Halogen Bonding in Crystal Engineering - Halogen Bonding: Fundamentals and Applications - page 104

Halogen Bonding in Crystal Engineering

Pierangelo Metrangolo 1,2 ( )·GiuseppeResnati 1,2 ( )·TullioPilati 3 ·

Serena Biella 1,2
1 Laboratory of Nanostructured Fluorinated Materials (NFMLab),
Department of Chemistry, Materials and Chemical Engineering “Giulio Natta”,
Politecnico di Milano, 7, via Mancinelli, 20131 Milano, Italy
[e-mail]; [e-mail]
2 Como Campus, Politecnico di Milano, 7, via Castelnuovo, 22100 Como, Italy
3 C.N.R.-Institute of Molecular Sciences and Technologies, Università di Milano,
19, via Golgi, 20133 Milano, Italy

1 I tr cti n ................................... 106

2 General Features of XB ............................. 107

2.1 RelativeEffectivenessofXBvs.HB ...................... 109

2.2 XBandElectronDensityAroundHalogenAtoms .............. 110

2.3 StructureandRoleoftheHalocarbon..................... 114

2.4 StructureandRoleoftheHalocarbonPartner ................ 115

2.5 DirectionalityofXB............................... 116

3 Halogen-Bonded Supramolecular Architectures ............... 118

3.1 1DArchitectures................................. 119

3.2 2DArchitectures................................. 122

3.3 3DArchitectures................................. 125

4 cl si s ................................... 129

References ....................................... 130

Abstract The term halogen bonding encompasses any non-covalent interaction involving
halogens as electrophilic species. High strength and directionality are the remarkable fea-
tures of halogen bonding that fully justify its use as a primary intermolecular interaction
to dictate molecular self-assembly processes. This chapter will outline the use of halogen
bonding in crystal engineering and will highlight the obtainment of heteromeric crystal
structures with complex topologies. Even though the use of halogen bonding is still in
its infancy, the growing interest in the field shown by the crystal engineering community
promises major advances in the future.

Keywords Halogen bonding · Supramolecular chemistry · Crystal engineering · Te c t o n ·
Top o l o g y

Abbreviations
BPE ( E )-1,2-Bis(4-pyridyl)ethylene
BPY Dipyridine
DABCO Diazabicyclooctane