Synthesis, Crystal Structure, Thermal Analysis and Magnetic Behavior of a Novel One-Dimensional Polymeric Pyridinium Chlorocuprate(II): (Hpy)2[Cu3Cl8(H2O)2]

✍ Scribed by Rahul Bhattacharya; Ashutosh Ghosh; Mau Sinha Ray; Lara Righi; Gabriele Bocelli; Siddhartha Chaudhuri; Roger D. Willett; Juan M. Clemente-Juan; Eugenio Coronado; Carlos J. Goméz-Garcia

• Publisher: John Wiley and Sons
• Year: 2003
• Tongue: English
• Weight: 186 KB
• Volume: 2003
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200300110

✦ Synopsis

Abstract

A one‐dimensional polymeric pyridinium chlorocuprate (HPy)~2~[Cu~3~Cl~8~(H~2~O)~2~], an intermediate between (HPy)CuCl~3~ and CuCl~2~·2H~2~O, has been synthesized and characterized by X‐ray analysis [monoclinic, __P__2~1~/c, a = 7.8950(10), b = 14.144(2), c = 9.921(10) Å, β = 99.20(2)°]. The structure contains [Cu~3~Cl~8~(H~2~O)~2~]~n~^2^^n^^−^ chains in which both square‐pyramidal and octahedral Cu^II^ exist. The chains are composed of linked [Cu~2~Cl~6~]^2−^ dimers and CuCl~2~(H~2~O)~2~ monomeric units. On being heated in the solid state the compound undergoes dehydration followed by dehydrohalogenation to produce a pyridine complex of Cu^II^: [Cu~3~Py~2~Cl~6~]. Other compounds, (HPy)~2~[CuCl~4~], CuPyCl~2~ and CuPy~2~Cl~2~, also produce [Cu~3~Py~2~Cl~6~] as an intermediate on thermal analysis. Magnetic studies reveal ferromagnetic coupling within the chains with an intradimer exchange coupling of 12.1 cm^−1^ and a dimer‐monomer exchange coupling of 1.34 cm^−1^. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)