INFLUENCE OF INTRAMOLECULAR COORDINATION ON THE AGGREGATION OF SODIUMPHENOLATE COMPLEXES - X-RAY STRUCTURES OF [NAOC6H4(CH(2)NME(2))-2](6)AND (2)-2,6-ME-4)(HOC6H2(CH(2)NME(2))(2)-2,6-ME-4)](2)

The structural characterization of two new sodium phenolate complexes, containing ortho-amino substituents, enables the influence of intramo lecular coordination on the aggregation of sodium phenolate complexes to be determined. Crystals of hexameric [NaOC6H4(CH(2)NMe(2))-2]6 (1a) are monoclinic, space group P2(1)/c, with a = 11.668(4) Angstrom, b = 18.146(4) Angstrom, c = 1.221(5) Angstrom, beta = 110.76(3) Angstrom, V = 2815.5(16) Angstrom(3), and Z = 2; R = 0.0736 for 2051 reflection s with I > 2.0 sigma(I). Complex la contains a unique Na6O6 core, cons isting of two face-fused cubes, with the ortho-amino substituent of ea ch phenolate coordinating to a sodium atom. In addition, two of the ph enolate ligands have an eta(2)-arene interaction with an additional so dium atom in the core. Crystals of dimeric (2)-2,6-Me-4)(HOC6H2(CH(2)N Me(2))(2)-2,6-Me-4)](2) (2b) are triclinic, space group P (1) over bar , with a = 10.0670(8) Angstrom, b = 10.7121(7) Angstrom, c = 27.131(3) Angstrom, alpha = 92.176(8)degrees, beta = 99.928(8)degrees, gamma = 106.465(6)degrees, V = 2752.1(4) Angstrom(3), and Z = 2; R = 0.0766 fo r 5329 reflections with I > 2.0 sigma(1). Dimeric complex 2b contains two phenolate ligands, which bridge the two sodium atoms, each coordin ating with one ortho-amino substituent to a sodium atom, while the sec ond available ortho-amino substituent remains pendant. The coordinatio n sphere of each sodium atom is completed by a (neutral) bidentate O,N -coordinated parent phenol molecule. The second ortho-amino substituen t of this neutral phenol is involved in a hydrogen bridge with its aci dic hydrogen. On the basis of these two new crystal structures and pre viously reported solid state structures for sodium phenolate complexes , it is shown that the introduction of first one and then two ortho-am ino substituents into the phenolate ligands successively lowers the de gree of association of these complexes in the solid state. In this pro cess, the basic Na2O2 building block of the molecular structures remai ns intact.