Face-to-Face Stacking and Saddle Distortion of 5,10,15,20-Tetra(4-hydroxyphenyl)porphyrinatocopper(II) in Two New Solvates

Abstract

The crystal structures of the methanol nitrobenzene sesquisolvate hemihydrate (1) and the 3.75-dimethyl sulfoxide solvate monohydrate (2) of 5,10,15,20-tetra(4-hydroxyphenyl)porphyrinatocopper(II) (CuTOHPP) are reported. Both 1 and 2 crystallise in the triclinic system with two molecules of the metalloporphyrin in the asymmetric unit (Z′ = 2). Compound 1 exhibits an extended two-dimensional hydrogen-bonded network in the crystal, whereas discrete hydrogen-bonded assemblies of CuTOHPP and solvent molecules are found in 2. Face-to-face stacking of the metalloporphyrin units and O–H⋯O hydrogen bonding interactions are identified as the most important solid-state organisational features in both 1 and 2. Saddle distortion of the metalloporphyrin units is encountered in both new solvates and there are no Cu⋯O interactions, despite four hydroxy groups on each porphyrin ligand and the presence of oxygen donor solvent molecules. The methanol nitrobenzene sesquisolvate hemihydrate and the 3.75-dimethyl sulfoxide solvate monohydrate of 5,10,15,20-tetra(4-hydroxyphenyl)porphyrinatocopper(II) both crystallise in the triclinic system with two molecules in the asymmetric unit (Z′ = 2), featuring face-to-face stacking of the saddle-distorted metalloporphyrin units.