Complexes of copper(II) formate with 2-(phenylamino)pyridine and 2-(methylamino)pyridine:: New copper paddle-wheel compounds

被引:15
作者
Barquín, Montserrat
Gonzalez Garmendia, Maria J.
Larrínaga, Liher
Pinilla, Elena
Torres, Maria R.
机构
[1] Univ Basque Country, EHU, Fac Ciencias Quim, Grp Quim Inorgan, San Sebastian 20080, Spain
[2] Univ Complutense, Fac Ciencias Quim, Lab Difracc Rayos X, E-28040 Madrid, Spain
[3] Univ Complutense, Fac Ciencias Quim, Dept Quim Inorgan, E-28040 Madrid, Spain
关键词
copper; hydrogen bonds; dimers; formate; antiferromagnetism; EPR;
D O I
10.1016/j.ica.2006.02.031
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The derivatives of Cu(HCOO)(2)center dot 4H(2)O with 2-(phenylamino)pyridine and 2-(methylamino)pyridine, [Cu-2(mu-HCOO)(4)(PhNHpy)(2)] (1), [Cu-2(mu-HCOO)(4)(MeNHpy)(2)] (2) and Cu(HCOO)(2)(MeNHpy)(2) (3), have been synthesized and characterized. Compounds 1 and 2 show the paddle-wheel structure of [Cu-2(mu-HCOO)(4)L-2], with four syn-syn bridging formato groups and two molecules of PhNHpy or MeNHpy coordinated to the axial positions, respectively. Intramolecular hydrogen bonds are formed in both cases: two in each dimer of I and four in the dimer of compound 2. The dimer units are oriented in two different directions. Dimers with the same orientation form rows along the "c" and the "a" axis in compounds 1 and 2, respectively, with a pi-pi stacking of the pyridine rings. In compound 1, an intercalation of the phenyl rings of contiguous rows of dimers gives rise to a succession of phenyl rings at a distance of 4.38 angstrom and an angle of 30.44 degrees between alternate rings. They are antiferromagnetic. Signals of the triplet state are observed in their EPR spectra and the zero-field splitting parameter has been determined. Compound 3 obeys the Curie Weiss law and the magnetic results indicate the absence of magnetic interaction between Cu(II) atoms. (c) 2006 Elsevier B.V. All rights reserved.
引用
收藏
页码:2424 / 2430
页数:7
相关论文
共 21 条
[1]   SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF COPPER(II) COMPOUNDS CONTAINING NITROGEN SULFUR DONOR LIGANDS - THE CRYSTAL AND MOLECULAR-STRUCTURE OF AQUA[1,7-BIS(N-METHYLBENZIMIDAZOL-2'-YL)-2,6-DITHIAHEPTANE]COPPER(II) PERCHLORATE [J].
ADDISON, AW ;
RAO, TN ;
REEDIJK, J ;
VANRIJN, J ;
VERSCHOOR, GC .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1984, (07) :1349-1356
[2]   Synthesis, spectroscopic and EPR results and crystal structure of copper(II) formato derivatives with pyrazine and dimethylpyrazines [J].
Barquín, M ;
Garmendia, MJG ;
Larrínaga, L ;
Pinilla, E ;
Torres, MR .
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 2005, 631 (11) :2210-2214
[3]   Synthesis, crystal structure, magnetic properties and EPR spectra of copper(II) acetate derivatives:: tetra-(μ-acetato)bis(2-methylaminopyridine)copper(II) and catena-poly(aquadiacetato-μ-3-aminomethylpyridine)copper(II).: Sheets formed by chains connected through hydrogen-bonds [J].
Barquín, M ;
Garmendia, MJG ;
Pacheco, S ;
Pinilla, E ;
Quintela, S ;
Seco, JM ;
Torres, MR .
INORGANICA CHIMICA ACTA, 2004, 357 (11) :3230-3236
[4]  
Bencini A.Gatteschi., 1990, EPR of Exchange Coupled Systems
[5]  
BUKOWSKASTRZYZE.M, 1966, ROCZ CHEM, V40, P567
[6]  
Carlin R. L, 1986, MAGNETOCHEMISTRY
[7]  
CATTERICK J, 1977, ADV INORG CHEM, V20, P291
[8]   Crystal structure, magnetic and spectroscopic properties of copper(II) formato dimethylformamide:: a new tetracarboxylato-bridged copper(II) dimer [J].
Cejudo, R ;
Alzuet, G ;
Borrás, J ;
Liu-González, M ;
Sanz-Ruiz, F .
POLYHEDRON, 2002, 21 (11) :1057-1061
[9]  
DEMEESTER P, 1973, J CHEM SOC DA, P2575
[10]  
DOEDENS RJ, 1976, PROGR INORG CHEM, V21, P209