SYNTHESIS, STRUCTURES, AND PROPERTIES OF THE MOLECULAR ASSEMBLIES OF COPPER(I) AND SILVER(I) COMPLEXES WITH PHENAZINE - NOVEL DONOR-ACCEPTOR AND HUGE POLYNUCLEAR COMPLEXES

Three copper(I) and two silver(I) complexes with phenazine (phz), [Cu2(phz)3(MeOH)2](phz)(PF6)2 (1), [Cu(phz)2(H2O)]ClO4(2), [Cu(phz)2(NO3)] (3), {[Ag(phz)]ClO4}infinity (4), and [Ag2(phz)(NO3)2]infinity (5), were synthesized, and their molecular structures and packings were determined by using single-crystal X-ray diffraction methods. 1 is composed of infinite stacks of alternating metal-free phz molecules and the dicopper complex cations [Cu2(PhZ)3(MeOH)2]2+ and gives a CT band from the latter to the former at 710 nm indicative of a donor-acceptor complex. One phz in 2 and an opposite phz in another molecule alternatively stacked to give infinite columns. The copper of 3 is coordinated to NO3- and phz in a tetrahedral geometry. The molecular packing of 4 is composed of infinite linear chains of -Ag-phz-Ag-phz- along the a axis and a pi-pi interaction of the phz molecules between the chains along the c axis. The 3D complex 5 is made of a 2D framework of six-membered rings of silvers, a weak Ag-O bonding, and a pi-pi interaction of phz molecules between the 2D sheets. Solvent and counteranion as well as metal ion have been shown to play an important role in the molecular packing of metal complexes with phz because they are coordinated to metal ion to change the complex structure. Crystal data: 1, triclinic P1BAR-, alpha = 13.008(2) angstrom, b = 13.694(2) angstrom, c = 7.789(1) angstrom, a = 102.50(1)-degrees, beta = 105.02(1)-degrees, gamma = 72.81 (1)-degrees, V - 1256.4(3) angstrom3, Z = 2, 3568 reflections, R = 0.069; 2, triclinic P1BAR, a = 10.811(4) angstrom, b = 12.576(3) angstrom, c = 8.992(1) angstrom, alpha = 105.20(1)-degrees, beta = 92.59(2)-degrees, gamma = 110.90(5)-degrees, V = 1089.0(5) angstrom3, Z = 2, 3579 reflections, R = 0.045; 3, monoclinic P2(1)/n, a = 10.686(2) angstrom, b = 26.937(1) angstrom, c = 7.219(2) angstrom, beta = 102.18(1)-degrees, V = 2031(1) angstrom3, Z = 4, 2256 reflections, R = 0.035; 4, triclinic P1BAR, a = 7.2044(6) angstrom, b = 12.943(2) angstrom, c = 7.138(2) angstrom, a = 98.64(2)-degrees, beta = 98.70(1)-degrees, gamma = 89.92-degrees, V = 650.3(2) angstrom3, Z = 2, 2275 reflections, R = 0.034; 5, monoclinic P2(1)/n, a = 5.007(3) angstrom, b = 19.454(2) angstrom, c = 7.248(6) angstrom, beta = 102.18(1)-degrees, V = 685.0(7) angstrom3, Z = 4, 2256 reflections, R = 0.035.