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Resonance‐Assisted O‐H ⃛ O Hydrogen Bonding: Its Role in the Crystalline Self‐Recognition of β‐Diketone Enols and its Structural and IR Characterization
Author(s) -
Bertolasi Valerio,
Gilli Paola,
Ferretti Valeria,
Gilli Gastone
Publication year - 1996
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19960020806
Subject(s) - hydrogen bond , enol , crystallography , crystal structure , chemistry , resonance (particle physics) , crystal (programming language) , molecule , characterization (materials science) , crystal engineering , stereochemistry , materials science , catalysis , nanotechnology , organic chemistry , physics , atomic physics , computer science , programming language
The fact that hydrogen bonding is normally stronger than other nonbonding attractive forces can be exploited for the rational design of molecular crystals with known packing features and specific physical properties (crystal engineering). In the present paper the problem of obtaining homodromous molecular chains controlled by strong O–H ⃛ O interactions is investigated, particular attention being paid to β‐ chains , that is, infinite hydrogen‐bonded chains of β‐diketone enol fragments ⃛ OCCCOH ⃛, which are linked by stronger‐than‐usual resonance‐assisted hydrogen bonds (RAHBs) and are intrinsically interesting as prototypes of a large family of switching proton bistate molecular devices. Accordingly, the crystal and molecular structures of thirteen new compounds containing the 1,3‐cyclopentanedione and 1,3‐cyclohexanedione fragment (or their heterocyclic analogues) were determined, and most of them were found to give the expected β‐chain packing pattern. Comparison with literature data makes it possible to identify seven fundamental β‐chain patterns, which can be shown to be selected by reason of the relative encumbrances of the substituents. Furthermore, a general analysis of all functional groups able to form strong OH ⃛ O bonds reveals a semiquantitative correspondence between the OH ⃛ O measurable parameters (O ⃛ O, H ⃛ O and OH distances, and ṽ(OH) IR stretching frequencies) and the hydrogen bond energy E HB , and a hierarchy of chemical functionalities that are well characterized by limited E HB ranges and that, in decreasing order of energy, can direct the crystal packing process.