Magneto-Structural Relationships in a Series of Dinuclear Oxalato-Bridged (Diphenyldipyrazolylmethane)copper(II) Complexes
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- 作者：Janet L. Shaw ; Gordon T. Yee ; Guangbin Wang ; David E. Benson ; Cagil Gokdemir ; and Christopher J. Ziegler
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：July 11, 2005
- 年：2005
- 卷：44
- 期：14
- 页码：5060 - 5067
- 全文大小：215K
- 年卷期：v.44,no.14(July 11, 2005)
- ISSN：1520-510X
文摘
A series of oxalato-bridged dinuclear copper(II) complexes of the general formula [Cu2(Pz2CPh2)2(X)2(
-C2O4)](X = Cl- (1), NO3- (2), ClO4- (3); Pz2CPh2 = diphenyldipyrazolylmethane) or [Cu2(Pz3m2CPh2)2(H2O)2(-C2O4)](NO3)2·H2O (4) (Pz3m2CPh2 = diphenylbis(3-methylpyrazolyl)methane) was synthesized where the axial ligand wassystematically varied to study its effect on structure and magnetic coupling. The structures of compounds 1, 2, and4 have been elucidated by single-crystal X-ray diffraction. [Cu2(Pz2CPh2)2(Cl)2(-C2O4)] and [Cu2(Pz2CPh2)2(NO3)2(-C2O4)] are isostructural and crystallize in the triclinic system, space group P
, Z = 2, with a = 8.6155(8) Å, b= 10.1435(9) Å, c = 11.3612(11) Å, 
chars/alpha.gif" BORDER=0> = 95.535(2)
, chars/beta2.gif" BORDER=0 ALIGN="middle"> = 110.303(2), and chars/gamma.gif" BORDER=0 > = 106.111(2) for 1 and with a= 8.863(7) Å, b = 10.241(9) Å, c = 11.425(10) Å, chars/alpha.gif" BORDER=0> = 98.985(14), chars/beta2.gif" BORDER=0 ALIGN="middle"> = 110.449(13), and chars/gamma.gif" BORDER=0 > = 103.664(14)for 2. [Cu2(Pz3m2CPh2)2(H2O)2(-C2O4)]·NO3·H2O crystallizes in the monoclinic system, space group C2/c, Z = 4,with a = 23.4588(14) Å, b = 8.8568(5) Å, c = 21.7818(13) Å, chars/alpha.gif" BORDER=0> = chars/gamma.gif" BORDER=0 > = 90, and chars/beta2.gif" BORDER=0 ALIGN="middle"> = 100.8890(10). Variable-temperature magnetic susceptibility studies indicate that all four compounds are strongly antiferromagnetically coupled(2J/k = -364, -344 cm-1 (2), -424 cm-1 (3), and -378 cm-1 (4)). Magnetic and EPR results are discussed withrespect to structural parameters to explore possible magneto-structural correlations.
-C2O4)](X = Cl- (1), NO3- (2), ClO4- (3); Pz2CPh2 = diphenyldipyrazolylmethane) or [Cu2(Pz3m2CPh2)2(H2O)2(-C2O4)](NO3)2·H2O (4) (Pz3m2CPh2 = diphenylbis(3-methylpyrazolyl)methane) was synthesized where the axial ligand wassystematically varied to study its effect on structure and magnetic coupling. The structures of compounds 1, 2, and4 have been elucidated by single-crystal X-ray diffraction. [Cu2(Pz2CPh2)2(Cl)2(-C2O4)] and [Cu2(Pz2CPh2)2(NO3)2(-C2O4)] are isostructural and crystallize in the triclinic system, space group P, Z = 2, with a = 8.6155(8) Å, b= 10.1435(9) Å, c = 11.3612(11) Å, chars/alpha.gif" BORDER=0> = 95.535(2), chars/beta2.gif" BORDER=0 ALIGN="middle"> = 110.303(2), and chars/gamma.gif" BORDER=0 > = 106.111(2) for 1 and with a= 8.863(7) Å, b = 10.241(9) Å, c = 11.425(10) Å, chars/alpha.gif" BORDER=0> = 98.985(14), chars/beta2.gif" BORDER=0 ALIGN="middle"> = 110.449(13), and chars/gamma.gif" BORDER=0 > = 103.664(14)for 2. [Cu2(Pz3m2CPh2)2(H2O)2(-C2O4)]·NO3·H2O crystallizes in the monoclinic system, space group C2/c, Z = 4,with a = 23.4588(14) Å, b = 8.8568(5) Å, c = 21.7818(13) Å, chars/alpha.gif" BORDER=0> = chars/gamma.gif" BORDER=0 > = 90, and chars/beta2.gif" BORDER=0 ALIGN="middle"> = 100.8890(10). Variable-temperature magnetic susceptibility studies indicate that all four compounds are strongly antiferromagnetically coupled(2J/k = -364, -344 cm-1 (2), -424 cm-1 (3), and -378 cm-1 (4)). Magnetic and EPR results are discussed withrespect to structural parameters to explore possible magneto-structural correlations.