Crystal supramolecularity: hexagonal arrays of sextuple phenyl embraces amongst chemically diverse compounds

The sextuple phenyl embrace (SPE) occurs widely between molecules with XR3 (R = aryl) moieties, and has at least quasi-three-fold symmetry. The SPE can have exact 3 symmetry, and therefore can be aligned with the principal axis of trigonal crystal lattices. Using the Cambridge Structural Database we report that this does occur in the crystals of a chemically diverse set of compounds, ranging from P(C6H4Me-4)(3) and Ph3CCO2H, through salts such as [Ph3PH+](2)[Ga2Cl6](2-) and [Ph3PMe+](2)[Cu4I6](2-), small molecules such as Ph3PAlMe3 and Ph3POs(CO)(3)PPh3, to larger molecules such as Ph3SiOTiN(CH2CH2O)(3) and Ph3PCu(mu-SPh)(3)U(mu-SPh)(3)-CuPPh3(thf)(6) (thf = tetrahydrofuran). The XR3 moieties and the SPEs occur in hexagonal nets, and this generic crystal structure type (in space groups <R(3)over bar>, <P(3)over bar>, R(3) over barc$, <P(3)over bar cl>) is named the hexagonal array of sextuple phenyl embraces, HASPE. The hexagonal nets can be planar, or puckered by expansion or compression along the trigonal axis. The linkages around these hexagonal nets can be further multiple phenyl embraces, or may be elongated substantially. The non-embracing sections of the molecules can occupy the centres of the hexagons. The HASPE lattice type shows considerable flexibility in order to accommodate diverse components, but the integrity of the SPEs is maintained, attesting to their strong contribution to the lattice energy. Lower symmetry portions of molecular structure, and lower symmetry supramolecular motifs such as the CO2H ... HO2C dimer, are forced to disorder by the dominant hexagonal array of SPEs. Quasi HASPE lattices with lower crystal symmetry have been recognised.