SYNTHESIS AND STRUCTURAL AND MAGNETIC-PROPERTIES OF MONONUCLEAR, DINUCLEAR, AND TETRANUCLEAR COPPER(II) COMPLEXES OF A 17-MEMBERED MACROCYCLIC LIGAND (HM3), CAPABLE OF FORMING ENDOGENOUS PHENOXIDE AND PYRIDAZINO BRIDGES - X-RAY CRYSTAL-STRUCTURES OF [CU2(M3)(MU-2-OME)(NO3)2], [CU4(M3)2(MU-3-OME)2(MU-2-CL)2CL2], [CU4(M3)2(MU-3-OET)2(MU-2-N3)2(N3)2](MEOH), [CU4(M3)2(MU-3-OME)2(NCS)4](DMF), AND [CU(M3)(NCS)2]

A series of copper(II) complexes, involving dinuclear, tetranuclear, and mononuclear derivatives, [Cu2(M3)(mu2-OMe)X2] (X = NO3 (I), CF3SO3 (II)), [Cu4(M3)2(mu3-OMe)2(mu2-Cl)2Cl2] (III), [Cu4(M3)2(mu3-OEt)2(mu2-N3)2(N3)2](MeOH) (IV), [Cu4(M3)2(mu3-OMe)2(NCS)4](DMF) (V), [Cu4(M3)2(mu3-OMe)2(mu2-Br)2Br2].2H2O (VI), and [Cu(M3)(NCS)2] (VII), have been synthesized by template condensation of 2,6-diformyl-4-methylphenol with 3,6-bis(2-aminoethyl)thio)pyridazine (1:1), in the presence of copper(II) salts, followed, in some cases, by addition of potentially coordinating anions. The tetranuclear complexes III-VI involve an effective dimerization of two dinuclear halves, with an unusual combination of mu3-alkoxy and mu2-anion bridges in III, IV, and VI and just mu3-alkoxy bridges in V. Single-crystal X-ray structures for I, III-V, and VII have been determined. I crystallized in the monoclinic system, space group P2(1)/n, with a = 8.6930(8) angstrom, b = 15.02(1) angstrom, c = 18.308(2) angstrom, beta = 90.890(7)-degrees, and Z = 4. Refinement by full-matrix least-squares procedures gave final residuals of R = 0.057 and R(W) = 0.049. III crystallized in the monoclinic system, space group P2(1)/n, with a = 11.045(2) angstrom, b = 16.054(6) angstrom, c = 12.309(2) angstrom, beta = 90.68(2)-degrees, and Z = 4. Refinement by full-matrix least-squares procedures gave final residuals of R = 0.032 and R(W) = 0.032. IV crystallized in the monoclinic system, space group P2(1)/n, with a = 11.077(3) angstrom, b = 15.153(4) angstrom, c = 16.492(2) angstrom, beta = 99.45(2)-degrees, and Z = 4. Refinement by full-matrix least-squares procedures gave final residuals of R = 0.059 and R(W) = 0.049. V crystallized in the monoclinic system, space group C2/c, with a = 27.316(5) angstrom, b = 22.170(4) angstrom, c = 11.036(4) angstrom, beta = 111.81(2)-degrees, and Z = 8. Refinement by full-matrix least-squares procedures gave final residuals of R = 0.056 and R(W) = 0.061. VII crystallized in the monoclinic system, space group P2/n, with a = 21.283(6) angstrom, b = 11.367(6) angstrom, c = 21.679(4) angstrom, beta = 116.73(1)-degrees, and Z = 8. Refinement by full-matrix least-squares procedures gave final residuals of R = 0.042 and R(W) = 0.035. Low magnetic moments are observed for all the polynuclear complexes, signifying the presence of intradimer antiferromagnetic coupling. This has been confirmed by variable-temperature magnetic studies, and strong exchange is observed within each dinuclear fragment (I-VI), with -2J > 445 cm-1 in all cases. Weak interdinuclear ferromagnetic exchange is apparent in two cases, but for complex IV, in which bridging azides link the dinuclear halves, much stronger antiferromagnetic interdimer coupling appears to exist.