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  • Title: Magneto-structural relationships in a series of dinuclear oxalato-bridged (diphenyldipyrazolylmethane)copper(II) complexes.
    Author: Shaw JL, Yee GT, Wang G, Benson DE, Gokdemir C, Ziegler CJ.
    Journal: Inorg Chem; 2005 Jul 11; 44(14):5060-7. PubMed ID: 15998034.
    Abstract:
    A series of oxalato-bridged dinuclear copper(II) complexes of the general formula [Cu2(Pz2CPh2)2(X)2(mu-C2O4)] (X = Cl- (1), NO3(-) (2), ClO4(-) (3); Pz2CPh2 = diphenyldipyrazolylmethane) or [Cu2(Pz(3m)2CPh2)2(H2O)2(mu-C2O4)](NO3)2 x H2O (4) (Pz(3m)2CPh2 = diphenylbis(3-methylpyrazolyl)methane) was synthesized where the axial ligand was systematically varied to study its effect on structure and magnetic coupling. The structures of compounds 1, 2, and 4 have been elucidated by single-crystal X-ray diffraction. [Cu2(Pz2CPh2)2(Cl)2(mu-C2O4)] and [Cu2(Pz2CPh2)2(NO3)2(mu-C2O4)] are isostructural and crystallize in the triclinic system, space group P, Z = 2, with a = 8.6155(8) A, b = 10.1435(9) A, c = 11.3612(11) A, alpha = 95.535(2) degrees, beta = 110.303(2) degrees, and gamma = 106.111(2) degrees for 1 and with a = 8.863(7) A, b = 10.241(9) A, c = 11.425(10) A, alpha = 98.985(14) degrees, beta = 110.449(13) degrees, and gamma = 103.664(14) degrees for 2. [Cu2(Pz(3m)2CPh2)2(H2O)2(mu-C2O4)] x NO3 x H2O crystallizes in the monoclinic system, space group C2/c, Z = 4, with a = 23.4588(14) A, b = 8.8568(5) A, c = 21.7818(13) A, alpha = gamma = 90 degrees, and beta = 100.8890(10) degrees. Variable-temperature magnetic susceptibility studies indicate that all four compounds are strongly antiferromagnetically coupled (2J/k = -364, -344 cm(-1) (2), -424 cm(-1) (3), and -378 cm(-1) (4)). Magnetic and EPR results are discussed with respect to structural parameters to explore possible magneto-structural correlations.
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