 0.040. Crystals of (4) are monoclinic, P2₁/n, a= 10.133(4), b= 18.388(5), c= 6.729(1)Å, β= 94.31(2)°, Z= 4; N₀= 889, R= 0.044. In (1)–(3), the species is a di-p-halogeno-bridged dimer with four-co-ordinate copper atoms. For (1), Cu–I are 2.589(1)–2.632(1)Å with Cu–N 2.078(6)–2.103(6); Cu ⋯ Cu is 2.609(2) and I ⋯ I, 4.454(2)Å. In (2), Cu–I are 2.673(1), 2.563(1), Cu–N, 2.094(6), 2.092(5); Cu ⋯ Cu is 3.024(2) and I ⋯ I, 4.276(1)Å. In (3), Cu–Br are 2.400(1), 2.559(1), Cu–N, 2.083(5), 2.085(4)Å; Cu ⋯ Cu is 3.097(1) and Br ⋯ Br, 3.876(1)Å. Complex (4) is mononuclear with the copper atom pseudo-trigonally planar co-ordinated by the bidentate aromatic ligand [Cu–N 2.060(6) and 2.057(5)Å] and the halide [Cu–Cl, 2.126(2)Å]. The role of the ligand and halide substituents on the complexity of the complex is examined.