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The Effect of HCl on the Copper( II ) Chloride/Pyridine/Water System: Synthesis, Properties and Crystal Structure of [(pyH) 2 CuCl 4 ] and [(pyH) 2 Cu 3 Cl 8 (H 2 O) 2 ] n
Author(s) -
Czugler Mátyás,
Kótai László,
Sreedhar Bojja,
Rockenbauer Antal,
Gács István,
Holly Sándor
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200212)2002:12<3298::aid-ejic3298>3.0.co;2-h
Subject(s) - chemistry , pyridinium , crystal structure , crystallography , hydrogen bond , pyridine , monomer , steric effects , square pyramidal molecular geometry , octahedron , copper , molecule , chloride , ligand (biochemistry) , inorganic chemistry , stereochemistry , polymer , medicinal chemistry , organic chemistry , biochemistry , receptor
Bis(pyridinium) tetrachlorocuprate monomer 1 and bis(pyridinium) octachlorodiaquatricuprate polymer 2 were synthesized and their crystal structures were determined. Both complexes contain pyridinium cations with bifurcated H‐bridges. These H‐bridges stabilize the monomeric structure of the tetrachlorocuprate anion together with the steric demand of the relatively large pyridinium ions in the crystal lattice of 1 . Conversely, at the lower pyridinium ion:copper( II ) ratio of 2 , the bifurcated hydrogen bonds reduce the electron density on the chloride ions in such a way that the electron repulsion decreases and coordination spheres with more ligand interactions develop. Obviously, water may be a successful competitor for ligand sites in 2 as well. The octahedral and square‐pyramidal structural units condense into polymeric chains which are stabilized by the interchain hydrogen bond networks of the water molecules. The structure motif of SP‐5‐[ OC ‐ 6 ‐ SP ‐ 5 ‐ SP ‐ 5 ]‐OC‐6 (−CuCl 5 ‐[CuCl 4 (OH 2 ) 2 ‐CuCl 5 CuCl 5 ]‐CuCl 4 (OH 2 ) 2 ‐) were observed in 2 , and the two neighboring square‐pyramidal units were found to be localized in a transoid position. The IR and ESR spectroscopical characterization of complexes was also performed.