Copper Complexes with N-Allylisoquinolinium Halides: Synthesis and Crystal Structures of [C9H7N(C3H5)]2Cu~(II)Cl_(2.86)Br_(1.14), [C9H7N(C3H5)Cu~IBr2] · H2O, and [C9H7N(C3H5)Cu~IBr2]

摘要

Crystals of the copper bromide complexes with N-allylisoquinolinium halides of the composition [C9H7N(C3H5)]2Cu~(II)Cl_(2.86)Br_(1.14) (I), [C9H7N(C3H5)]Cu~IBr2 · H2O (II), and [C9H7N(C3H5)]Cu~IBr2 (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 P2_1, a = 15.053(5) A, b = 10.486(4) A, c= 17.179(10) A, γ= 109.77(3)°, V = 2552(4) A~3, Z=4. The crystals of complex II are triclinic: space group P1, 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) A~3, Z = 2. The crystals of complex III are monoclinic: space group P2_1, a = 12.799(1) A, b = 7.692(1) A, c = 13.491(1) A, β = 111.08(1)°, V= 1239.3(2) A~3, Z = 4. The structure of compound I is built of the Cu~(II)X_4~(2-) 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)]2Cu2 Br4 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)]2Cu_2~IBr4}_n columns united through the C-H···Br contacts (H···Br 2.84(3)-2.92(4) A) into a three-dimensional framework.