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用2,6-二氰基吡啶与叠氮化钠在水热条件下原位合成了5种6-四氮唑-2-吡啶甲酸配合物:[Ni2(tepc)2(H2O)2](1),[Co2(tepc)2(H2O)4]2H2O(2),[Co2(tepc)2(H2O)4]4H2O(3),[Cu2(tepc)2(H2O)2](4)和{[Mn(tepc)(H2O)2]2H2O}n(5)(tepc=6-(tetrazol-5-yl)picolinate).这些配合物中配体均以三齿螯合的方式与金属离子配位.配合物1~4形成了双核离散型配合物,双核分子通过氢键作用连接成三维超分子结构.配合物5中的单核螯合单元间通过Mn–O配位键连接成为一维配位聚合物链,链间通过氢键连接成为整个配合物的晶体结构.氢键拓扑网络分析表明,配合物1和2可简化成NaCl型的6-连接pcu拓扑网,配合物3则可简化成一种8-连接hex拓扑网,配合物4可简化成一种新型双结点十连接拓扑网络(310·426·58·6)(38·426·510·6),配合物5则可简化成一种新型的(5,10)双结点三维网络(32·47·5)(34·421·513·67).本文不仅详细地分析了这些配合物晶体结构中氢键与拓扑网络之间的关系,而且还讨论了氰基的水解反应与四氮唑成环反应间的关系,以及金属离子的电子特征、结晶条件与晶体结构之间的关系.
Five kinds of 6-tetrazolium-2-pyridinecarboxylic acid complexes were synthesized in situ using 2,6-dicyanopyridine and sodium azide under hydrothermal conditions: [Ni2 (tepc) 2 (H2O) 2] 1], [Co2 (tepc) 2 (H2O) 4] 2H2O (2), [Co2 (tepc) 2 (H2O) 4] 4H2O (3), [Cu2 (tepc) 2 {(Mn (tepc) (H2O) 2] 2H2O} n (5) (tepc = 6- (tetrazol-5-yl) picolinate) The ligands in these complexes are all chelated with metal ions The complexes 1 ~ 4 form a binuclear discrete complex, which is connected to a three-dimensional supramolecular structure through hydrogen bonding. The mononuclear chelate units in complex 5 are connected by Mn-O coordination bonds into one-dimensional Coordination polymer chain, the chain through the hydrogen bond to become the crystal structure of the entire complex.H hydrogen bond topology network analysis showed that complexes 1 and 2 can be simplified into NaCl type 6-connected pcu topology network, the complex 3 can be Reduced to an 8-connected hex topology network, Complex 4 simplifies to a new two-junction, ten-junction topology network (310 · 426 · 58 · 6) (38 · 426 · 510 · 6). Complex 5 simplifies Into a new kind of (5,10) dual-node three-dimensional network (32.47.55) (34.411.513.37) .In this paper, we not only analyzed the crystal structure of these complexes The relationship between the hydrogen and the topology of the network, but also discusses the hydrolysis reaction with a cyano tetrazolium ring into the relationship between the reaction, and the electrical characteristics of the metal ion, the relationship between the crystal structure and the crystallization conditions.