A SIMPLE SYNTHETIC ROUTE TO N,N'-DIALKYL-2,11-DIAZA[3.3](2,6)-PYRIDINOPHANES - CRYSTAL-STRUCTURES OF N,N'-DI-TERT-BUTYL-2,11-DIAZA[3.3](2,6)PYRIDINOPHANE AND ITS COPPER(II) COMPLEX
A SIMPLE SYNTHETIC ROUTE TO N,N'-DIALKYL-2,11-DIAZA[3.3](2,6)-PYRIDINOPHANES - CRYSTAL-STRUCTURES OF N,N'-DI-TERT-BUTYL-2,11-DIAZA[3.3](2,6)PYRIDINOPHANE AND ITS COPPER(II) COMPLEX
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DOI：
10.1016/s0277-5387(00)81683-6
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发表时间：
1994-03-01
期刊：
影响因子：
2.6
通讯作者：
PENG, SM
中科院分区：
文献类型：
--
作者：
CHE, CM;LI, ZY;PENG, SM
2，6-二（溴甲基）吡啶与伯胺反应，得到12元N，N '-二烷基-2，11-二氮杂[3.3]（2，6）吡啶并吡喃。本文报道了N，N '-二叔丁基-2，11-二氮杂[3.3]（2，6）吡啶并苯（4）及其铜（Ⅱ）衍生物[Cu（4）Cl_2]（7）的晶体结构。7中的平均轴向Cu-N（叔胺）距离为2.490埃，明显长于Cu（6）Cl 2中的相关值2.347埃。H2O.4在4中，两个平面吡啶环不在同一平面上，但大致平行，大环的12个原子构成syn chair-chair构象。在配合物7中，铜（II）离子采用扭曲的八面体几何形状，其中叔胺氮原子跨越轴向位置近似垂直于由两个吡啶氮和氯配体形成的正方形平面。Cu-N（叔胺）、Cu-N（吡啶）和Cu-Cl的平均距离分别为2.49（2）、2.03（2）和2.287（7）埃。
Reaction of 2,6-bis(bromomethyl)pyridine with primary amines gave the 12-membered N,N'-dialkyl-2,11-diaza[3.3](2,6)pyridinophanes. The structures of N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane (4) and its copper(II) derivative [Cu(4)Cl2] (7) have been characterized by X-ray crystal analysis. The average axial Cu-N (tertiary amine) distance of 2.490 angstrom in 7 is appreciably longer than the related value of 2.347 angstrom in Cu(6)Cl2 . H2O.4 In 4, the two planar pyridyl rings are not in the same plane, but roughly parallel and the 12 atoms of the macrocyclic ring constitute a syn chair-chair conformation. In complex 7, the copper(II) ion adopts a distorted octahedral geometry, in which the tertiary amine nitrogen atoms span axial positions approximately normal to the square plane formed by the two pyridine nitrogens and the chloro ligands. The average Cu-N (tertiary amine), Cu-N(pyridine) and Cu-Cl distances are 2.49(2), 2.03(2) and 2.287(7) angstrom, respectively.