SELECTIVE DERIVATIZATION OF AZA MACROCYCLES

A range of selectively functionalised compounds derived from 1,4,7-tri azacyclononane ([9]aneN(3)), including thylpropyl)-1,4,7-triazacyclono nane-1-carbaldehyde (H(2)L(1)), 1-benzyl-4,7-bis(2-hydroxy-2-methylpro pyl)-1, 4,7-triazacyclononane (H(2)L(2)) and (2-hydroxy-2-methylpropyl )-1,4,7-triazacyclononane (H(2)L(3)). has been prepared. The structure of H(2)L(3) . CHCl3 shows a disordered macrocyclic ring with the majo r conformer refining to a site occupancy of 0.663(8), and both disorde red rings adopting a [333] conformation. The pendant alcohol arms were not disordered and were found to be hydrogen bonded to a CHCl3 solvat e molecule with H ... O(1) and H ... O(4) distances of 1.73 and 1.81 A ngstrom respectively. The structure of Na[Cu(H(2)L(1))(NCMe)][BF4](2)[ NO3] shows the copper(II) centre in the [Cu(H(2)L(1))(NCMe)](2+) catio n bound to two amine donors and two alcohol donors of H(2)L(1) and to a MeCN molecule. The Cu-N bond lengths lie in the range 1.984(3)-2.015 (3) Angstrom. Both alcohol donors are protonated, with one short Cu-O( 16) bond of 1.963(3) Angstrom and one long Cu-O(21) bond of 2.252(3) A . There is also a sixth longer-range interaction of the copper(II) cen tre with the amide N [N(1)] of H(2)L(1) at a distance of 2.611(5) Angs trom, confirmed by the loss of planarity of the C(2)-C(9)-N(1)-C(10)-O (11)-H(10) amide fragment to give a dihedral angle between the planes defined by C(2)-C(9)-N(1) and N(1)-C(10)-O(11)-H(10) of 27.1(4)degrees . The structure is completed by interaction of O(11) with a Na+ ion wh ich itself bridges to BF4- counter anions leading to a central infinit e core of [Na(BF4)(2)](-) aggregates onto which are attached the [Cu(H (2)L(1))(NCMe)](2+) cations. The complex [Cu(H(2)L(2))(OH2)][NO3](2) s hows the six-co-ordinate copper(II) centre bound to the three amine an d two alcohol donors of H(2)L(2) and to one water molecule. There are four short bonds [to N(7), N(4), O(40) and O(1)] in the range 1.961(5) -2.073(6) Angstrom and two longer bonds to N(1) and O(70) at 2.308(5) and 2.313(5) Angstrom respectively. The H atoms of the water molecule [O(1)] and one of the pendant arms [O(40)] also make hydrogen-bonding contacts with the nitrate counter ions.