Ferrer Sacramento, Lloret Francesc, Bertomeu Ignacio, Alzuet Gloria, Borrás Joaquín, García-Granda Santiago, Liu-González Malva, Haasnoot Jaap G
Departament de Química Inorgànica, Universitat de València, 46100 Burjassot, Valencia, Spain.
Inorg Chem. 2002 Nov 4;41(22):5821-30. doi: 10.1021/ic020179+.
New copper(II) complexes of the cyclic trinuclear type with 1,2,4-triazole ligands, Cu(3)(mu(3)-OH)(aaat)(3)(H(2)O)(3)(2).H(2)O [Haaat = 3-acetylamino-5-amino-1,2,4-triazole] (1) and ([Cu(3)(mu(3)-OH)(aat)(3)(mu(3)-SO(4))].6H(2)O)(n) [Haat = 3-acetylamino-1,2,4-triazole] (2), have been prepared and characterized by X-ray crystallography and magnetic measurements. Compound 1, the first reported with the ligand (H)aaat, consists of discrete trinuclear cations, associated NO(3)(-) anions and lattice water molecules. Compound 2 consists of unusual chains of trinuclear units with a tridentate sulfato group linking the trimeric units and water molecules stabilizing the crystal lattice. In both complexes, 1 and 2, the trinuclear [Cu(3)(OH)L(3)] unit contains a pyramidal Cu(3)-mu(3)OH core, and an almost flat Cu(3)N(6) ring formed by the N,N-bridging triazolato groups. The Cu...Cu' intratrimeric distances are 3.35-3.37-3.39 A in 1 and 3.34-3.34-3.36 A in 2. The copper atoms are five-coordinated with a distorted square-pyramidal geometry. Magnetic measurements have been performed in the 1.9-300 K temperature range. In the high-temperature region (T > 90 K), experimental data could be satisfactorily reproduced by using an isotropic exchange model, H = -J(S(1)S(2) + S(2)S(3) + S(1)S(3)), with J = -194.6 cm(-1) and g = 2.08 for 1, and J = -185.1 cm(-1) and g = 2.10 for 2. The magnitude of the antiferromagnetic exchange in both complexes is discussed on the basis of their structural features by comparison with reported N,N-pheripherically bridged trinuclear systems. In order to fit the experimental magnetic data at low temperature, an antisymmetric exchange term, H(AS) = G(S(1)xS(2) + S(2)xS(3) + S(1)xS(3)), had to be introduced, with G = 27.8 (1) and 31.0 (2) cm(-1). Crystal data: C(12)H(27)Cu(3)N(17)O(14) (1) (MW = 824.13) crystallizes in the triclinic space group, P(-)1, Z = 2, with the cell dimensions a = 8.852(2) A, b = 11.491(3) A, c = 15.404(3) A, alpha = 70.43(3) degrees, beta = 75.11(2) degrees, gamma = 88.43(2) degrees, and V = 1423.8(5) A(3), D(calcd) = 1.922 g cm(-)(3); the final agreement values were R1 = 0.0822 and wR2 = 0.2300 for 4989 unique reflections. C(12)H(28)Cu(3)N(12)O(14)S (2) (MW = 787.14) crystallizes in the triclinic space group, P(-)1, Z = 2, with the cell dimensions a = 7.146(6) A, b = 14.26(1) A, c = 15.35(2) A, alpha = 109.0(9) degrees, beta = 93.6(9) degrees, gamma = 99.5(7) degrees, and V = 1448(2) A(3), D(calcd) = 1.806 g cm(-3); the final agreement values were R1 = 0.0628 and wR2 = 0.1571 for 3997 "observed" reflections.
具有1,2,4 - 三唑配体的环状三核型新型铜（II）配合物，Cu(3)(μ(3)-OH)(aaat)(3)(H(2)O)(3)(2).H(2)O [Haaat = 3 - 乙酰氨基 - 5 - 氨基 - 1,2,4 - 三唑]（1）和([Cu(3)(μ(3)-OH)(aat)(3)(μ(3)-SO(4))].6H(2)O)(n) [Haat = 3 - 乙酰氨基 - 1,2,4 - 三唑]（2），已通过X射线晶体学和磁性测量进行了制备和表征。化合物1是首次报道含有配体（H）aaat，由离散的三核阳离子、相关的NO(3)(-)阴离子和晶格水分子组成。化合物2由不寻常的三核单元链组成，一个三齿硫酸根连接三聚体单元，水分子稳定晶格。在配合物1和2中，三核[Cu(3)(OH)L(3)]单元包含一个金字塔形的Cu(3)-μ(3)OH核心，以及由N,N - 桥连三唑基团形成的几乎扁平的Cu(3)N(6)环。1中三聚体内Cu...Cu'距离为3.35 - 3.37 - 3.39 Å，2中为3.34 - 3.34 - 3.36 Å。铜原子为五配位，具有扭曲的四方锥几何构型。在1.9 - 300 K温度范围内进行了磁性测量。在高温区域（T > 90 K），使用各向同性交换模型H = -J(S(1)S(2) + S(2)S(3) + S(1)S(3))，对于1，J = -194.6 cm(-1)且g = 2.08；对于2，J = -185.1 cm(-1)且g = 2.10，实验数据能够得到满意的再现。通过与报道的N,N - 周边桥连三核体系比较，基于它们的结构特征讨论了两种配合物中反铁磁交换的大小。为了拟合低温下的实验磁性数据，必须引入一个反对称交换项H(AS) = G(S(1)xS(2) + S(2)xS(3) + S(1)xS(3))，对于1，G = 27.8 (1)；对于2，G = 31.0 (2) cm(-1)。晶体数据：C(12)H(27)Cu(3)N(17)O(14)（1）（分子量 = 824.13）在三斜空间群P(-)1中结晶，Z = 2，晶胞参数a = 8.852(2) Å，b = 11.491(3) Å，c = 15.404(3) Å，α = 70.43(3)°，β = 75.11(2)°，γ = 88.43(2)°，V = 1423.8(5) Å(3)，D(calcd) = 1.922 g cm(-)(3)；对于4989个独立反射，最终一致性值R1 = 0.0822，wR2 = 0.2300。C(12)H(28)Cu(3)N(12)O(14)S（2）（分子量 = 787.14）在三斜空间群P(-)1中结晶，Z = 2，晶胞参数a = 7.146(6) Å，b = 14.26(1) Å，c = 15.35(2) Å，α = 109.0(9)°，β = 93.6(9)°，γ = 99.5(7)°，V = 1448(2) Å(3)，D(calcd) = 1.806 g cm(-3)；对于3997个“观测”反射，最终一致性值R1 = 0.0628，wR2 = 0.1571。
