Molecular Self-Assemblies 5: An Analysis of the Vector Properties of Hydrogen Bonding in Crystal Engineering

• Main Authors: PERLSTEIN, Jerry, STEPPE, Kevin
• Format: text
• Language: English
• Published: Institutional Knowledge at Singapore Management University 1996
• Subjects: Numerical Analysis and Scientific Computing; Software Engineering
• Online Access: https://ink.library.smu.edu.sg/sis_research/72; http://dx.doi.org/10.1021/ja9543412
• Institution: Singapore Management University

Kitaigorodskii's aufbau principle (KAP) is used to analyze hydrogen bonding as a vector for the packing of molecules in the crystalline solid state. Using the CFF91 force field to compute the moleculemolecule interaction potential, we find that the signature for hydrogen bonding of NH and OH donor groups with N or O acceptors is a positive value for the nonbonded van der Waals term of the hydrogen atom involved in the H-bond. The H-bond may occur as a vector in any one or more of the four stages of KAP. We categorize these vectors as types 14 with 16 possible subtypes depending upon the number of KAP stages in which the H-bond appears. Within the constraints of the force field description, the H-bond then becomes a specific vector contribution to the packing of one or more substructures of the complete crystal. Of the 16 possible vector subtypes we illustrate 12 of them using crystal structure data from the Cambridge Structural Database. Knowing the vector subtype, we show how it is possible to locate the local minima representing the packing geometry of the substructures using Monte Carlo simulation methods. The establishment of quantitative signatures for vector types within KAP substructures and their relationship to crystal engineering is discussed.