Pentanuclear homoleptic M5L6 Mn(II), Co(II), Zn(II)) complexes formed by strict self-assembly

A series of trigonal bipyramidal pentanuclear complexes involving the alkox o-diazine ligands poap and p3oap, containing the M-5[mu -O](6) core is desc ribed, which form by a strict self-assembly process. [Co-5(poap-H)(6)](ClO4 )(4). 3H(2)O (1), [Mn-5(poap-H)(6)](ClO4)(4).3.5CH(3)OH .H2O (2), [Mn-5(p3o ap-H)(6)](ClO4)(4). CH3CH2OH . 3H(2)0 (3), and [Zn-5-(poap-H)(6)](ClO4)(4). 2.5H(2)O (4) are homoleptic pentanuclear complexes, where there is an exact match between the coordination requirements of the five metal ions in the cluster, and the available coordination pockets in the polytopic ligand. [Z n-4(poap)(poap-H)(3)(H2O)(4)] (NO3)(5).1.5H(2)O (5) is a square [2 x 2] gri d with a Zn-4[mu -O](4) core, and appears to result from the presence of NO 3, Which is thought to be a competing ligand in the self-assembly. X-ray st ructures are,reported for 1, 4, and 5. 1 crystallized in the monoclinic sys tem, space group P2(1)/n with a = 13.385(l) Angstrom, b = 25.797(2) Angstro m, c = 28.513(3) Angstrom, beta= 98.704(2)degrees, and Z = 4. 4 crystallize d in the triclinic system, space group P1 with a = 13.0897(9) Angstrom, b = 18.889(1) Angstrom, c = 20.506(2) Angstrom, alpha = 87.116(1)degrees, beta =74.280(2)degrees, gamma = 75.809(2)degrees, and Z = 2. 5 crystallized in the monoclinic system, space group P2(1)/n with a = 14.8222(7) Angstrom, b = 21.408(1) Angstrom, c = 21.6197(9) Angstrom, beta =90.698(1)degrees, and Z = 4. Compounds 1-3 exhibit intramolecular antiferromagnetic coupling.