Chaudhri Nivedita, Brückner Christian, Zeller Matthias
Department of Chemistry, University of Connecticut, Storrs, CT 06269-3060, USA.
Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN, 47907-2084, USA.
Acta Crystallogr E Crystallogr Commun. 2022 Mar 15;78(Pt 4):392-398. doi: 10.1107/S2056989022002729. eCollection 2022 Apr 1.
The title chlorin, , hydrogen-bonded to di-methyl-amino-pyridine (DMAP), CHNO·CHN, and its corresponding zinc(II) complex, , axially coordinated to ethyl-enedi-amine (EDA), [Zn(CHNO)]·CHN, were isolated and crystallized by adventitious reduction of the corresponding osmate esters by DMAP and EDA, respectively. Known since 1996 and, , used for the preparation of a wide range of (planar and non-planar) chlorin analogues (so-called pyrrole-modified porphyrins), their conformational analyses in the solid state are important benchmarks. Both macrocycles are only modestly distorted from planarity and both are slightly more non-planar than the corresponding dimeth-oxy-derivative, but less planar than a free-base -penta-fluoro-phenyl-based osmate ester. NSD analyses provide qu-anti-tative and qualitative analyses of the distortion modes. One origin of the non-planarity is presumably the avoidance of the eclipsed configuration of the two diols on the pyrroline moiety; the resulting deformation of the pyrroline translates in some cases into the macrocycle. The structure of features voids making up 26% of the unit-cell volume filled with highly disordered solvate mol-ecules (chloro-form and hexa-nes). crystallized with a 13.6 (4)% occupied solvate methanol mol-ecule.
二氢卟吩（chlorin）（ ）与二甲基氨基吡啶（DMAP，CHNO·CHN）形成氢键，其相应的锌（II）配合物（ ）与乙二胺（EDA）轴向配位，[Zn(CHNO)]·CHN，分别通过DMAP和EDA对相应锇酸酯的偶然还原而分离并结晶。自1996年以来已知，并且 ，用于制备各种（平面和非平面）二氢卟吩类似物（所谓的吡咯修饰卟啉），它们在固态下的构象分析是重要的基准。两个大环仅略微偏离平面性，并且两者都比相应的二甲氧基衍生物略微更非平面，但比游离碱五氟苯基锇酸酯更平面。NSD分析提供了畸变模式的定量和定性分析。非平面性的一个来源可能是避免吡咯啉部分上两个二醇的重叠构型；吡咯啉产生的变形在某些情况下会转化为大环。 的结构具有占单位晶胞体积26%的空隙，其中填充有高度无序的溶剂化分子（氯仿和己烷）。 结晶时含有13.6 (4)%被占据的溶剂化甲醇分子。
