Coordination modes of the 1,3-dithiosquarate (1,3-dtsq) ligand. Syntheses, crystal structures, and magnetic properties of [Ni(tren)(1,3-dtsq)(H2O)] and [Ni-2(tren)(2)(1,3-dtsq)](ClO4)(2) [tren equals tris(2-aminoethyl)amine]

被引:22
作者
Calatayud, ML
Castro, I
Sletten, J
Cano, J
Lloret, F
Faus, J
Julve, M
Seitz, G
Mann, K
机构
[1] UNIV VALENCIA, FAC QUIM, DEPT QUIM INORGAN, E-46100 BURJASSOT, VALENCIA, SPAIN
[2] UNIV BERGEN, KJEMISK INST, N-5007 BERGEN, NORWAY
[3] UNIV MARBURG, INST PHARMAZEUT CHEM, D-35032 MARBURG, GERMANY
基金
美国国家科学基金会;
关键词
D O I
10.1021/ic951393j
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The first X-ray crystallographic stucture determinations of metal complexes of the 1,3-dithiosquarate (1,3-dtsq, dianion of 3-hydroxy-4-mercapto-2-thioxo-3-cyclobuten-1-one) are reported herein. Compounds [Ni(tren)(1,3-dtsq)(H2O)] (C10H20N4NiO3S) (1) and [Ni-2(tren)(2)(1,3-dtsq)](ClO4)(2) (C16H36Cl2N8Ni2O10S2) (2) (where tren is tris(2-aminoethyl)amine) both crystallize in the monoclinic system, space group P2(1)/c, with a = 8.519(1) Angstrom, b = 13.931(1) Angstrom, c = 13.587(3) Angstrom, beta = 106.705(8)degrees, and Z = 4 for 1 and a = 8.663(1) Angstrom, b = 14.496(2) Angstrom, c = 11.617(2) Angstrom, beta = 98.135(9)degrees, and Z = 2 for 2. The structure of 1 consists of mononuclear, neutral [Ni(tren)(1,3-dtsq)(H2O)] complex units, whereas that of 2 is made up of dinuclear dithiosquarate-bridged cations, [Ni-2(tren)(2)(1,3-dtsq)](2+), and uncoordinated perchlorate anions. The nickel environment is distorted octahedral in both cases, the tren group acting as a tetradentate ligand through its four nitrogen atoms and the dithiosquarate being monodentately coordinated through one of the sulfur atoms in 1 and bridging bis-bidentate in 2. A water molecule which is hydrogen bonded to the neighboring carbonyl-oxygen atom of the dithiosquarate completes the octahedron around the metal atom in 1. The intradimer metal-metal separation in 2 is 7.096(1) Angstrom. Variable-temperature magnetic susceptibility measurements of complex 2 reveal the occurrence of a weak intramolecular antiferromagnetic coupling. The ability of the 1,3-dithiosquarate ligand to transmit electronic effects between metal ions has been analyzed through extended Huckel calculations. The theoretical influence of the position (1,2-dithiosquarate versus 1,3-dithiosquarate) and the number of sulfur (1,2,3,4-tetrathiosquarate) atoms on the exchange coupling through bis-bidentate thiosquarates is also considered.
引用
收藏
页码:2858 / 2865
页数:8
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