The stereochemistry of Bis(α,α'-diimine)copper(I) complexes: the crystal and molecular structures of Bis(2,9-dimethyl-1,10-phenanthroline)copper(I) bromide hydrate, Bis(4,4',6,6'-tetramethyl-2,2'-bipyridine)copper(I) chloride dihydrate, and Bis(2,9-dimethyl-1,10-phenanthroline)copper(I) nitrate dihydrate (a redetermination)

Abstract

The crystal structures of the title compounds have been determined by single-crystal X-ray diffraction methods at 295 K, and refined by least-squares methods. Crystal data for [Cu(Cl₄H₁₂N₂)₂] Br.H₂O (1) are: monoclinic, P2₁/c, a 14.067(4), b 17.687(6), c 10.337(5) Å, β 91.04(3)º, with R 0.038, R' 0.040 for 1855 'observed' reflections. Crystal data for [Cu(Cu₁₄H₁₂N₂)₂] C1.2H₂O (2) are: triclinic, P1, a 15.305(2), b 13.164(2), c 7.344(3) Å, α 83.03(3), β 93.83(3), γ 108. 11260(3)º, with R 0.051, R' 0.053 for 1293 'observed' reflections. Crystal data for [Cu(Cl₄H₁₂N₂)₂] Br.H₂O (3) are: triclinic, P1, a 7.619(2), b 11.967(3), c 15.534(3) Å, α 71.26(1), β 82.13(1), γ 86.86(2)º, with R 0.043, R' 0.052 for 2335 'observed' reflections. The anionic and solvent species are uncoordinated in all three compounds. Cu-N bond lengths range from 2.027(5) to 2.053(5) Å. The copper(1) environment (CuN₄) in each complex shows considerable distortion from tetrahedral geometry. N-Cu-N intraligand angles range from 81.0(2) to 83.0(2)º, while N-Cu-N interligand angles range from 114.7(2) to 135.2(2)º. The variation in interligand angles can be described in terms of three independent rotations of ligand 2 about an orthogonal axial system defined by ligand 1.