Temperature Tuned Synthesis of Zinc N,N-bis-(1(2)H-tetrazol-5-yl)-amine Complexes : From Zn3O Cluster-Based 3-Connected 63-hcb and (3,6)-Connected (43)2(46)-kgd Layers to Zn5(OH)4 Chain-Based 3D Open Framework
Temperature Tuned Synthesis of Zinc N,N-bis-(1(2)H-tetrazol-5-yl)-amine Complexes : From Zn3O Cluster-Based 3-Connected 63-hcb and (3,6)-Connected (43)2(46)-kgd Layers to Zn5(OH)4 Chain-Based 3D Open Framework
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DOI：
10.1021/cg800248b
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发表时间：
2008-06
影响因子：
3.8
通讯作者：
T. Jiang;Xian‐Ming Zhang
中科院分区：
文献类型：
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作者：
T. Jiang;Xian‐Ming Zhang
在Zn（II）离子存在下，双氰胺和叠氮化合物在120、150和180 °C水热原位[2 + 3]环加成反应分别生成[Zn 4 O（Hbta）3（H2O）6] 1、[Zn 7（OH）2（Hbta）6（H2O）6] 2和[Zn 5（OH）4（bta）2]·2 H2O 3（H3 bta = N，N-双-（1（2）H-四唑-5-基）-胺）. 1晶体属六方晶系P62 c空间群，具有3-连通63-hcb拓扑结构，其中Zn_3 O团簇和不饱和三配位Zn（II）离子作为3-连通节点; 2在三角空间群P3 c1中结晶并且也显示出层状结构，（6）-连通（43）2（46）-kgd拓扑结构，其中Zn_3 O团簇和六配位Zn（II）位分别作为3-连通节点和6-连通节点; 3是由Zn 5（OH）4链构建的3D有机-无机杂化开放框架。三重去质子化的bta 3 −阴离子首次在3中观察到，罕见的三配位Zn（II）离子在1中发现。结构与合成条件的关系分析表明，1是一个多环芳烃。
Hydrothermal in situ [2 + 3] cycloaddition reaction of dicyanamide and azide in the presence of Zn(II) ions at 120, 150, and 180 °C generated [Zn4O(Hbta)3(H2O)6] 1, [Zn7(OH)2(Hbta)6(H2O)6] 2, and [Zn5(OH)4(bta)2]·2H2O 3 (H3bta = N,N-bis-(1(2)H-tetrazol-5-yl)-amine), respectively. 1crystallizes in hexagonal space group P62c and shows a layered structure with 3-connected 63-hcb topology in which Zn3O clusters and unsaturated three-coordinate Zn(II) ions function as 3-connected nodes; 2crystallizes in trigonal space group P3c1 and also shows a layered structure with (3,6)-connected (43)2(46)-kgd topology in which Zn3O clusters and six-coordinated Zn(II) sites function as 3-connected nodes as 6-connected nodes, respectively; 3 is a 3D organic−inorganic hybrid open framework constructed by Zn5(OH)4 chains. The triply deprotonated bta3− anion is first observed in 3, and rare three-coordinate Zn(II) ions are revealed in 1. Analysis of relationship between structure and synthesis condition reveals that 1 is a m...