Crystal structure of 2,3-dimeth­oxy-meso-tetra­kis(penta­fluoro­phen­yl)morpholino­chlorin methyl­ene chloride 0.44-solvate

The title morpholino­chlorin, C(46)H(16)F(20)N(4)O(3), was crystallized from hexa­ne/methyl­ene chloride as its 0.44 methyl­ene chloride solvate, C(46)H(16)F(20)N(4)O(3)·0.44CH(2)Cl(2). The morpholino­chlorin was synthesized by stepwise oxygen insertion into a porphyrin using a ‘breaking and mending strategy’: NaIO(4)-induced diol cleavage of the corresponding 2,3-di­hydroxy­chlorin with in situ methanol-induced, acid-catalyzed intra­molecular ring closure of the inter­mediate secochlorins bis­aldehyde. Formally, one of the pyrrolic building blocks was thus replaced by a 2,3-di­meth­oxy­morpholine moiety. Like other morpholino­chlorins, 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 inter­actions involving the fluorine atoms of the penta­fluoro­phenyl substituents, dominated by C—H⋯F inter­actions, and augmented by short fluorine⋯fluorine contacts, C—F⋯π inter­actions, and one severely slipped π-stacking inter­action between two penta­fluoro­phenyl rings. The solvate methyl­ene chloride mol­ecule 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%.