Copper complexes with N-allylisoquinolinium halides: Synthesis and crystal structures of [C9H7N(C3H5)]2CuIICl2.86Br1.14, [C9H7N(C3H5)CuIBr2] · H2O, and [C9H7N(C3H5)CuIBr2

Abstract

Crystals of the copper bromide complexes with N-allylisoquinolinium halides of the composition [C9H7N(C3H5)]2CuIICl2.86Br1.14 (I), [C9H7N(C3H5)]CuIBr2 · H2O (II), and [C9H7N(C3H5)]CuIBr2 (III) are prepared by ac electrochemical synthesis, and their structures are studied by X-ray diffraction analysis (DARCh-1 (for I) and KUMA/CCD (for II and III) diffractometers). The crystals of compound I are monoclinic: space group P21/n, a = 15.053(5) A, b = 10.486(4) A, c = 17.179(10) A, γ = 109.77(3)°, V = 2552(4) A3, Z = 4. The crystals of complex II are triclinic: space group P\(\overline 1 \), a = 7.040(1) A, b = 7.610(2) A, c = 12.460(2) A, α = 79.54(3)°, β = 86.73(3)°, γ = 89.51(1)°, V = 655.4(2) A3, Z = 2. The crystals of complex III are monoclinic: space group P21/n, a = 12.799(1) A, b = 7.692(1) A, c = 13.491(1) A, β = 111.08(1)°, V = 1239.3(2) A3, Z = 4. The structure of compound I is built of the CuIIX42− tetrahedra and N-allylisoquinolinium cations united by the C-H···X contacts into corrugated layers. The crystal structure of π-complex II is formed of dimers of the composition [C9H7(C3H5)]2 Cu2IBr4 forming layers in the direction of the z axis due to the C-H···X contacts. An important role in structure formation belongs to water molecules that cross-link the organometallic layers through the O-H···X contacts into a three-dimensional framework. When kept in the mother liquor for 6 months, the crystals of compound II transformed into crystals of compound III, whose structure consists of {[C9H7(C3H5)]2Cu2IBr4}n columns united through the C-H···Br contacts (H···Br 2.84(3)−2.92(4) A) into a three-dimensional framework.