A synchrotron study of [5,10,15,20-tetrakis(3-cyanophenyl)porphyrinato-κ4N5,N10,N15,N20]copper(II) nitrobenzene trisolvate at 80 K.
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(C48H24N8)]·3C6H5NO2, has been determined at 80 K by synchrotron single-crystal X-ray diffraction. CuTCNPP exhibits a C2h-symmetric ααββ conformation, despite an unsymmetrical crystal environment, and is situated on a crystallographic centre of symmetry. The CuIIion 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.
Lehrstuhl für Analytische Chemie, Ruhr-Universität Bochum, Universitätsstrasse 150, 44780 Bochum, Germany.
Rüdiger W
RW
Seidel
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
Richard
R
Goddard
Deutsches Textilforschungszentrum Nord-West gGmbH, Institut an der Universtiät Duisburg-Essen, Adlerstrasse 1, 47798 Krefeld, Germany.
Thomas
T
Mayer-Gall
Institut für Anorganische Chemie, Rheinisch-Westfälische Technische Hochschule Aachen, Landoltweg 1, 52074 Aachen, Germany.
Iris M
IM
Oppel
copper(II); crystal structure; fourfold symmetry; planar macrocycle; porphyrin; synchrotron