Supramolecular Networks in Crystalline Inclusion Complexes Formed from a New Host: 2,2-Bis(4-hydroxy-3-phenylphenyl)-1<i>H</i>-indene-1,3(2<i>H</i>)-dione

A scissors-shaped compound, 2,2-bis(4-hydroxy-3-phenylphenyl)-1H-indene-1,3(2H)-dione (1), has been prepared as a new host species for crystalline host–guest complexes. Compound 1 afforded complexes of 1:1 host-to-guest ratio with acetone, EtOH, and CH2Cl2, and a 2:3 complex with benzene. The crystal structures of these complexes were elucidated. In all four crystals, a side-by-side dimer linked by head-to-tail >CO···HO– hydrogen bonds is formed and functions as the building unit of supramolecular networks. Except for (1)2(benzene)3, the complexes featured intermolecular carbonyl–carbonyl interactions resulting in all-planar antiparallel alignment with markedly short C···O distances (< 3.15 Å). In (1)(EtOH), the four-centered interaction including two hydroxyl and two carbonyl groups was observed and designated as a quasi-bifurcated hydrogen bonding motif. Such a four-centered interaction has been observed to occur widely in crystal structures as proved by database searches from the Cambridge Structural Database (CSD). In all the crystals, the host molecules formed a channel-type void occupied by guest molecules. The crystal structure of the desolvated crystals of 1 has been elucidated for its polycrystalline solids by ab initio structure determination from powder X-ray diffraction data followed by the Rietveld refinement.