Synthesis of zigzag-chain and cyclic-octanuclear calcium complexes and hexanuclear bulky aryl-phosphate sodium complexes with ortho-amide groups: structural transformation involving a network of inter- and intramolecular hydrogen bonds

J Am Chem Soc. 2002 Feb 13;124(6):1052-9. doi: 10.1021/ja011457r.

Abstract

Three new polynuclear Ca(II)- and Na(I) phosphate complexes with two strategically oriented bulky amide groups, 2,6-(PhCONH)(2)C(6)H(3)OPO(3)H(2), were synthesized, including one with a zigzag-chain, [Ca(II)[O(3)POC(6)H(3)-2,6-(NHCOPh)(2)](H(2)O)(4)(EtOH)](n), a cyclic-octanuclear form, [Ca(II)(8)[O(3)POC(6)H(3)-2,6-(NHCOPh)(2)](8)(O=CHNMe(2))(8)(H(2)O)(12)], and a hexanuclear complex, (NHEt(3))[Na(3)[O(3)POC(6)H(3)-2,6-(NHCOPh)(2)](2)(H(2)O)(MeOH)(7)]. X-ray crystallography revealed that all have an unsymmetric ligand position due to the bulky amide groups. A dynamic transformation of the Ca(II) zigzag-chain structure to the cyclic-octanuclear complex was induced by changing coordination of DMF molecules, which caused a reorganization of the intermolecular/intramolecular hydrogen bond network.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amides / chemical synthesis*
  • Amides / chemistry
  • Calcium / chemistry*
  • Crystallography, X-Ray
  • Hydrogen Bonding
  • Magnetic Resonance Spectroscopy
  • Models, Molecular
  • Molecular Structure
  • Organophosphates / chemical synthesis*
  • Organophosphates / chemistry
  • Polycyclic Aromatic Hydrocarbons / chemical synthesis*
  • Polycyclic Aromatic Hydrocarbons / chemistry
  • Spectrophotometry, Infrared

Substances

  • Amides
  • Organophosphates
  • Polycyclic Aromatic Hydrocarbons
  • Calcium