Cooperative and Anticooperative Effects in the Cocrystals of Mono- and Diazanaphthalenes with meso-1,2-Diphenyl-1,2-ethanediol.
In: Crystal Growth & Design, Jg. 3 (2003) ; Nr. 2, S. 175-181
Zeitschriftenaufsatz / Fach: Chemie
Meso-1,2-Diphenyl-1,2-ethanediol (1) as a H-bond donor and azanaphthalenes as H-bond acceptors form cocrystals, mostly in the ratio of 1:2. The x-ray structures provide detailed information on the binding motifs that consist of strong O-H...N H bonds and C-H...p interactions between C-H bonds of the heterocycles and the Ph rings of meso-1,2-diphenyl-1,2-ethanediol. These motifs are found whenever a N atom is in the 2-position of the naphthalene skeleton (isoquinoline (3), quinazoline (2), and phthalazine (4)). N atoms in the 1,3- and 2,3-positions, 1,3-diazanaphthalene (quinazoline) (2) and 2,3-diazanaphthalene (phthalazine) (4), alter the crystal lattice only in the case of phthalazine, due to addnl. H-bond- and p-stacking interactions. If a N atom is present in 1-position of naphthalene, 1,5-diazanaphthalene (naphthyridine) (5), the bonding motif consists of O-H...N H bridges between the N atoms in the 1- and 5-positions and the O-H groups of 1 leading to infinite strings of alternating naphthyridine and diol mols. C-H...p interactions are found in this case between C-H groups of the adjacent six-membered pyridyl ring and the Ph group attached to the C atom which is not involved in the formation of O-H...N H bonds as in the other three cases. This motif enables the incorporation of a second naphthyridine mol. without leading to addnl. H bonds, but with two C-H...p interactions. Attempts to generate cocrystals between 1 and 1-azanaphthalene (quinoline) as well as a tri-cocrystal between 1, 5, and naphthalene which should be of interest in this context have failed so far. Further attempts at cocrystn. of diazanaphthalenes with 1 also failed, which demonstrates the fine-tuned balance of cooperative and anticooperative effects for secondary intermol. interactions.