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  Global Journal of Inorganic Chemistry. Volume 1, Issue 1 (2010) pp. 34-41
  Research Article
 
Synthesis, X-ray structure and thermal behavior of isomorphous silver-deficient channel lattice frameworks with general formula [(Ag0.25/M0.25)(H2O)]@[Ag2M(C2O4)3].4H2O (M = CoIII, CrIII)
  Michel M. Bélombéa,*, Justin Nenwaa, Olivier T. Tenea, Boniface P. T. Fokwab  
     
a Inorganic Chemistry Department, Faculty of Science, P.O. Box 812, University of Yaounde I, Yaounde, Center Region, Cameroon
b Institute for Inorganic Chemistry, RWTH Aachen University, D-52056 Aachen, Germany

   
  Abstract  
 

     Two isomorphous silver-deficient oxalatometalate salts, viz. [(Ag0.25/Co0.25)(H2O)] @[Ag2Co(C2O4)3].4H2O (1) and [(Ag0.25/Cr0.25)(H2O)]@[Ag2Cr(C2O4)3].4H2O (2), have been synthesized in water and fully characterized by elemental analysis, single crystal X-ray structure determination, vibrational and electronic spectra, and by thermogravimetry. Compounds 1 and 2 crystallize as interesting three-dimensional coordination polymer networks that surround isolated nanochannels parallel to the c axis, encapsulating guest water clusters. In both crystal structures, the respective Co1 and Cr1 centers are each pseudo-octahedrally chelated by three oxalato ligands with usual propeller orientation. The Ag1 centers (on two-fold axes) are in strongly distorted octahedral coordination of two trans-chelating oxalato ligands lying within the equatorial plane and two axial monodentate oxalato ligands. The Ag2 centers, in general positions, are pentacoodinated by one chelating and three singly linked oxalato ligands. The Ag3/Co2 or Ag3/Cr2 sites, also in general positions, are occupied  by 0.75AgI/0.25CoIII or 0.75AgI/0.25CrIII atom pairs, and are pentacoordinated to one chelating, two monodentate oxalato and one aqua ligands. The bulk structure is consolidated by O-H…O bridgings within the nanochannels, and by coulombic interactions. The shortest intermetallic distances are Ag3/Co2–Ag3/Co2V = 3.241(2) Å and Ag3/Cr2–Ag3/Cr2V = 3.226(2) Å.

     
  Keywords  
  Crystal structure; nanochannels; silver-deficient coordination polymers; metal(III) oxalates; water clusters  
     
   
   
   
   
     

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