Influence of Intramolecular Coordination on the Aggregation of Sodium Phenolate Complexes. X-ray Structures of [NaOC6H4(CH2NMe2)-2]6 and [Na(OC6H2(CH2NMe2)2-2,6-Me-4)(HOC6H2(CH2NMe2)2-2,6-Me-4)]2
- 1 January 1996
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 35 (5) , 1195-1200
- https://doi.org/10.1021/ic950856i
Abstract
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 [NaOC6H4(CH2NMe2)-2]6 (1a) are monoclinic, space group P21/c, with a = 11.668(4) Å, b = 18.146(4) Å, c = 14.221(5) Å, β = 110.76(3) Å, V = 2815.5(16) Å3, and Z = 2; R = 0.0736 for 2051 reflections with I > 2.0σ(I). Complex 1a contains a unique Na6O6 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 η2-arene interaction with an additional sodium atom in the core. Crystals of dimeric [(NaOC6H2(CH2NMe2)2-2,6-Me-4)(HOC6H2(CH2NMe2)2-2,6-Me-4)]2 (2b) are triclinic, space group P1̄, with 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) Å3, and Z = 2; R = 0.0766 for 5329 reflections with I > 2.0σ(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 Na2O2 building block of the molecular structures remains intact.Keywords
This publication has 20 references indexed in Scilit:
- A Proposal for Positive Cooperativity in Anion−Cation Binding in Yttrium and Lutetium Complexes Based on o-Amino-Substituted Phenolate Ligands. On the Way to Coordination Polymers by Self-Assembly. Molecular Structures of [ClLu(OAr)3Na] (X-ray) and [ClY(OAr‘)3Y(OAr‘)3Na] (X-ray and 89Y-NMR)Inorganic Chemistry, 1996
- Versatility in Phenolate Bonding in Organoaluminum Complexes Containing Mono- and Bis-ortho-Chelating Phenolate Ligands. X-ray Structures of Al{OC6H2(CH2NMe2)2-2,6-Me-4}3, Al(Me)2{OC6H2(CH2NMe2)2-2,6-Me-4}.cntdot.N-AlMe3, and Al(Me)2{OC6H2(CH2NMe2)2-2,6-Me-4}.cntdot.N-AlMe3.cntdot.O-AlMe3Organometallics, 1995
- An alkali metal phenoxide with an unusual dimeric crystal structure: [Na(OC6H3But-2,6)(µ-Me2SO)(Me2SO)]2Journal of the Chemical Society, Chemical Communications, 1995
- Cooperative Binding of Na+ and Cl- in Na{M[OC6H2(CH2NMe2)2-2,6-Me-4]3Cl}: Synthesis (M = Lu, Y) and X-Ray Structure (M = Lu) of New Heterometallic Complexes of Lutetium and Yttrium Containing Bis(o-amino)phenolate LigandsInorganic Chemistry, 1994
- A New Type of .mu.4-Oxo-Bridged Copper Tetramer: Synthesis, X-ray Molecular Structure, Magnetism and Spectral Properties of (.mu.4-Oxo)tetrakis(.mu.-bromo)bis(.mu.-2,6-bis(morpholinomethyl)-4-methylphenolato)tetracopper(II) and (.mu.4-Oxo)tetrakis(.mu.-benzoato)bis(.mu.-2,6-bis(morpholinomethyl)-4-methylphenolato)tetracopper(II)Inorganic Chemistry, 1994
- Mononuclear tungsten(VI) phenylimido phenoxide and alkoxide complexes with intramolecular amine coordination: molecular structure of WCl3(=NPh)[OC6H2(CH2NMe2)2-2,6-Me-4]Inorganic Chemistry, 1993
- Synthesis, structure, and reactivity of polymetallic sodium and lanthanum 4-methylphenoxide complexesInorganic Chemistry, 1993
- Solvation of aggregates of lithium phenolates by hexamethylphosphoric triamide. HMPA causes both aggregation and deaggregationJournal of the American Chemical Society, 1992
- The first lithium phenolate with a trinuclear structure and the tetranuclear product of 1 : 1 addition of lithium iodide; X-ray structures of [LiOAr]3 and [Li2(OAr)I]2[OAr = OC6H2(CH2NMe2)2-2,6-Me-4]Journal of the Chemical Society, Chemical Communications, 1992
- Structural factors controlling the aggregation of lithium phenolates in weakly polar aprotic solventsJournal of the American Chemical Society, 1988