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A New Class of Heterobinuclear Complexes: Crystal Structure and Magnetism of Copper(II)‐Nickel(II) Complexes Incorporating Two Different Macrocyclic Ligands
Author(s) -
Gao EnQing,
Tang JinKui,
Liao DaiZheng,
Jiang ZongHui,
Yan ShiPing,
Wang GengLin
Publication year - 2001
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/1522-2675(20010418)84:4<908::aid-hlca908>3.0.co;2-q
Subject(s) - chemistry , nickel , crystallography , copper , crystal structure , magnetism , ion , magnetic susceptibility , tetrahedral molecular geometry , infrared spectroscopy , stereochemistry , condensed matter physics , organic chemistry , physics
Three novel oxamido‐bridged heterobinuclear copper(II)‐nickel(II) complexes incorporating two different tetraazamacrocyclic compounds were synthesized and characterized by IR, ESR, and electronic spectra. They are of the formulas [(CuL 1 )Ni( rac ‐cth)](ClO) 42 ⋅H 2 O ( 1 ), [Cu(L 2 )Ni( rac ‐cth)](ClO 4 ) 2 ⋅0.5 EtOH ( 2 ), and [(CuL 3 )Ni( rac ‐cth)](ClO 4 ) 2 ⋅H 2 O ( 3 ). L 1 , L 2 , and L 3 are the dianions of diethyl 5,6,7,8,16,17‐hexahydro‐6,7‐dioxo‐15 H ‐dibenzo[ e , n ][1,4,8,12]tetraazacyclopentadecine‐13,19‐dicarboxylate, diethyl 5,6,7,8,15,16‐hexahydro‐6,7‐dioxodibenzo[1,4,8,11]tetraazacyclotetracine‐13,18‐dicarboxylate, and diethyl 5,6,7,8,15,16‐hexahydro‐15‐methyl‐6,7‐dioxodibenzo[1,4,8,11]tetraazacyclotetradecine‐13,18‐dicarboxylate, respectively, and rac ‐cth is rac ‐5,7,7,12,14,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane. The crystal structures of 1 and 2 were determined by single‐crystal X‐ray analysis. The Ni II ion is pseudooctahedrally coordinated. The coordination geometry around the Cu II ion in 2 is slightly distorted square planar, while that in 1 shows significant distortion towards a tetrahedral structure. The temperature dependence of the magnetic susceptibility for 1 and 2 was analyzed by means of the Hamiltonian Hˆ =−2 J Sˆ 1 ⋅ Sˆ 2 , leading to J =−63.9 and −67.4 cm −1 for 1 and 2 , respectively.