Reactions of Cu(hfacac)2•H2O (hfacac = hexafluoroacetylacetonate) with bidentate ligands.: Preparation, characterization, and X-ray structures of the molecular complexes Cu(hfacac)2(pyrazine)2 and Cu(hfacac)2(3-cyanopyridine)2 and the one-dimensional coordination polymers Cu(hfacac)2(1,2-bis(4-pyridyl)ethane) and Cu(hfacac)2(4,4′-trimethylenebipyridine)

被引:117
作者
Dong, YB [1 ]
Smith, MD [1 ]
Layland, RC [1 ]
zur Loye, HC [1 ]
机构
[1] Univ S Carolina, Dept Chem & Biochem, Columbia, SC 29208 USA
关键词
D O I
10.1021/ic9906104
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reactions of Cu(hfacac)(2). H2O (hfacac = hexafluoroacetylacetonate) with pyrazine, 3-cyanopyridine, 1,2-bis(4-pyridyl)ethane, and 4,4'-trimethylenebipyridine in methylene chloride have been studied. Two types of products were obtained and crystallographically characterized: compounds 1 (Cu(hfacac)(2)(pyrazine)(2), orthorhombic, Pbca; a = 9.839(2) Angstrom, b = 17.984(2) Angstrom, c = 13.572(2) Angstrom, Z = 4) and 2 (Cu(hfacac)(2)(3-cyanopyridine)(2), triclinic, P (1) over bar, a = 13.175(2) Angstrom, b = 13.955(2) Angstrom, c = 7.936(2) Angstrom, alpha = 104.29(2)degrees, beta = 105.90 degrees, gamma = 81.47(1)degrees, Z = 2) were isolated as molecular complexes, while compounds 3 (Cu(hfacac)(2)(1,2-bis(4-pyridyl)ethane, monoclinic, P2(1)/c, a = 7.922(1) Angstrom, b = 16.266(4) Angstrom, c = 10.163(2) Angstrom, beta = 93.83(1)degrees Z = 2) and 4 (Cu(hfacac)(2)(4,4'-trimethylenebipyridine), monoclinic, Pc, a = 7.940(1) Angstrom, b = 9.691(2) Angstrom, c = 18.539(3) Angstrom, beta = 95.83(2)degrees, Z = 2) were isolated as one-dimensional infinite polymeric chains. The structures were further characterized by infrared spectroscopy, thermogravimetry, and elemental analysis; additionally, the magnetic behavior of all compounds was investigated and found to follow the Curie law. All four compounds feature similar 4 + 2 pseudooctahedral coordination environments around the Cu(II) centers composed of square-planar Cu(hfacac)(2) units with the N-donor ligands occupying the trans positions. The length of the N-donor ligands determines the formation of either molecular complexes (1 and 2, short ligands) or infinite polymeric structures (3 and 4, longer ligands). Important C-F ... H-C hydrogen-bonding interactions in compounds 1 and 3 play a significant role in aligning the molecules and the polymer strands in the crystalline solids.
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页码:5027 / 5033
页数:7
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