CRYSTAL-STRUCTURE AND SPECTROSCOPIC AND MAGNETIC-PROPERTIES OF 2 NOVEL MONO(MU-HALO) COPPER(II) CHAINS WITH AN UNUSUAL ZIGZAG ARRANGEMENT - [CU(C13H13N3)X]PF6 (X=CL,BR)

被引:45
作者
CORTES, R
LEZAMA, L
DELARRAMENDI, JIR
MADARIAGA, G
MESA, JL
ZUNIGA, FJ
ROJO, T
机构
[1] UNIV BASQUE COUNTRY, DEPT QUIM INORGAN, E-48080 BILBAO, SPAIN
[2] UNIV BASQUE COUNTRY, DEPT FIS MAT CONDENSADA, E-48080 BILBAO, SPAIN
关键词
D O I
10.1021/ic00108a006
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Three new compounds [Cu(C13H13N3)Cl)(PF6).nH(2)O [n = 1 (1); n = 0 (2)] and [Cu(C13H13N3)Br](PF6) (3), where C13H13N3 = pepci = N-(2-pyridylethyl)pyridine-2-carbaldimine, have been synthesized and the crystal structures of 2 and 3 determined at room temperature. Both compounds crystallize in the orthorhombic system, space group Pc2(1)b and Z = 16, with cell parameters of a = 7.804(2) Angstrom, b = 24.686(4) Angstrom, c = 34.376(9) Angstrom, and V = 6623(3) Angstrom(3) for compound 2 and a = 7.904(3) Angstrom, b = 24.816(3) Angstrom, c = 34.289(4) Angstrom, and V = 6726(3) Angstrom(3) for compound 3. The structure of 2 was refined to an R value of 0.068 (R(w) = 0.055), while the structure of 3 was refined to R = 0.071 (R(w) = 0.067). Both structures consist of [Cu(pepci)X](+) (X = Cl, Br) cations which stack along the a axes and PF6- anions sited in the interchain space. In the stack, two successive copper complexes ate in an alternating orientation, to give a novel zigzag mono(mu-halide) chain structure. There are four independent [Cu(pepci)X](PF6) molecules in the unit cell, which are repeated four times. The chloro compounds 1 and 2 are not isostructural phases, compound 1 being characterized as a dimer. Magnetic properties of the compounds have been investigated down to 4 K. The chloro complexes exhibit weak antiferromagnetic interactions, while the bromo one is ferromagetic. The magnetic susceptibility data for both chains (2 and 3) have been fitted by using a linear chain model. The obtained parameters are J/k = -2.0 K (1.39 cm(-1)) (2) and J/k = +1 K (0.70 cm(-1)) (3). However, the data corresponding to complex 1 have been fitted to a dimer system, with an exchange coupling constant of -3.0 K (2.09 cm(-1)). Magneto-structural correlations in the chloro-bridged chains have been analyzed by using extended Huckel molecular orbital calculations.
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页码:778 / 786
页数:9
相关论文
共 43 条
[1]  
Albright T. A., 1985, ORBITAL INTERACTIONS
[2]   MAGNETIC EXCHANGE INTERACTIONS IN ONE-DIMENSIONAL COOPER(II) COMPOUNDS [J].
ALEMANY, P ;
ALVAREZ, S .
CHEMISTRY OF MATERIALS, 1990, 2 (06) :723-728
[3]  
[Anonymous], 1974, INT TABLES XRAY CRYS, VIV
[4]   HIGH-TEMPERATURE SERIES EXPANSIONS FOR SPIN-1-2 HEISENBERG MODEL BY METHOD OF IRREDUCIBLE REPRESENTATIONS OF SYMMETRIC GROUP [J].
BAKER, GA ;
RUSHBROOKE, GS ;
GILBERT, HE .
PHYSICAL REVIEW, 1964, 135 (5A) :1272-+
[5]   PREPARATION, CRYSTAL AND MOLECULAR-STRUCTURE OF AQUADICHLOROCAFFEINECOPPER(II) [J].
BANDOLI, G ;
CINGIBIAGINI, M ;
CLEMENTE, DA ;
RIZZARDI, G .
INORGANICA CHIMICA ACTA, 1976, 20 (01) :71-78
[6]  
BELTRANPORTER D, 1987, NATO ARW SERIES, P433
[7]   ANOMALOUS PARAMAGNETISM OF COPPER ACETATE [J].
BLEANEY, B ;
BOWERS, KD .
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1952, 214 (1119) :451-465
[8]   LINEAR MAGNETIC CHAINS WITH ANISOTROPIC COUPLING [J].
BONNER, JC ;
FISHER, ME .
PHYSICAL REVIEW, 1964, 135 (3A) :A640-+
[9]   STRUCTURAL CHARACTERIZATION OF DICHLORO[2-(2-METHYLAMINOETHYL)PYRIDINE]COPPER(II) [J].
BREAM, RA ;
ESTES, ED ;
HODGSON, DJ .
INORGANIC CHEMISTRY, 1975, 14 (07) :1672-1675
[10]   SIR88 - A DIRECT-METHODS PROGRAM FOR THE AUTOMATIC SOLUTION OF CRYSTAL-STRUCTURES [J].
BURLA, MC ;
CAMALLI, M ;
CASCARANO, G ;
GIACOVAZZO, C ;
POLIDORI, G ;
SPAGNA, R ;
VITERBO, D .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1989, 22 :389-393