Journal of Molecular Modeling

, 20:2101 | Cite as

Theoretical study of the complementarity in halogen–bonded complexes involving nitrogen and halogen as negative sites

  • Mehdi D. Esrafili
  • Mahshad Vakili
  • Mohammad Solimannejad
Original Paper
First Online:
Received:
Accepted:

Abstract

This article analyzes the interplay between X···N and X···X halogen bonds interactions in NCX···NCX···XCH3 complexes, where X=Cl and Br. To better understand the properties of these systems, the corresponding dyads were also studied. These effects are studied theoretically in terms of geometric and energetic features of the complexes, which are computed by ab initio methods. The estimated values of cooperative energy (E coop) are all negative with much larger E coop in absolute value for the NCBr···NCBr···BrCH3 system. The effect of X···N on the properties of X···X is larger than that of X···X bonding on the properties of X···N. These results can be understood in terms of the electrostatic potentials of the negative sites with which the positive regions on the halogens are interacting. The nature of halogen bond interactions of the complexes is analyzed using parameters derived from the energy decomposition analysis.

Figure

Interplay between halogen bond and halogen···halogen interaction

Keywords

Ab initio Dispersion Electrostatic potential Halogen bond Halogen–halogen bond 
This is a preview of subscription content, log in to check access.

References

  1. 1.
    El-Sheshtawy HS, Bassil BS, Assaf KI, Kortz U, Nau WM (2012) Halogen bonding inside a molecular container. J Am Chem Soc 134:19935–19941CrossRefGoogle Scholar
  2. 2.
    Parker AJ, Stewart J, Donald KJ, Parish CA (2012) Halogen bonding in DNA base pairs. J Am Chem Soc 134:5165–5172CrossRefGoogle Scholar
  3. 3.
    Metrangolo P, Carcenac Y, Lahtinen M, Pilati T, Rissanen K, Vij A, Resnati G (2009) Nonporous organic solids capable of dynamically resolving mixtures of diiodoperfluoroalkanes. Science 323:1461–1464CrossRefGoogle Scholar
  4. 4.
    Riley KE, Hobza P (2008) Investigations into the nature of halogen bonding including symmetry adapted perturbation theory analyses. J Chem Theory Comput 4:232–242CrossRefGoogle Scholar
  5. 5.
    Aakeröy CB, Fasulo M, Schultheiss N, Desper J, Moore C (2007) Structural competition between hydrogen bonds and halogen bonds. J Am Chem Soc 129:13772–13773CrossRefGoogle Scholar
  6. 6.
    Politzer P, Murray JS (2013) Halogen bonding and beyond: factors influencing the nature of CN–R and SiN–R complexes with F–Cl and Cl2. Theor Chem Acc 131:1114–1123CrossRefGoogle Scholar
  7. 7.
    Politzer P, Lane P, Concha MC, Ma YG, Murray JS (2007) An overview of halogen bonding. J Mol Model 13:305–311CrossRefGoogle Scholar
  8. 8.
    Politzer P, Murray JS, Concha MC (2007) Halogen bonding and the design of new materials: organic bromides, chlorides and perhaps even fluorides as donors. J Mol Model 13:643–650CrossRefGoogle Scholar
  9. 9.
    Riley KE, Murray JS, Politzer P, Concha MC, Hobza P (2009) Br · · · O complexes as probes of factors affecting halogen bonding: interactions of bromobenzenes and bromopyrimidines with acetone. J Chem Theory Comput 5:155–163CrossRefGoogle Scholar
  10. 10.
    Riley KE, Murray JS, Fanfrlík J, Řezáč J, Solá RJ, Concha MC, Ramos FM, Politzer P (2011) Halogen bond tunability I: the effects of aromatic fluorine substitution on the strengths of halogen-bonding interactions involving chlorine, bromine, and iodine. J Mol Model 17:3309–3318CrossRefGoogle Scholar
  11. 11.
    Politzer P, Riley KE, Bulat FA, Murray JS (2012) Perspectives on halogen bonding and other σ-hole interactions: Lex parsimoniae (Occam’s Razor). Comput Theor Chem 998:2–8CrossRefGoogle Scholar
  12. 12.
    Murray JS, Lane P, Clark T, Riley KE, Politzer P (2012) σ-Holes, π-holes and electrostatically-driven interactions. J Mol Model 18:541–548CrossRefGoogle Scholar
  13. 13.
    Politzer P, Murray JS, Clark T (2013) Halogen bonding and other σ-hole interactions: a perspective. Phys Chem Chem Phys 15:11178–11189CrossRefGoogle Scholar
  14. 14.
    Politzer P, Murray JS (2013) Halogen bonding: an interim discussion. Chem Phys Chem 14:278–294CrossRefGoogle Scholar
  15. 15.
    Clark T, Hennemann M, Murray JS, Politzer P (2007) Halogen bonding: the σ-hole. J Mol Model 13:291–296CrossRefGoogle Scholar
  16. 16.
    Duarte DJR, de las Vallejos MM, Peruchena NM (2010) Topological analysis of aromatic halogen/hydrogen bonds by electron charge density and electrostatic potentials. J Mol Model 16:737–748CrossRefGoogle Scholar
  17. 17.
    Esrafili MD, Ahmadi B (2012) A theoretical investigation on the nature of Cl · · · N and Br · · · N halogen bonds in F-Ar-X · · · NCY complexes (X = Cl, Br and Y = H, F, Cl, Br, OH, NH2, CH3 and CN). Comput Theor Chem 997:77–82CrossRefGoogle Scholar
  18. 18.
    Bundhun A, Ramasami P, Murray JS, Politzer P (2013) Trends in σ-hole strengths and interactions of F3MX molecules (M = C, Si, Ge and X = F, Cl, Br, I). J Mol Model 19:2739–2746CrossRefGoogle Scholar
  19. 19.
    Lu Y, Zou J, Wang Y, Jiang Y, Yu Q (2007) Ab Initio investigation of the complexes between bromobenzene and several electron donors: some insights into the magnitude and nature of halogen bonding interactions. J Phys Chem A 111:10781–10788CrossRefGoogle Scholar
  20. 20.
    Politzer P, Murray JS, Clark T (2010) Halogen bonding: an electrostatically-driven highly directional noncovalent interaction. Phys Chem Chem Phys 12:7748–7757CrossRefGoogle Scholar
  21. 21.
    Riley KE, Murray JS, Fanfrlík J, Řezáč J, Solá RJ, Concha MC, Ramos FM, Politzer P (2013) Halogen bond tunability II: the varying roles of electrostatic and dispersion contributions to attraction in halogen bonds. J Mol Model 19:4651–4659CrossRefGoogle Scholar
  22. 22.
    Awwadi FF, Willett RD, Peterson KA, Twamley B (2006) The nature of halogen · · · halogen synthons: crystallographic and theoretical studies. Chem Eur J 12:8952–8960CrossRefGoogle Scholar
  23. 23.
    Ramasubbu N, Parthasarathy R, Murray-Rust P (1986) Angular preferences of intermolecular forces around halogen centers: preferred directions of approach of electrophiles and nucleophiles around the carbon-halogen bond. J Am Chem Soc 108:4308–4314CrossRefGoogle Scholar
  24. 24.
    Bach A, Lentz D, Luger P (2001) Charge density and topological analysis of pentafluorobenzoic acid. J Phys Chem A 105:7405–7412CrossRefGoogle Scholar
  25. 25.
    Matta CF, Castillo N, Boyd RJ (2005) Characterization of a closed-shell fluorine − fluorine bonding interaction in aromatic compounds on the basis of the electron density. J Phys Chem A 109:3669–3681CrossRefGoogle Scholar
  26. 26.
    Landolt-Bornstein (1950) Atoms and Ions, vol. 1. Part 1. Springer, BerlinGoogle Scholar
  27. 27.
    Baker RJ, Colavita PE, Murphy DM, Platts JA, Wallis JD (2012) Fluorine–fluorine interactions in the solid state: an experimental and theoretical study. J Phys Chem A 116:1435–1444CrossRefGoogle Scholar
  28. 28.
    Barceló-Oliver M, Estarellas C, García-Raso A, Terrón A, Frontera A, Quiñonero D, Mata I, Molins E, Deyà PM (2010) Experimental and theoretical study of uracil derivatives: the crucial role of weak fluorine–fluorine noncovalent interactions. Cryst Eng Comm 12:3758–3767CrossRefGoogle Scholar
  29. 29.
    Li QZ, Sun L, Liu XF, Li WZ, Cheng J, Zeng YL (2012) Enhancement of iodine–hydride interaction by substitution and cooperative effects in NCX–NCI–HMY complexes. ChemPhysChem 13:3997–4002CrossRefGoogle Scholar
  30. 30.
    Esrafili MD, Beheshtian J, Hadipour NL (2011) Computational study on the characteristics of the interaction in linear urea clusters. Int J Quantum Chem 111:3184–3195CrossRefGoogle Scholar
  31. 31.
    Alkorta I, Blanco F, Elguero J (2009) A computational study of the cooperativity in clusters of interhalogen derivatives. Struct Chem 20:63–71CrossRefGoogle Scholar
  32. 32.
    Esrafili MD, Hadipour NL (2011) Characteristics and nature of halogen bonds in linear clusters of NCX (X = Cl, and Br): an ab initio, NBO and QTAIM study. Mol Phys 109:2451–2460CrossRefGoogle Scholar
  33. 33.
    Grabowski SJ (2013) Cooperativity of hydrogen and halogen bond interactions. Theor Chem Acc 132:1347–1356CrossRefGoogle Scholar
  34. 34.
    Zhao Q, Feng D, Hao J (2011) The cooperativity between hydrogen and halogen bond in the XY···HNC···XY (X, Y = F, Cl, Br) complexes. J Mol Model 17:2817–2823CrossRefGoogle Scholar
  35. 35.
    Li QZ, Sun L, Liu XF, Li WZ, Cheng J, Zeng YL (2012) Enhancement of iodine–hydride interaction by substitution and cooperative effects in NCX–NCI–HMY complexes. Chem Phys Chem 13:3997–4002CrossRefGoogle Scholar
  36. 36.
    Solimannejad M, Malekani M, Alkorta I (2013) Substituent effects on the cooperativity of halogen bonding. J Phys Chem A 117:5551–5557CrossRefGoogle Scholar
  37. 37.
    Li Q, Lin Q, Li W, Cheng J, Gong B, Sun J (2008) Cooperativity between the halogen bond and the hydrogen bond in H3N · · · XY · · · HF complexes (X, Y = F, Cl, Br). Chem Phys Chem 9:2265–2269CrossRefGoogle Scholar
  38. 38.
    Esrafili MD (2012) Investigation of H-bonding and halogen-bonding effects in dichloroacetic acid: DFT calculations of NQR parameters and QTAIM analysis. J Mol Model 18:5005–5016CrossRefGoogle Scholar
  39. 39.
    Esrafili MD, Solimannejad M (2013) Revealing substitution effects on the strength and nature of halogen-hydride interactions: a theoretical study. J Mol Model 19:3767–3777CrossRefGoogle Scholar
  40. 40.
    Esrafili MD, Mohammadirad N (2013) Insights into the strength and nature of carbene · · · halogen bond interactions: a theoretical perspective. J Mol Model 19:2559–2566CrossRefGoogle Scholar
  41. 41.
    Cavallo G, Metrangolo P, Pilati T, Resnati G, Sansotera M, Terraneo G (2010) Halogen bonding: a general route in anion recognition and coordination. Chem Soc Rev 39:3772–3783CrossRefGoogle Scholar
  42. 42.
    Wang F, Ma N, Chen Q, Wang W, Wang L (2007) Halogen bonding as a new driving force for layer-by-layer assembly. Langmuir 23:9540–9542CrossRefGoogle Scholar
  43. 43.
    Metrangolo P, Neukirch H, Pilati T, Resnati G (2005) Halogen bonding based recognition processes: A world parallel to hydrogen bonding. Acc Chem Res 38:386–395CrossRefGoogle Scholar
  44. 44.
    Boys SF, Bernardi F (1970) The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors. Mol Phys 19:553–566CrossRefGoogle Scholar
  45. 45.
    Su P, Li H (2009) Energy decomposition analysis of covalent bonds and intermolecular interactions. J Chem Phys 131:014102CrossRefGoogle Scholar
  46. 46.
    Schmidt MW, Baldridge KK, Boatz JA, Elbert ST, Gordon MS, Jensen JH, Koseki S, Matsunaga N, Nguyen KA, Su SJ, Windus TL, Dupuis M, Montgomery JA (1993) General atomic and molecular electronic structure system. J Comput Chem 14:1347–1363CrossRefGoogle Scholar
  47. 47.
    Bulat FA, Toro-Labbe A, Brinck T, Murray JS, Politzer P (2010) Quantitative analysis of molecular surfaces: areas, volumes, electrostatic potentials and average local ionization energies. J Mol Model 16:1679–1691CrossRefGoogle Scholar
  48. 48.
    Bondi A (1964) van der Waals volumes and radii. J Phys Chem 68:441–451CrossRefGoogle Scholar
  49. 49.
    Esrafili MD, Mohammdian-Sabet F, Esmailpour P (2013) Theoretical study on cooperative effects between X ⋯ N and X ⋯ Carbene halogen bonds (X = F, Cl, Br and I). J Mol Model 19:4797–4804CrossRefGoogle Scholar
  50. 50.
    Esrafili MD (2013) A theoretical investigation of the characteristics of hydrogen/halogen bonding interactions in dibromo-nitroaniline. J Mol Model 19:1417–1427CrossRefGoogle Scholar
  51. 51.
    Xantheas SS (2000) Cooperativity and hydrogen bonding network in water clusters. Chem Phys 258:225–231CrossRefGoogle Scholar
  52. 52.
    Hobza P, Zahradnik R, Muller-Dethlefs K (2006) The world of non-covalent interactions. Coll Czech Chem Commun 71:443–531CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Mehdi D. Esrafili
    • 1
  • Mahshad Vakili
    • 1
  • Mohammad Solimannejad
    • 2
  1. 1.Laboratory of Theoretical Chemistry, Department of ChemistryUniversity of MaraghehMaraghehIran
  2. 2.Quantum Chemistry Group, Department of Chemistry, Faculty of SciencesArak UniversityArakIran

Personalised recommendations