Crystal structure of cis-7,8-dihy-droxy-5,10,15,20-tetra-phenyl-chlorin and its zinc(II)-ethyl-enedi-amine complex

Acta Crystallogr E Crystallogr Commun. 2022 Mar 15;78(Pt 4):392-398. doi: 10.1107/S2056989022002729. eCollection 2022 Apr 1.

Abstract

The title chlorin, 2PhH2 , hydrogen-bonded to di-methyl-amino-pyridine (DMAP), C44H32N4O2·C7H10N2, and its corresponding zinc(II) complex, 2PhZn, axially coordinated to ethyl-enedi-amine (EDA), [Zn(C44H30N4O2)]·C2H8N2, were isolated and crystallized by adventitious reduction of the corresponding osmate esters by DMAP and EDA, respectively. Known since 1996 and, inter alia, 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 meso-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 vic-cis diols on the pyrroline moiety; the resulting deformation of the pyrroline translates in some cases into the macrocycle. The structure of 2PhH2 features voids making up ca 26% of the unit-cell volume filled with highly disordered solvate mol-ecules (chloro-form and hexa-nes). 2PhZn crystallized with a 13.6 (4)% occupied solvate methanol mol-ecule.

Keywords: crystal structure; hydro­porphyrins; meso-phenyl­chlorins; porphyrinoids; β-hy­droxy­chlorin.

Grants and funding

This work was funded by National Science Foundation, Directorate for Mathematical and Physical Sciences grants CHE-1625543 and CHE-1800361 to M. Zeller and C. Brückner.