Hogerheide Marinus P., Ringelberg Stéphanie N., Janssen Maurits D., Boersma Jaap, Spek Anthony L., van Koten Gerard
Department of Metal-Mediated Synthesis, Debye Institute, and Department of Crystal and Structural Chemistry, Bijvoet Center for Biomolecular Research, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands.
Inorg Chem. 1996 Feb 28;35(5):1195-1200. doi: 10.1021/ic950856i.
The structural characterization of two new sodium phenolate complexes, containing ortho-amino substituents, enables the influence of intramolecular coordination on the aggregation of sodium phenolate complexes to be determined. Crystals of hexameric NaOC(6)H(4)(CH(2)NMe(2))-2 (1a) are monoclinic, space group P2(1)/c, with a = 11.668(4) Å, b = 18.146(4) Å, c = 14.221(5) Å, beta = 110.76(3) Å, V = 2815.5(16) Å(3), and Z = 2; R = 0.0736 for 2051 reflections with I > 2.0sigma(I). Complex 1a contains a unique Na(6)O(6) core, consisting of two face-fused cubes, with the ortho-amino substituent of each phenolate coordinating to a sodium atom. In addition, two of the phenolate ligands have an eta(2)-arene interaction with an additional sodium atom in the core. Crystals of dimeric (NaOC(6)H(2)(CH(2)NMe(2))(2)-2,6-Me-4)(HOC(6)H(2)(CH(2)NMe(2))(2)-2,6-Me-4) (2b) are triclinic, space group P&onemacr;, with a = 10.0670(8) Å, b = 10.7121(7) Å, c = 27.131(3) Å, alpha = 92.176(8) degrees, beta = 99.928(8) degrees, gamma = 106.465(6) degrees, V = 2752.1(4) Å(3), and Z = 2; R = 0.0766 for 5329 reflections with I > 2.0sigma(I). Dimeric complex 2b contains two phenolate ligands, which bridge the two sodium atoms, each coordinating with one ortho-amino substituent to a sodium atom, while the second available ortho-amino substituent remains pendant. The coordination sphere of each sodium atom is completed by a (neutral) bidentate O,N-coordinated parent phenol molecule. The second ortho-amino substituent of this neutral phenol is involved in a hydrogen bridge with its acidic hydrogen. On the basis of these two new crystal structures and previously reported solid state structures for sodium phenolate complexes, it is shown that the introduction of first one and then two ortho-amino substituents into the phenolate ligands successively lowers the degree of association of these complexes in the solid state. In this process, the basic Na(2)O(2) building block of the molecular structures remains intact.
对两种含有邻氨基取代基的新型酚钠配合物的结构表征，使得能够确定分子内配位对酚钠配合物聚集的影响。六聚体NaOC(6)H(4)(CH(2)NMe(2))-2 (1a)的晶体为单斜晶系，空间群P2(1)/c，a = 11.668(4) Å，b = 18.146(4) Å，c = 14.221(5) Å，β = 110.76(3) Å，V = 2815.5(16) Å(3)，Z = 2；对于2051个I > 2.0σ(I)的反射，R = 0.0736。配合物1a包含一个独特的Na(6)O(6)核心，由两个面融合的立方体组成，每个酚盐的邻氨基取代基与一个钠原子配位。此外，两个酚盐配体与核心中的另一个钠原子存在η(2)-芳烃相互作用。二聚体(NaOC(6)H(2)(CH(2)NMe(2))(2)-2,6-Me-4)(HOC(6)H(2)(CH(2)NMe(2))(2)-2,6-Me-4) (2b)的晶体为三斜晶系，空间群P&onemacr;，a = 10.0670(8) Å，b = 10.7121(7) Å，c = 27.131(3) Å，α = 92.176(8)°，β = 99.928(8)°，γ = 106.465(6)°，V = 2752.1(4) Å(3)，Z = 2；对于5329个I > 2.0σ(I)的反射，R = 0.0766。二聚体配合物2b包含两个酚盐配体，它们桥连两个钠原子，每个配体与一个邻氨基取代基配位到一个钠原子上，而第二个可用的邻氨基取代基保持悬垂。每个钠原子的配位球由一个（中性）双齿O,N配位的母体酚分子完成。该中性酚的第二个邻氨基取代基与其酸性氢形成氢键。基于这两种新的晶体结构以及先前报道的酚钠配合物的固态结构，结果表明，在酚盐配体中依次引入一个然后两个邻氨基取代基会相继降低这些配合物在固态中的缔合程度。在此过程中，分子结构的基本Na(2)O(2)结构单元保持完整。
