Abstract

Transition metal carboxylates with O- and N-donor ligands are interesting for their structural features. Seven novel isonicotinamide(inic)-based metal complexes of [Cd(inic)₂(L1)₂(H₂O)₂] · 2H₂O (1) (L1 = 2-chloronicotinate), [Cd(inic)₂(L2)₂(H₂O)₂] (2) (L2 = 2,4-dichlorobenzoate), [Cu(inic)₂(L3)₂] (3) (L3 = 4-chlorophenoxyacetate), [Cu₃(inic)₆(L4)₂(HL4)₂(H₂O)₂] · 2H₂O (4) (L4 = azelate), [Zn(inic)₂(L1)₂(H₂O)₂] · (inic) · H₂O (5), [Zn(inic)(L5)(H₂O)₄] (6) (L5 = 3-nitrophthalate) and [Zn₂(inic)₂(L6)₂] · 5H₂O (7) (L6 = 1,4-cyclohexanedicarboxylate) have been obtained by the introduction of the carboxylates by the common solution method and are structurally featured by different techniques of EA, IR spectra, TG and SCXRD analysis. The X-ray studies told that these complexes display mononuclear to trinuclear structures with octahedral/square-pyramidal geometry around the Zn²⁺, trigonal bipyramidal/octahedral at the Cu²⁺ and octahedral for the Cd²⁺. The inic in 1–7 are coordinated only in monodentate fashion with its ring N, while 5 has the lattice inic. The carboxylates coordinated to the metal in monodentate, chelating bidentate and bridging bidentate fashions. The pair of complementary N-H···O H-bonds from the CONH₂ of the inic were found in all compounds except 7. Except 1 and 2, all other compounds bear the CH-O contacts from the pyridine CH of the inic. The intricate intra- and intermolecular classical H-bonds, CH-N, CH-O, CH-Cl, CH₂-O, O-N, O-O, Cl-O, Cl-Cl, CH-π, CH₂-π, C-π, N-π, Cl-π and π-π associations are elucidated by the X-ray crystallographic studies, which push the discrete complexes into high-dimensional ordered supramolecular structures.

摘要

具有 O 和 N 供体配体的过渡金属羧酸盐因其结构特征而令人感兴趣。[Cd(inic) ₂ (L1) ₂ (H ₂ O) ₂ ] · 2H ₂ O (1) (L1  =  2-氯烟酸盐)、[Cd(inic) ₂ ( L2) ₂ (H ₂ O) ₂ ] (2) (L2  =  2,4-二氯苯甲酸盐), [Cu(inic) ₂ (L3) ₂ ] (3) (L3 = 4-氯苯氧基乙酸盐), [Cu ₃ (inic) ) ₆ (L4) ₂(HL4) ₂ (H ₂ O) ₂ ] · 2H ₂ O (4) (L4 = azelate), [Zn(inic) ₂ (L1) ₂ (H ₂ O) ₂ ] · (inic) · H ₂ O ( 5) , [Zn(inic)(L5)(H ₂ O) ₄ ] (6) (L5 = 3-硝基邻苯二甲酸酯) 和 [Zn ₂ (inic) ₂ (L6) ₂ ] · 5H ₂ O (7)(L6 = 1,4-环己烷二羧酸盐) 是通过常用溶液法引入羧酸盐而获得的，并通过 EA、IR 光谱、TG 和 SCXRD 分析的不同技术在结构上进行了表征。X 射线研究表明，这些配合物显示出单核到三核结构，在 Zn ²⁺周围具有八面体/方形锥体几何形状，在 Cu ²⁺处为三角双锥体/八面体，而 Cd ²⁺则为八面体。1 – 7中的 inic仅与其环 N 以单齿方式协调，而5有格子 inic。羧酸盐以单齿、螯合双齿和桥接双齿方式与金属配位。除了7外，所有化合物中都发现了来自 inic的 CONH ₂的一对互补的 NH…O氢键。除了1和2 之外，所有其他化合物都带有来自 inic 的吡啶 CH 的 CH-O 触点。复杂的分子内和分子间经典 H 键，CH-N、CH-O、CH-Cl、CH ₂ -O、ON、OO、Cl-O、Cl-Cl、CH-π、CH ₂ -π、C -π、N-π、Cl-π 和 π-π 结合由 X 射线晶体学研究阐明，将离散复合物推向高维有序超分子结构。