Structure of complexes formed in the CuX 2-Cu-N- allylisoquinolinium chloride system (X = Cl, Br)

The crystals of N-allylisoquinolinium chlorides of the compositions [C 9H 7N(C 3H 5)] 2Cu IICl 4 (I), [C 9H 7N(C 3H 5)]Cu ICl 2·H 2O (II), and [C 9H 7N(C 3H 5)]Cu ICl 1.43Br 0.57·H 2O (III) were prepared by alternating-current electrosynthesis. X-ray diffraction analysis (using diffractometer models DARCH1 for I, STOE for II, and KUMA/CCD for III, MoK α radiation) showed that the crystals of I are monoclinic, space group P2 1/n, a = 14.91(1) Å, b = 10.41(1) Å, c = 16.90(1) Å, γ = 109.73(8)°, V = 2470(8) Å 3, Z = 4. The crystals of isostructural compounds II and III are triclinic, space group Par 1, Z = 2; crystals II: a = 7.2446(6) Å, b = 7.4379(6) Å, c = 12.110(1) Å, α = 80.95(1)°, β = 85.55(1)°, γ = 86.60(1)°, V = 641.8(2) Å 3; crystals III: a = 7.253(2) Å, b = 7.459(4) Å, c = 12.151(5) Å, α = 80.82(4)°, β = 83.73(3)°, γ = 86.81(4)°, V = 644.6(9) Å 3. The structure of I is composed of Cu IICl 4 2- tetrahedra and N-allylisoquinolinium cations united by C-H⋯Cl hydrogen bonds in corrugated layers. The crystal structures of π-complexes II and III are built of [C 9H 7(C 3H 5)] 2Cu 2 IX 4 dimers, which form layers along the c axis due to the C-H⋯X hydrogen bonds. An important role in the structure formation is played by water molecules, which crosslink the organometallic layers to form a three-dimensional framework through the O-H⋯X contacts.