page_title: Halogen bond
section_title: Bonding
hierarchical_section_title: Halogen bond / Bonding
caption_attribution_description: English: Molecular complex between iodine monochloride and trimethyl amine
context_page_description: A halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity.
context_section_description: Comparison between hydrogen and halogen bonding:
  Hydrogen bonding
  Halogen bonding
  In both cases, A (the hydrogen/halogen bond acceptor) is the atom, group, or molecule that donates electrons to the electron poor species H-D or X-D (the hydrogen or halogen bond donors respectively). H is the hydrogen atom involved in hydrogen bonding, and X is the halogen atom involved in halogen bonding. Note the halogen bond donor accepts electrons while the halogen bond acceptor donates electrons.
  A parallel relationship can easily be drawn between halogen bonding and hydrogen bonding (HB). In both types of bonding, an electron donor/electron acceptor relationship exists. The difference between the two is what species can act as the electron donor/electron acceptor. In hydrogen bonding, a hydrogen atom acts as the electron acceptor and forms a non-covalent interaction by accepting electron density from an electron rich site (electron donor). In halogen bonding, a halogen atom is the electron acceptor. Simultaneously, the normal covalent bond between H or X and D weakens, so the electron density on H or X appears to be reduced. Electron density transfers results in a penetration of the van der Waals volumes.
  Halogens participating in halogen bonding include: iodine (I), bromine (Br), chlorine (Cl), and sometimes fluorine (F). All four halogens are capable of acting as XB donors (as proven through theoretical and experimental data) and follow the general  trend: F < Cl < Br < I, with iodine normally forming the strongest interactions.
  Dihalogens (I₂, Br₂, etc.) tend to form strong halogen bonds. The strength and effectiveness of chlorine and fluorine in XB formation depend on the nature of the XB donor. If the halogen is bonded to an electronegative (electron withdrawing) moiety, it is more likely to form stronger halogen bonds.
  For example, iodoperfluoroalkanes are well-designed for XB crystal engineering. In addition, this is also why F₂ can act as a strong XB donor, but fluorocarbons are weak XB donors because the alkyl group connected to the fluorine is not electronegative. In addition, the Lewis base (XB acceptor) tends to be electronegative as well and anions are better XB acceptors than neutral molecules.
  Halogen bonds are strong, specific, and directional interactions that give rise to well-defined structures. Halogen bond strengths range from 5–180 kJ/mol. The strength of XB allows it to compete with HB, which are a little bit weaker in strength. Halogen bonds tend to form at 180° angles, which was shown in Odd Hassel’s studies with bromine and 1,4-dioxane in 1954. Another contributing factor to halogen bond strength comes from the short distance between the halogen (Lewis acid, XB donor) and Lewis base (XB acceptor). The attractive nature of halogen bonds result in the distance between the donor and acceptor to be shorter than the sum of van der Waals radii. The XB interaction becomes stronger as the distance decreases between the halogen and Lewis base.
caption: Figure 2: XB in complex between iodine monochloride and trimethylamine.
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