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

Abstract

A one‐dimensional polymeric pyridinium chlorocuprate (HPy)2[Cu3Cl8(H2O)2], an intermediate between (HPy)CuCl3 and CuCl2·2H2O, has been synthesized and characterized by X‐ray analysis [monoclinic, P21/c, a = 7.8950(10), b = 14.144(2), c = 9.921(10) Å, β = 99.20(2)°]. The structure contains [Cu3Cl8(H2O)2]n2n− chains in which both square‐pyramidal and octahedral CuII exist. The chains are composed of linked [Cu2Cl6]2− dimers and CuCl2(H2O)2 monomeric units. On being heated in the solid state the compound undergoes dehydration followed by dehydrohalogenation to produce a pyridine complex of CuII: [Cu3Py2Cl6]. Other compounds, (HPy)2[CuCl4], CuPyCl2 and CuPy2Cl2, also produce [Cu3Py2Cl6] 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)

Halide-bridged polymers of divalent metals with donor ligands – structures and properties

“…Within chain polymers of Cu(II), Jahn-Teller distortions are responsible for the coexistence of less regular polyhedra such as distorted square-planar and elongated octahedral [175] or squarepyramidal and elongated octahedral coordination [176,177].…”

catena-Poly[1,4-dihydroxy-1,4-diazoniabicyclo[2.2.2]octane [aquatri-μ-chlorido-trichloridodicuprate(II)]]

“…The structural properties of chlorocuprates continue to be of interest because of their wide variety of stereochemical features and unexpected oligomeric species (Smith, 1976), as well as their significance for the elucidation of magnetostructural correlations (Manfredini et al, 1990;Bhattacharya et al, 2003) and the study of phase transitions (Bloomquist et al, 1988;Zhang et al, 2010Zhang et al, , 2012. Hydrated chlorocuprates, due to the possibility of their forming hydrogen bonds, are more complicated structurally than chlorocuprates.…”

“…Hydrated chlorocuprates, due to the possibility of their forming hydrogen bonds, are more complicated structurally than chlorocuprates. Among the hydrated chlorocuprates, many types of monomeric and polymeric species, such as [CuCl 2 (H 2 O) 2 ] species (Pabst & Bats, 1985;Sarangarajan et al, 2008), [CuCl(H 2 O)] À complexes (Valle & Ettorre, 1992;Manfredini et al, 1990), [CuCl 4 (H 2 O)] 2À compounds (Dobrzycki & Wozniak, 2008) and [Cu 2 Cl 5 (H 2 O)] À (Bond & Willett, 1987, 1989 and [Cu 3 Cl 8 (H 2 O) 2 ] 2À species (Bhattacharya et al, 2003), have been reported in recent decades. However, to the best of our knowledge, the [Cu 2 Cl 6 (H 2 O)] 2À species has not been reported previously.…”

Structural and spectroscopic properties of bis-3-picolinium 1,8-naphthalimide tetrachlorocuprate

“…The tetrachlorocuprates have interesting structural properties [1][2][3][4][5][6]. Depending on the cations tetrachlorocuprates show thermochromicity [7][8][9].…”