STRUCTURE OF A DIOXYGEN ADDUCT OF (1-METHYLIMIDAZOLE)-MESO-TETRAKIS(ALPHA-ALPHA-ALPHA-ALPHA-ORTHO-PIVALAMIDOPHENYL)PORPHINATOIRON(II) - IRON DIOXYGEN MODEL FOR HEME COMPONENT OF OXYMYOGLOBIN
STRUCTURE OF A DIOXYGEN ADDUCT OF (1-METHYLIMIDAZOLE)-MESO-TETRAKIS(ALPHA-ALPHA-ALPHA-ALPHA-ORTHO-PIVALAMIDOPHENYL)PORPHINATOIRON(II) - IRON DIOXYGEN MODEL FOR HEME COMPONENT OF OXYMYOGLOBIN
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DOI：
10.1021/ic50182a012
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发表时间：
1978-01-01
影响因子：
4.6
通讯作者：
COLLMAN, JP
中科院分区：
文献类型：
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作者：
JAMESON, GB;RODLEY, GA;COLLMAN, JP
单(l-甲基咪唑)(双氧)-meotetrakis(a, a, a, ao-新戊酰氨基苯基)卟啉铁(II),[Fe (TpivPP)(l-Me-imid)(02)]-!/2 (C6H6)'1/2 (N2C4H6)的溶剂化物的结构已使用计数器方法收集的三维X射线衍射数据确定。晶体对称性与单斜空间群C2/c或Cc一致。晶胞参数为 a= 18.690 (3) Á、b= 19.154 (3) Á、c= 18.638 (3) Á、ß= 91.00 (1) 和 Z= 4。空间群 C2/c 中结构的最小二乘细化导致传统 R 因子（在 F 上）为 0.109，使用 I> 1784 次反射一个。晶体结构由 Fe (TpivPP)(l-Me-imid)(02) 单体单元组成，苯或 1-甲基咪唑分子占据不对称单元中的一个溶剂化位点。双氧以端接弯曲键模式与铁原子配位。 Fe-0 分离度为 1.75 (2) Á。由于分子具有双重对称性，1-甲基咪唑基团和末端氧原子是无序的。叔丁基和末端氧原子也发现了额外的无序，它们也可以占据两个晶体学独立位点中的任一个，因此表现出整体四重无序。两个晶体学上独立的 0-0 间距为 1.15 (4) 和 1.17 (4) Á，各自的 Fe-0-0 键角为 133 (2) 和 129 (2)。 0-0 分离度可能被低估多达 0.15 A。Fe-N 分离度为 1.99 (1) 和 1。 97 (1) A 并且铁原子从卟啉氮原子的平均平面向双氧配体位移 0.03 A。 Fe-Nimy 分离度为 2.07 (2) A。有限的质量差的数据以及结构许多部分的无序和高热运动阻碍了精确的结构分析。
The structure of a solvate of mono (l-methylimidazole)(dioxygen)-meiotetrakis (a, a, a, ao-pivalamidophenyl) porphinatoiron (II),[Fe (TpivPP)(l-Me-imid)(02)]-!/2 (C6H6)'1/2 (N2C4H6), has been determined using three-dimensional x-ray diffraction data collected by counter methods. Crystal symmetry is consistent with the monoclinic space groups C2/c or Cc. The unit cell parameters are a= 18.690 (3) Á, b= 19.154 (3) Á, c= 18.638 (3) Á, ß= 91.00 (1), and Z= 4. Least-squares refinement of the structure in space group C2/c has led to a conventional R factor (on F) of 0.109 using 1784 reflections with I> a¡. The crystal structure consists of monomeric units of Fe (TpivPP)(l-Me-imid)(02) with benzene or 1-methylimidazole molecules occupying one solvate site in the asymmetric unit. Dioxygen is coordinated to the iron atom in the end-on bent bond mode. The Fe-0 separation is 1.75 (2) Á. As a consequence of the twofold symmetry imposed on the molqcule, the 1-methylimidazole group and the terminal oxygen atom are disordered. Additional disorder is found for the tert-butyl groups and for the terminal oxygen atom which can also occupy either of two crystallographically independent sites andwhich thus exhibits overall fourfold disorder. The two crystallographically independent 0-0 separations are 1.15 (4) and 1.17 (4) Á and the respective Fe-0-0 bond angles are 133 (2) and 129 (2). The 0-0 separations may be underestimated by as much as 0.15 A. The Fe-N,^ separations are 1.99 (1) and1. 97 (1) A and the iron atom is displaced 0.03 A from the mean plane of the porphinato nitrogen atoms toward the dioxygen ligand. The Fe-Nimy separation is 2.07 (2) A. Precise structure analysis is prevented by limited data of poor quality and by the disorder and high thermal motion of many parts of the structure.