A synchrotron study of [5, 10, 15, 20‐tetrakis(3‐cyanophenyl)porphyrinato‐κ4N5, N10, N15, N20]copper(II) nitrobenzene trisolvate at 80 K. Issue 11 (7th October 2016)

• Record Type: Journal Article
• Authors: Seidel, Rüdiger W.; Goddard, Richard; Mayer-Gall, Thomas; Oppel, Iris M.
• Is Part Of: Acta crystallographica. Volume 72:Issue 11(2016)
• Page Start: 861
• Page End: 866
• Publication Date: 2016-10-07
• Subjects: porphyrin -- crystal structure -- planar macrocycle -- fourfold symmetry -- copper(II) -- synchrotron; Crystallography -- Periodicals; Crystals -- Periodicals; 548.3
• DOI: 10.1107/S2053229616015515
• Languages: English
• ISSNs: 2053-2296

Abstract

Abstract : [5, 10, 15, 20‐Tetrakis(3‐cyanophenyl)porphyrinato]copper(II) exhibits a C 2 h ‐symmetric ααββ conformation, despite an unsymmetrical crystal environment, and is situated on a crystallographic centre of symmetry. The Cu II ion adopts a genuine square‐planar coordination by the four pyrrole N atoms. Abstract : Porphyrin assemblies display interesting photophysical properties and a relatively high thermal stability. Moreover, meso ‐functionalized porphyrins with virtually fourfold symmetry can be relatively readily synthesized from pyrrole and the appropriate aldehyde. A number of metallo derivatives of 5, 10, 15, 20‐tetrakis(4‐cyanophenyl)porphyrin, where the N atom of the linear cyano group can act both as a donor for coordination bonds or as an acceptor for hydrogen bonds, have been structurally characterized by single‐crystal X‐ray analysis. The supramolecular and structural chemistry of the corresponding 2‐ and 3‐cyanophenyl isomers of the parent porphyrin, however, has remained largely unexplored. The crystal structure of [5, 10, 15, 20‐tetrakis(3‐cyanophenyl)porphyrinato]copper(II) (CuTCNPP) nitrobenzene trisolvate, [Cu(C48 H24 N8 )]·3C6 H5 NO2, has been determined at 80 K by synchrotron single‐crystal X‐ray diffraction. CuTCNPP exhibits a C 2 h ‐symmetric ααββ conformation, despite an unsymmetrical crystal environment, and is situated on a crystallographic centre of symmetry. The Cu II ion adopts a genuine square‐planar coordination by the four pyrrole N atoms. The 24‐membered porphyrin ring system shows no marked deviation from planarity. In the crystal, the CuTCNPP molecules and two nitrobenzene molecules are face‐to‐face stacked in an alternating fashion, resulting in corrugated layers. The remaining nitrobenzene guest molecule per CuTCNPP resides in the region between four neighbouring columnar stacks of CuTCNPP and sandwiched nitrobenzene molecules, and is disordered over four positions about a centre of symmetry.