Churchill Serena B S, Sharma Meenakshi, Brückner Christian, Zeller Matthias
Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060, USA.
Department of Chemistry, Purdue University, 560 Oval Dr., W. Lafayette, IN 47907-2084, USA.
Acta Crystallogr E Crystallogr Commun. 2020 Jul 7;76(Pt 8):1222-1228. doi: 10.1107/S2056989020009093. eCollection 2020 Aug 1.
The title morpholino-chlorin, CHFNO, was crystallized from hexa-ne/methyl-ene chloride as its 0.44 methyl-ene chloride solvate, CHFNO·0.44CHCl. The morpholino-chlorin was synthesized by stepwise oxygen insertion into a porphyrin using a 'breaking and mending strategy': NaIO-induced diol cleavage of the corresponding 2,3-di-hydroxy-chlorin with methanol-induced, acid-catalyzed intra-molecular ring closure of the inter-mediate secochlorins bis-aldehyde. Formally, one of the pyrrolic building blocks was thus replaced by a 2,3-di-meth-oxy-morpholine moiety. Like other morpholino-chlorins, the macrocycle of the title compound adopts a ruffled conformation, and the modulation of the porphyrinic π-system chromophore induces a red-shift of its optical spectrum compared to its corresponding chlorin analog. Packing in the crystal is governed by inter-actions involving the fluorine atoms of the penta-fluoro-phenyl substituents, dominated by C-H⋯F inter-actions, and augmented by short fluorine⋯fluorine contacts, C-F⋯π inter-actions, and one severely slipped π-stacking inter-action between two penta-fluoro-phenyl rings. The solvate methyl-ene chloride mol-ecule is disordered over two independent positions around an inversion center with occupancies of two × 0.241 (5) and two × 0.199 (4), for a total site occupancy of 88%.
标题化合物吗啉代二氢卟吩（CHFNO）以其0.44的二氯甲烷溶剂化物CHFNO·0.44CH₂Cl的形式从己烷/二氯甲烷中结晶出来。吗啉代二氢卟吩是通过使用“断裂与修复策略”将氧逐步插入卟啉中合成的：用NaIO诱导相应的2,3 - 二羟基二氢卟吩二醇裂解，并通过甲醇诱导、酸催化中间体开链二氢卟吩双醛的分子内环合。形式上，其中一个吡咯结构单元因此被一个2,3 - 二甲氧基吗啉部分取代。与其他吗啉代二氢卟吩一样，标题化合物的大环采取褶皱构象，并且卟啉π - 体系发色团的调制导致其光谱相对于相应的二氢卟吩类似物发生红移。晶体中的堆积由涉及五氟苯基取代基氟原子的相互作用控制，主要是C - H⋯F相互作用，并通过短的氟⋯氟接触、C - F⋯π相互作用以及两个五氟苯环之间的一个严重滑移的π - 堆积相互作用增强。溶剂化的二氯甲烷分子在一个反演中心周围的两个独立位置上无序排列，占有率分别为两个×0.241（5）和两个×0.199（4），总位点占有率为88%。
