Hydrothermal syntheses and structural chemistry of Mn(II), Co(II) and Ni(II) coordination polymers with xylyl-diphosphonate ligands

Tiffany M. Smith, Diona Symester, Kathryn Perrin, Jose Vargas, Michael Tichenor, Charles J. O'Connor, Jon A Zubieta

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The hydrothermal reactions of the appropriate metal salt, a xylyldiphosphonic acid and a secondary organonitrogen chelating ligand yielded a series of coordination polymers of the M(II)/xylyldiphosphonate/(organoimine chelate family) with M(II) represented by Mn(II), Co(II) and Ni(II); the 1,2-, 1,3- and 1,4-isomers of xylyldiphosphonate; and the organoimine chelate present as 2,2'-bipyridine (bpy), o-phenanthroline (o-phen) or tetra-2-pyridinylpyrazine (tpyprz). Several representative structural types were observed related to the constraints imposed by the xylyldiphosphonate ligand: the two-dimensional materials [Mn(bpy)(1,2-HO3PC8H8PO 3H)] (1), [Mn(o-phen)(1,2-HO3PC8H 8PO3H)] (4) and [Co(o-phen)(1,2-HO3PC 8H8PO3H)] (7) constructed from {M 2(N^N)2(HO3PR)2} clusters linked through the xylyl backbone of the ligands; the network structures of the series [M(bpy)(1,3-HO3PC8H8PO3H)] (MMn (2), Co (6), Ni (12) and [M(o-phen)(1,3-HO3PC8H 8PO3H)] (MMn (5) and Co (8)) which consists of {M 2(N^N)2(HO3PR)2}n chains linked through the xylyl tethers; and the virtual two-dimensional series [M(N^N)2(1,4-H2O3PC8H 8PO3H2)(1,4-HO3PC8H 8PO3H)] (MMn, N^Nbpy (3); MCo, N^No-phen (10); and MNi, N^No-phen (14)) which contain one-dimensional {M(N^N)2(1,4-H 2O3PC8H8PO3H 2)}n 2n+ chains hydrogen-bonded to (HO3PC8H8PO 3H)2- anions to provide expansion in two dimensions. The unique example of a three-dimensional material is [Co(o-phen)(1,4-HO 3PC8H8PO3H)] (9). The tpyprz containing compounds [M(tpyprz)(1,2-HO3PC8H 8PO3H)] (MCo (11), Ni (15)) and [Ni2(tpyprz)(1, 4-HO3PC8H8PO3H)]·4H 2O (16) are one-dimensional.

Original languageEnglish (US)
Pages (from-to)46-59
Number of pages14
JournalInorganica Chimica Acta
StatePublished - 2013



  • Co(II) and Ni(II)
  • Co(II) and Ni(II) coordination polymers
  • Coordination polymers of Mn(II)
  • Hydrogen-bonded coordination polymers
  • Magnetic properties of Mn(II)
  • Metal-xylyldiphosphonate compounds

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

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