Crystal Engineering (in four lectures)

1 June 2012 1Lecture 1 RUB

http://www.amazon.de/Crystal-Engineering-

Textbook-Gautam-

Desiraju/dp/9814366862/ref=sr_1_fkmr0_1?

ie=UTF8&qid=1338473179&sr=8-1-fkmr0

From molecules to crystals

http://www.cosmosmagazine.com

/news/2403/17-molecules-

altered-human-history-molecules-

changed-wold?page=0%2C2

A crystal is a very precise and specific type

of molecular assembly

Assemblies of molecules. How do molecules associate

with each other. In specific

ways?

The molecule is

paramount in chemistry

Why molecules?

Crystal engineering teaches us how to bring

molecules together exactly as we want.

1 June 2012 2Lecture 1 RUB

Concept of Molecularity

Zero, One, Two and Three-dimensional Molecules

Molecule Dimensionality Molecularity

Naphthalene 0D 3D

Fullerene

PdCl2 1D 2D

Graphite 2D 1D

Diamond 3D 0D

Lecture 1 RUB1 June 2012 3

Crystal structure The arrangement of atoms, molecules, or ions that constitutes the internal structure of a crystal.

Crystal A solid form of a substance with a definite and periodic internal structure.

an external shape made up of symmetrically arranged plane surfaces.

gives a discrete X-ray diffraction pattern. atoms, ions or molecules are in some degree of order. a manifestation of mutual recognition.enthalpic factors gain over entropy.

Crystal Engineering The understanding of intermolecular interactions in the context of crystal packing and the utilization of such

understanding in the design of new solids with desired physical and chemical properties.

1 June 2012 4Lecture 1 RUB

X-ray Crystallography

Organic Solid State Chemistry

The Crystal as a Supramolecular Entity

Modern Crystal Engineering

Horizontal and Vertical Divisions of Chemistry

Organic Crystal Engineering

Properties of Crystals

Summary and time line

Topics to be covered today

Lecture 1 RUB1 June 2012 5

X-ray crystallography

Visualization of a crystal as a periodic arrayHexachlorobenzene and Urotropin were the earliest

organic crystal structures to be determined

One of the fundamental questions of crystal engineering is

Given the molecular structure of a compound, what is its crystal

structure?

Lecture 1 RUB1 June 2012 6

Gerhard M. J. Schmidt

(1919–1971)

Organic solid state chemistry

Lecture 1 RUB1 June 2012 7

Supramolecular chemistry The chemistry of molecular assemblies, intermolecular

bonds, non-covalent interactions and hydrogen bonds.

The crystal as a supramolecular entity

signifies that which is beyond the molecule

concerned with strategies for the controlled organization of

multiple components into complex matter

In the context of crystal engineering, crystals are ordered supramolecular systems, and crystallization is

an impressive display of periodic molecular assembly.

Lecture 1 RUB1 June 2012 8

How crystal engineering is set up

It is a horizontal discipline

What do we do?

Make crystals by using interactions (lecture 2)

How do we do it?

Synthetic strategies (lecture 3)

Why do we do it?

Properties (lecture 4)

Lecture 1 RUB1 June 2012 9

1921: W. H. Bragg relates the crystal structures of naphthalene and anthracene.

1935: J. D. Bernal advocates the study of groups of crystal

structures.1948: H. M. Powell describes the β-hydroquinone structure as

a network.1955: R. Pepinsky uses the term crystal engineering, the first

time anyone does so.1964: G. M. J. Schmidt publishes a series of papers in

Journal of the Chemical Society on the solid state

chemistry of cinnamic acids and other alkenes.1971: G. M. J. Schmidt formally introduces the term crystal

engineering in his paper in Pure and Applied Chemistry.

Crystal Engineering Time Line

Lecture 1 RUB1 June 2012 10

1989: G. R. Desiraju’s book Crystal Engineering. The Design of Organic Solids is published signifying the beginning of

modern organic crystal engineering.

1990: M. C. Etter identifies the hydrogen bond as an important design element in crystal construction.

1991: J. D. Dunitz terms the crystal as a supramolecule par excellence in his paper.

1995: The relationship between crystal engineering and organic synthesis is highlighted in a review by G. R. Desiraju.

1995: O. M. Yaghi describes selective binding and removal of

guest molecules in a porous metal organic framework structure.

2011: The first textbook devoted exclusively to crystal engineering is published (is co-authored by G. R. Desiraju,

J. J. Vittal and A. Ramanan).

Crystal Engineering Time Line

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How crystals are stabilized

Next lecture - Intermolecular interactions

The crystal structure of a moleculeA free energy minimum that results from a balance of

attractive and repulsive forces.

Anisotropic interactions – long rangeElectrostatic interactions

ionic interactions (salts)

Strong and weak hydrogen bonds (O–H···O, C–H···O)

Interactions between heteroatoms(halogen···halogen)

Intermolecular interactions in molecules are of two types

Lecture 1 RUB1 June 2012 16

Isotropic interactions – short range