Inorganic Chemistry, Vol.34, No.9, 2356-2366, 1995
Magnetostructural Correlations in Mu(2)-1,1-Azide-Bridged Dicopper(II) Complexes .2. Dominant Antiferromagnetic Coupling with Azide Bridge Angles Exceeding 108-Degrees - X-Ray Structures of (Cu-2(PAP)(Mu(2)-N-3)Br-3)Center-Dot-CH2Cl2, (Cu-2(Pap6Me)(Mu(2)-N-3)(Mu(2)-Br)Br-2)Center-Dot-1.68H(2)O, (Cu-2(Pap6Me)(Mu(2)-N-3)(Mu(2)-H2O)(NO3)(2))(NO3)Center-Dot-0.75Ch(3)Oh, (Cu-2(Pan)(Mu(2)-N-3)(Mu(2)-NO3)(NO3)(2))Center-Dot-CH3OH-Center-Dot-CH3CN, and (Cu-2(Ppd35Me)(Mu(2)-N-3)Br-3(CH3OH))
Dinuclear copper(II) complexes involving a combination of a mu(2)-1,2-diazine (pyridazine or phthalazine) and a mu(2)-1,1-azide bridge have been shown to exhibit net antiferromagnetism, with the azide actually contributing to total spin exchange as an antiferromagnetic bridge. X-ray structures for the complexes [Cu-2(PAP)(mu(2)-N-3)Br-3]. CH2Cl2 (1), [Cu-2(PAP6Me)(mu(2)-N-3)(mu(2)-Br)Br-2]. 1.68H(2)O (3), [Cu-2(PAP6Me)(mu(2)-N-3)(mu(2)-H2O)(NO3)2](NO3). 0.75CH(3)OH (4), [Cu-2(PAN)(mu(2)-N-3)(mu(2)-NO3>(NO3)(2)]CH3OH . CH3CN (5), and [Cu-2(PPD35Me)(mu(2)-N-3)Br-3(CH3OH)] (12) show azide bridge angles in the range 108.7-122.5 degrees. Compound 1 crystallized in the monoclinic system, space group P2(1)/c, with a = 13.390(3) Angstrom, b = 11.992(3) Angstrom, c = 16.658(2) Angstrom, beta = 106.97(1)degrees, and Z = 4 (R = 0.036, R(W) = 0.026). Compound 3 crystallized in the monoclinic system, space group P2(1)/m, with a = 8.227(4) Angstrom, b = 15.719(4) Angstrom, c = 10.168(6) Angstrom, beta = 100.89(5)degrees, and Z = 2 (R = 0.052 and R(W) = 0.040). Compound 4 crystallized in the monoclinic system, space group P2(1)/m, with a = 8.028(6) Angstrom, b = 16.752(7) Angstrom, c = 21.795(7) Angstrom, beta = 95.85(5)degrees, and Z = 4 (R = 0.075, R(W) = 0.062). Compound 5 crystallized in the monoclinic system, space group C2/c, with a 18.419(4) Angstrom, b = 23.004(2)) Angstrom, c = 14.545(2) Angstrom, beta = 97.54(1)degrees, and Z = 8 (R = 0.070, R(W) = 0.051). Compound 12 crystallized in the orthorhombic system, space group Pbca (No. 61), with a = 25.241(6) Angstrom, b = 14.458(3) Angstrom, c = 12.810(3) Angstrom, and Z = 8 (R = 0.052, R(W) = 0.041). Other complexes include [Cu-2(PAP6Me)(mu(2)-N-3)Cl-3]. CH2Cl2 (2), [Cu-2(PPD)(mu(2)-N-3)X(3)]. yCH(3)OH . zH(2)O (X = Cl, y = 0.5, z = 1.5 (6); X = Br, y = 0, z = 0.5 (7)), [Cu-2(PPD)(mu(2)-N-3)(N-3)(2)]X (X = NO3 (8), X = ClO4 (9), X = CF3SO3 (10)), [Cu-2(PPD35Me(mu(2)-N-3)Cl-3]. CH3OH (11) (PAP = 1,4-bis(2’-pyridylamino)phthalazine, PAP6Me = 1,4-bis((6’-methyl-2-pyridyl) amino)phthalazine, PAN = 1,4-bis(2-pyridylamino)naphthalazine, PPD = 3,6-bis(1-pyrazolyl)pyridazine, PPD35Me = 3,6-bis(3-dimethyl-1-pyrazolyl)pyridazine).
Keywords:BINUCLEAR COPPER(II) COMPLEXES;CRYSTAL-STRUCTURE;SPECTROSCOPIC COMPARISONS;EXCHANGE INTERACTION;DINUCLEAR COMPLEX;EXOGENOUS BRIDGES;LIGANDS;HYDROXO;STABILIZATION;METHEMOCYANIN