Learning outcomes of the course unit
Description of the main intermolecular interactions responsible for crystal structural organization. Introduction to the model of supramolecular synthons. Classification and exemplification of common structural patterns and stereochemical requirements for designing solid state organic/inorganic hybrid compounds. Use of the Cambridge Structural Database for structure analysis. Use of single crystal structure determination by X-ray diffraction.
Basic knowledge of solid state chemistry.
Course contents summary
Nature of intermolecular interactions. Close packing principle and symmetry for molecular crystals. Kitaigorodski's aufbau principle for rationalizing structural patterns. Analysis of the main intermolecular interactions responsible for structural organization: electrostatic interactions, conventional hydrogen bond, weak hydrogen bond, p-p interactions, metallophylic interactions, halogen-halogen interactions, aromatic interdigitation. Definition of supramolecular synthons. Classification and exemplification of common structural patterns for solid state organic/inorganic hybrid compounds: networks of hydrogen bond assembled coordination compounds, diamondoid networks, inorganic helices, coordination polymers, porous networks. Phenomenum of interpenetration. Illustration of stereochemical requirements for designing supramolecular coordination compounds as polyhedral aggregates, monodimensional, bidimensional, and tridimensional polymers. Exercitations: analysis of structural patterns by using the Cambridge Crystallographic Database software. Single crystal structure determination by X-ray diffraction.
Reference to the original literature for the main course subjects.
Close packing principle:
-A. Gavezzotti, ‘Crystal Packing’, IUCr Pamphlet Series, International Union of Crystallography, 2001.
- J. Perlstein ‘Introduction to packing patterns and packing energetics of crystalline self-assembled structures’, Crystal Engineering: From Molecules and Crystals to Materials, Ed. D. Braga, F. Grepioni, G. Orpen, NATO Sciences Series, Vol. C538, Kluwer Academic Publishers, 1999, p. 23-26.
- G. Gilli, ‘Molecules and Molecular Crystals’, in ‘Fundamental of Crystallography’, Ed. C. Giacovazzo, Oxford University Press, 1992, p. 468 – 478.
- G.R. Desiraju ‘ Hydrogen bridges in crystal engineering: interactions without borders’, Acc. Chem. Res., 2002, 35, 565-573.
- C. Janiak, A critical account on p-p stacking in metals complexes with aromatic nitrogen-containing ligands’, J. Chem. Soc., Dalton Trans., 2000, 3885-3896.
- H. Schmidbaur, ‘The Aurophilicity Phenomenon: A Decade of Experimental Findings, Theoretical Concepts and Emerging Applications’, Gold Bull., 2000, 33, 3-10.
- Desiraju, Gautam R. ‘Supramolecular synthons in crystal engineering - a new organic synthesis’. Angewandte Chemie, International Edition in English (1995) 34(21), 2311-27
Structural patterns and crystal engineering:
- C. V. Krishnamohan Sharma ‘Designing Advanced Materials As Simple As Assembling Lego® Blocks!’ • Journal of Chemical Education Vol. 78 , 617
- Kumar Biradha ‘Crystal engineering: from weak hydrogen bonds to co-ordination bonds’ CrystEngComm, 2003, 5(66), 374–384
- D. Braga, F. Grepioni ‘Intermolecular Interactions in Nonorganic Crystal Engineering’ Acc. Chem. Res. 2000, 33, 601-608
- Stuart R. Batten ‘Topology of interpenetration’ CrystEngComm, 2001, 18, 1–7
Supramolecular stereochemistry, polyhedra and polymers:
- P. J. Stang, B. Olenyuk ‘Self-Assembly, Symmetry, and Molecular Architecture: Coordination as the Motif in the Rational Design of Supramolecular Metallacyclic Polygons and Polyhedra’ ACCOUNTS OF CHEMICAL RESEARCH / VOL. 30, 1997, 502
- Xiao-Chun Huang, Jie-Peng Zhang, Xiao-Ming Chen ‘A New Route to Supramolecular Isomers via Molecular Templating: Nanosized Molecular Polygons of Copper(I) 2-Methylimidazolates’ J. AM. CHEM. SOC. 2004, 126, 13218-13219
Lectures, exercises on databases
Assessment methods and criteria