Abstract

The title compound, [Ni(C64H33F10N5S2)]·xCH2Cl2, consists of discrete NiII porphyrin complexes, in which the five-coordinate NiII cations are in a distorted square-pyramidal coordination geometry. The four porphyrin nitro-gen atoms are located in the basal plane of the pyramid, whereas the pyridine N atom is in the apical position. The porphyrin plane is strongly distorted and the NiII cation is located above this plane by 0.241 (3) Å and shifted in the direction of the coordinating pyridine nitro-gen atom. The pyridine ring is not perpendicular to the N4 plane of the porphyrin moiety, as observed for related compounds. In the crystal, the complexes are linked via weak C-H⋯F hydrogen bonds into zigzag chains propagating in the [001] direction. Within this arrangement cavities are formed, in which highly disordered di-chloro-methane solvate mol-ecules are located. No reasonable structural model could be found to describe this disorder and therefore the contribution of the solvent to the electron density was removed using the SQUEEZE option in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9-18].

Highlights

  • The title compound, [Ni(C64H33F10N5S2)]ÁxCH2Cl2, consists of discrete NiII porphyrin complexes, in which the five-coordinate NiII cations are in a distorted square-pyramidal coordination geometry

  • The four porphyrin nitrogen atoms are located in the basal plane of the pyramid, whereas the pyridine N atom is in the apical position

  • The porphyrin plane is strongly distorted and the NiII cation is located above this plane by 0.241 (3) Aand shifted in the direction of the coordinating pyridine nitrogen atom

Read more

Summary

Chemical context

NiII porphyrins are emerging in a number of applications including photoswitchable MRI contrast agents (Venkataramani et al, 2011; Dommaschk et al, 2014, 2015a,b), redox catalysts (Eom et al, 1997; Han et al, 2015) or catalysts in the hydrogen evolution reaction (HER) (Han et al, 2016; Solis et al, 2016; Maher et al, 2019). The NiII cation is shifted 0.241 (3) Aout of the porphyrin N4 plane towards the pyridine nitrogen atom, which is slightly shorter than that in the derivative without the methyl group [0.250 (3) A , Fig. 5]. This is the case for the Ni—N distance to the pyridine N atom of 2.106 (3) A , compared to 2.112 (2) Ain the derivative.

Structural commentary
Supramolecular features
Database survey
Synthesis and crystallization
Findings
Refinement

Talk to us

Join us for a 30 min session where you can share your feedback and ask us any queries you have

Schedule a call

Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.