化学学报 ›› 2000, Vol. 58 ›› Issue (6): 675-682. 上一篇    下一篇

研究论文

铜(Ⅱ)与α,β-不饱和酸根和乙酰胺配合物的合成、 表征、晶体结构和磁性

王尧宇;时茜;史启祯;高忆慈   

  1. 西北大学化学系.西安(710069);兰州大学化学系.兰州(730000)
  • 发布日期:2000-06-15

Syntheses, characterization, crystal structure and magnetic properties of copper(Ⅱ) α,β-unsaturated carboxylate complexes with acetamide

Wang Yaoyu;Shi Qian;Shi Qizhen;Gao Yici   

  1. Northwest Univ, Dept Chem.Xian(710069);Lanzhou Univ, Dept Chem. Lanzhou(730000)
  • Published:2000-06-15

合成了铜(Ⅱ)与丙烯酸根和乙酰胺及铜(Ⅱ)与α-甲基丙烯酸根和乙酰胺两种配合物,进行了元素分析、红外光谱、电子光谱、ESR谱和变温磁化等研究,确定配合物的组成为Cu~2A~4(C~2H~5NO)~2,其中A=CH~2=CHCOO^-,CH~2=C(CH~3)COO^-;C~2H~5NO=乙酰胺,测定了它们的晶体结构。Cu~2(CH~2=CHCOO)~4(C~2H~5NO)~2(1)晶体属单斜晶系,P2~1/c群;晶胞参数:a=1.5333(5)nm,b=1.0044(3)nm,c=1.6184(7)nm,β=115.28(3)°;Z=4;最终偏离因子R=0.0701。Cu~2[CH~2=C(CH~3)COO]~4(C~2H~5NO)~2(2)晶体属三斜晶系,P1群;晶胞参数:a=0.93327(11)nm,b=1.12484(11)nm,c=1.3740(6)nm,α=94.90(2)°,β=108.409(14)°,γ=110.556(5)°;Z=2;最终偏离因子R=0.0351。配合物中Cu(Ⅱ)具有畸变的四角锥形配位环境,两个Cu(Ⅱ)由四个α,β-不饱和酸根桥联,在Cu(Ⅱ)的端位各有一个乙酰胺分子以O原子配位。Cu(Ⅱ)-Cu(Ⅱ)间具有一对称中心。配合物1中Cu(Ⅱ)-Cu(Ⅱ)间距离为0.26302(13)nm,配合物2中Cu(Ⅱ)-Cu(Ⅱ)间距离为0.26383(4)nm。变温磁化率研究表明,两种配合物中Cu(Ⅱ)-Cu(Ⅱ)间具有强烈的反铁磁性偶合作用。

关键词: 铜络合物, 乙酰胺P, 晶体结构, 甲基丙烯酸P, 元素分析, 红外分光光度法, 电子自旋共振

Two copper(Ⅱ) α,β-unsaturated carboxylate complexes with acetamide, Cu~2(CH~2=CHCOO)~4(C~2H~5NO)~2(1) and Cu~2[CH~2=C(CH~3) COO]~4(C~2H~5NO)~2(2), have been synthesized and characterized by elemental analyses, IR, ESR, electronic spectra and magnetic studies. The single crystal X-ray diffraction study of two complexes shows that complex 1 crystallizes in the monolinic space group with P2~1/c, a=1.5333(5) nm, b=1.0044(3) nm, c=1.6184(7) nm, β=115.28(3)°, Z=4, and R=0.0701, while complex 2 is triclinic, with space group P1, a=0. 93327(11) nm, b=1.12484(11) nm, c=1.3740(6) nm, α=94.90(2)°, β=108. 409(14)°,γ=110.556(5)°, Z=2 and R=0.0351. Two copper(Ⅱ) atoms are bridged by four α,β-unsaturated carboxylate groups, with each copper(Ⅱ) atom coordinated with an acetamide molecule in the axial position, forming a distorted square pyramidal configuration. The symmetric center is between the two copper(Ⅱ) atoms. The Cu-Cu bond distance is 0.26302(13) nm for the complex 1 and 0.26383(4)nm for the complex 2. The Cu-Cu distance and magnetic studies suggest that there exist antiferromagnetic interaction between two copper(Ⅱ) atoms.

Key words: COPPER COMPLEX, ACETAMIDE P, CRYSTAL STRUCTURE, METHYLPROPENOIC ACID P, ELEMENTAL ANALYSIS, INFRARED SPECTROPHOTOMETRY, ELECTRON SPIN RESONANCE

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