含有R2NCH2CH(OH)CH2NR2（R = H，CH3）的多核铜（II）配合物中的互补性和反互补性：晶体结构与磁性研究

Complementarity and countercomplementarity in polynuclear copper(II) complexes with R2NCH2CH(OH)CH2NR2 (R = H, CH3): crystal structures and magnetic study.

作者信息

El Fallah M Salah, Badyine Fatima, Vicente Ramon, Escuer Albert, Solans Xavier, Font-Bardia Mercè

机构信息

Departament de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028, Barcelona, Spain.

出版信息

Dalton Trans. 2006 Jun 28(24):2934-42. doi: 10.1039/b516392g. Epub 2006 Mar 13.

DOI:10.1039/b516392g

PMID:16770451

Abstract

The syntheses, structural characterization and magnetic behavior of five new copper(II) polynuclear compounds with formulae [Cu4(mu2-CH3COO)2(mu-bdmap)2(micro(1,5)-dca)2(dca)2(H2O)2] 1, [Cu2(mu2-CH3COO)(mu-bdap)(mu(1,1,5)-dca)(mu(1,3)-dca)]n 2, [Cu4(mu2-CH3COO)2(mu-bdmap)2(mu(1,1)-NCS)2(NCS)2] 3, [Cu2(mu2-CH3COO)(mu-bdap)(NCS)2] 4 and [Cu2(mu(1,3)-N3)(mu-bdmap)(N3)2]n 5 in which bdmapH is 1,3-bis(dimethylamino)-2-propanol, bdapH is 1,3-bis(amino)-2-propanol and dca is the anionic dicyanamide ligand, are reported herein. Tetranuclear complex 1 crystallizes in the monoclinic system, space group P2(1)/n, with unit cell parameters a = 8.284(8), b = 21.52(1), c = 11.432(3) A, beta = 105.19(2) degrees , Z = 2. Bi-dimensional complex 2 crystallizes in the triclinic system, space group P1, with unit cell parameters a = 8.184(5), b = 8.792(2), c = 10.887(2) A, alpha = 75.65(2), beta = 76.55(3), gamma = 74.36(3) degrees , Z = 2. Tetranuclear complex 3 crystallizes in the triclinic system, space group P1, with unit cell parameters a = 8.455(4), b = 9.114(9), c = 12.744(8) A, alpha = 104.62(8), beta = 99.86(6), gamma = 106.10(8) degrees, Z = 1. Dinuclear complex 4 crystallizes in the triclinic system, space group P1, with unit cell parameters a = 8.15(1), b = 8.18(2), c = 11.44(1) A, alpha = 69.39(2), beta = 80.36(2), gamma = 80.37(2) degrees , Z = 2. One-dimensional complex 5 crystallizes in the orthorhombic system, space group P2(1)2(1)2(1), with unit cell parameters a = 20.45(4), b = 11.36(3), c = 6.43(1) A, Z = 4. The magnetic behavior of all the complexes has been checked giving a bulk antiferromagnetic coupling in all the cases with |J| values in the range 109-144 cm(-1) for 1-4. Compound 5 is diamagnetic in the 2-300 K range of temperatures. The found J values 1-5 for can be justified from the structural data taking into account the orbital countercomplementarity for 1-4 and the orbital complementarity for 5.

摘要

本文报道了五种新的铜（II）多核化合物的合成、结构表征及磁行为，其化学式分别为[Cu4(μ2-CH3COO)2(μ-bdmap)2(μ(1,5)-dca)2(dca)2(H2O)2] 1、[Cu2(μ2-CH3COO)(μ-bdap)(μ(1,1,5)-dca)(μ(1,3)-dca)]n 2、[Cu4(μ2-CH3COO)2(μ-bdmap)2(μ(1,1)-NCS)2(NCS)2] 3、[Cu2(μ2-CH3COO)(μ-bdap)(NCS)2] 4和[Cu2(μ(1,3)-N3)(μ-bdmap)(N3)2]n 5，其中bdmapH为1,3-双（二甲氨基）-2-丙醇，bdapH为1,3-双（氨基）-2-丙醇，dca为阴离子型双氰胺配体。四核配合物1结晶于单斜晶系，空间群为P2(1)/n，晶胞参数a = 8.284(8)，b = 21.52(1)，c = 11.432(3) Å，β = 105.19(2)°，Z = 2。二维配合物2结晶于三斜晶系，空间群为P1，晶胞参数a = 8.184(5)，b = 8.792(2)，c = 10.887(2) Å，α = 75.65(2)，β = 76.55(3)，γ = 74.36(3)°，Z = 2。四核配合物3结晶于三斜晶系，空间群为P1，晶胞参数a = 8.455(4)，b = 9.114(9)，c = 12.744(8) Å，α = 104.62(8)，β = 99.86(6)，γ = 106.10(8)°，Z = 1。双核配合物4结晶于三斜晶系，空间群为P1，晶胞参数a = 8.15(1)，b = 8.18(2)，c = 11.44(1) Å，α = 69.39(2)，β = 80.36(2)，γ = 80.37(2)°，Z = 2。一维配合物5结晶于正交晶系，空间群为P2(1)2(1)2(1)，晶胞参数a = 20.45(4)，b = 11.36(3)，c = 6.43(1) Å，Z = 4。已对所有配合物的磁行为进行了检测，结果表明在所有情况下均存在体反铁磁耦合，对于1 - 4，|J|值在109 - 144 cm(-1)范围内。化合物5在2 - 300 K温度范围内呈抗磁性。考虑到1 - 4的轨道反互补性和5的轨道互补性，从结构数据可以解释所发现的1 - 5的J值。