A Two-Dimensional Oxamate- and Oxalate-Bridged CuIImnII motif: Crystal Structure and Magnetic Properties of (Bu4N)2[Mn2{Cu(opba)}2ox]

被引：31
作者：
Marinho, Maria V. [1 ]
Simoes, Tatiana R. G. [2 ]
Ribeiro, Marcos A. [2 ,3 ]
Pereira, Cynthia L. M. [2 ]
Machado, Flavia C. [4 ]
Pinheiro, Carlos B. [3 ]
Stumpf, Humberto O. [2 ]
Cano, Joan [5 ]
Lloret, Francesc [1 ]
Julve, Miguel [1 ]
机构：
[1] Univ Valencia, Fac Quim, Inst Ciencia Mol, Dept Quim Inorgan, Paterna 46980, Valencia, Spain
[2] Univ Fed Minas Gerais, ICEX, Dept Quim, BR-31270901 Belo Horizonte, MG, Brazil
[3] Univ Fed Minas Gerais, ICEX, Dept Fis, BR-31270901 Belo Horizonte, MG, Brazil
[4] Univ Fed Juiz de Fora, ICE, Dept Quim, BR-36036330 Juiz De Fora, MG, Brazil
[5] Univ Valencia, FGUV, Paterna 46980, Valencia, Spain
来源：
INORGANIC CHEMISTRY | 2013年 / 52卷 / 15期
关键词：
MOLECULE-BASED MAGNETS; DECOUPLED CELL METHOD; SINGLE-CHAIN MAGNETS; X-RAY; SUPRAMOLECULAR STRUCTURES; COORDINATION-COMPOUNDS; COPPER(II) COMPLEXES; BIMETALLIC CHAINS; BUILDING-BLOCK; MU-OXALATO;
D O I：
10.1021/ic401038c
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
A new compound of formula (Bu4N)(2)[M(n)2{Cu(opba)}(2)ox] (1) [Bu4N+ = tetra-n-butylammonium cation, H4opba = 1,2-phenylenebis(oxamic acid), and H(2)ox = oxalic acid] has been synthesized and magnetostructurally investigated. The reaction of manganese(II) acetate, [Cu(opba)](2-), and ox(2-) in dimethyl sulfoxide yielded single crystals of 1. The structure of 1 consists of heterobimetallic oxamato-bridged (CuMnII)-Mn-II chains which are connected through bis-bidentate oxalate coordinated to the manganese(II) ions to afford anionic heterobimetallic layers of 6(3)-hcb net topology. The layers are interleaved by n-Bu4N+ counterions. Each copper(II) ion in 1 is four-coordinate in a square planar environment defined by two amidate-nitrogen and two carboxylate-oxygen atoms from the two oxamate groups of the obpa ligand. The manganese(II) ion is six-coordinate in a somewhat distorted octahedral surrounding that is built by two oxalate-oxygen and four carbonyl-oxygen atoms from two [Cu(opba)](2-) units. The magnetic properties of 1 in the temperature range 1.9-300 K correspond to those expected for the coexistence of intralayer antiferromagnetic interactions of the type copper(1I) manganese(11) across oxamato and manganese(II)-manganese(II) through oxalato bridges plus a weak spin canting in the very low temperature domain. Simulation of the magnetic data through quantum Monte Carlo methodology reveals the magnitude of the intralayer magnetic interactions [J(CuMn) = 32.5(3) cm(-1), and J(CuMn) = 2.7(3) cm(-1)], their values being within the range of those previously observed in lower nuclearity systems.
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页码：8812 / 8819
页数：8
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