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“栅栏”卟啉(穴状配体-222)氯[中-α,α,α,α-四(邻-新戊酰胺基苯基)卟啉合]铁(II)正己烷单溶剂合物的适度畸变

A moderate distortion of the `picket-fence' porphyrin (cryptand-222)potassium chlorido[meso-α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrinato]ferrate(II) n-hexane monosolvate.

作者信息

Yu Qiang, Liu Diansheng, Li Xiangjun, Li Jianfeng

机构信息

Research Institute of Applied Chemistry and College of Chemistry and Chemical Engineering, Shanxi University, Taiyuan, Shanxi 030006, People's Republic of China.

College of Materials Science and Opto-electronic Technology, University of Chinese Academy of Sciences, Yianqi Lake, Huairou District, Beijing 101408, People's Republic of China.

出版信息

Acta Crystallogr C Struct Chem. 2015 Oct;71(Pt 10):856-9. doi: 10.1107/S2053229615015478. Epub 2015 Sep 18.

Abstract

As representative porphyrin model compounds, the structures of `picket-fence' porphyrins have been studied intensively. The title solvated complex salt {systematic name: (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane)potassium(I) [5,10,15,20-tetrakis(2-tert-butanamidophenyl)porphyrinato]iron(II) n-hexane monosolvate}, [K(C18H36N2O6)][Fe(C64H64N8O4)Cl]·C6H14 or [K(222)][Fe(TpivPP)Cl]·C6H14 [222 is cryptand-222 or 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, and TpivPP is meso-α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrinate(2-)], [K(222)][Fe(TpivPP)Cl]·C6H14, is a five-coordinate high-spin iron(II) picket-fence porphyrin complex. It crystallizes with a potassium cation chelated inside a cryptand-222 molecule; the average K-O and K-N distances are 2.81 (2) and 3.05 (2) Å, respectively. One of the protecting tert-butyl pickets is disordered. The porphyrin plane presents a moderately ruffled distortion, as suggested by the atomic displacements. The axial chloride ligand is located inside the molecular cavity on the hindered porphyrin side and the Fe-Cl bond is tilted slightly off the normal to the porphyrin plane by 4.1°. The out-of-plane displacement of the metal centre relative to the 24-atom mean plane (Δ24) is 0.62 Å, indicating a noticeable doming of the porphyrin core.

摘要

作为典型的卟啉模型化合物,“栅栏”卟啉的结构已得到深入研究。标题溶剂化配合物盐{系统名称:(4,7,13,16,21,24 - 六氧杂 - 1,10 - 二氮杂双环[8.8.8]二十六烷)钾(I)[5,10,15,20 - 四(2 - 叔丁酰胺基苯基)卟啉合]铁(II)正己烷单溶剂化物},[K(C₁₈H₃₆N₂O₆)][Fe(C₆₄H₆₄N₈O₄)Cl]·C₆H₁₄或[K(222)][Fe(TpivPP)Cl]·C₆H₁₄ [222为穴状配体 - 222或4,7,13,16,21,24 - 六氧杂 - 1,10 - 二氮杂双环[8.8.8]二十六烷,且TpivPP为中位 - α,α,α,α - 四(邻新戊酰胺基苯基)卟啉酸根(2 - )],[K(222)][Fe(TpivPP)Cl]·C₆H₁₄,是一种五配位高自旋铁(II)栅栏卟啉配合物。它结晶时,钾阳离子螯合在穴状配体 - 222分子内部;平均K - O和K - N距离分别为2.81 (2) Å和3.05 (2) Å。其中一个保护叔丁基栅栏是无序的。如原子位移所示,卟啉平面呈现适度的起伏扭曲。轴向氯配体位于受阻卟啉侧的分子腔内,且Fe - Cl键相对于卟啉平面法线略微倾斜4.1°。金属中心相对于24原子平均平面(Δ24)的面外位移为0.62 Å,表明卟啉核心有明显的隆起。

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