Skip to main content
Springer Nature Link
Log in

Ab initio investigation of the competition of pnicogen, halogen, and hydrogen bonds resulting from the interactions between cyanophosphine and hypohalous acids

  • Original Paper
  • Published:
Journal of Molecular Modeling Aims and scope Submit manuscript

Abstract

Context

The complexes formed as a result of the interactions between cyanophosphine (CP, H2PCN) and hypohalous acid molecules (HOX, X = F, Cl, Br, and I) were studied by employing ab initio computations conducted at the MP2/aug-cc-pVTZ level. Three types of complexes were acquired (I, II, and III) as a result of the (O∙∙∙P) pnicogen bond, the (N∙∙∙H) hydrogen bond, and the (N∙∙∙X) halogen bond interaction, respectively. The results of harmonic vibrational frequency calculations with no imaginary frequencies confirmed the structures as minima. In addition, given the interaction energy of the complexes, hydrogen bond complexes of structure II have the highest stability compared to other structures. In all studied complexes, the strength of the interactions depended on the electronegativity of the halogen atoms. The characteristics and nature of the whole three types of complexes were examined and evaluated with natural bond orbital (NBO), atom in molecules (AIM), molecular electrostatic potential (MEP) maps, non-covalent interaction (NCI) index, and electron density difference (EDD) analyses.

Method

The optimization of all complexes and corresponding monomers was conducted through the ab initio method, employing the MP2 level along with the aug/cc-pVTZ basis set for all atoms, except for the iodine (I) atom, for which the aug-cc-pVTZ (PP) basis set was employed. Subsequent frequency calculations were executed to ascertain the minimum energy state of the complexes at the MP2 level and the aug/cc-pVTZ basis set, utilizing Gaussian09 software. The MEP maps of the monomers were generated using the analysis-surface suite (WFA-SAS) software package. To probe the orbital interactions within the studied complexes, NBO analysis was performed employing NBO software. The assessment of bond nature, topological features, and electron density values at critical points for the studied complexes was undertaken using AIMAll software. The NCI index was derived utilizing Multiwfn software, and its three-dimensional representation was rendered using VMD software.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+
from $39.99 /Month
  • Starting from 10 chapters or articles per month
  • Access and download chapters and articles from more than 300k books and 2,500 journals
  • Cancel anytime
View plans

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

Explore related subjects

Discover the latest articles, books and news in related subjects, suggested using machine learning.

Data availability

The data that support the findings of this study are available on request from the corresponding author.

References

  1. Alkorta I, Blanco F, Solimannejad M, Elguero J (2008) Competition of hydrogen bonds and halogen bonds in complexes of hypohalous acids with nitrogenated bases. J Phys Chem A 112. https://doi.org/10.1021/jp806101t

  2. Gilli G, Gilli P (2009) The nature of the hydrogen bond: outline of a comprehensive hydrogen bond theory. Oxford university press

    Book  Google Scholar 

  3. Moradkhani M, Naghipour A, Abbasi Tyula Y (2023) Competition and interplay between Hydrogen, Tetrel, and Halogen bonds from interactions of COCl2 and HX (X = F, Cl, Br, and I). Comput Theor Chem 1223:114099. https://doi.org/10.1016/j.comptc.2023

    Article  CAS  Google Scholar 

  4. Zhang X, Zeng Y, Li X, Meng L, Zheng S (2011) A computational study on the nature of the halogen bond between sulfides and dihalogen molecules. Struct Chem 22:567–576. https://doi.org/10.1007/s11224-011-9732-0

    Article  CAS  Google Scholar 

  5. Murray JS, Lane P, Politzer P (2008) Simultaneous σ-hole and hydrogen bonding by sulfur- and selenium-containing heterocycles. Int J Quantum Chem 108:2770–2781. https://doi.org/10.1002/qua.21753

    Article  CAS  Google Scholar 

  6. Murray JS, Lane P, Clark T, Politzer P (2007) σ-hole bonding: molecules containing group VI atoms. J Mol Model 13:1033–1038. https://doi.org/10.1007/s00894-007-0225-4

    Article  CAS  PubMed  Google Scholar 

  7. Politzer P, Lane P, Concha MC, Ma Y, Murray JS (2007) An overview of halogen bonding. J Mol Model 13:305–311. https://doi.org/10.1007/s00894-006-0154-7

    Article  CAS  PubMed  Google Scholar 

  8. Clark T, Hennemann M, Murray JS, Politzer P (2007) Halogen bonding: the σ-hole. J Mol Model 13:291–296. https://doi.org/10.1007/s00894-006-0130-2

    Article  CAS  PubMed  Google Scholar 

  9. Bauzá A, Ramis R, Frontera A (2014) Computational study of anion recognition based on tetrel and hydrogen bonding interaction by calix[4]pyrrole derivatives. Comput Theor Chem 1038:67–70. https://doi.org/10.1016/j.comptc.2014.04.010

    Article  CAS  Google Scholar 

  10. Alkorta I, Elguero J, Del Bene JE (2013) Pnicogen-bonded cyclic trimers (PH 2 X) 3 with X = F, Cl, OH, NC, CN, CH 3 , H, and BH 2. J Phys Chem A 117:4981–4987. https://doi.org/10.1021/jp403651h

    Article  CAS  PubMed  Google Scholar 

  11. Solimannejad M, Gharabaghi M, Scheiner S (2011) SH···N and SH···P blue-shifting H-bonds and N···P interactions in complexes pairing HSN with amines and phosphines. J Chem Phys 134:024312. https://doi.org/10.1063/1.3523580

    Article  CAS  PubMed  Google Scholar 

  12. Thomas SP, Jayatilaka D, Guru Row TN (2015) S⋯O chalcogen bonding in sulfa drugs: insights from multipole charge density and X-ray wavefunction of acetazolamide. Phys Chem Chem Phys 17:25411–25420. https://doi.org/10.1039/C5CP04

    Article  CAS  PubMed  Google Scholar 

  13. Thomas SP, Satheeshkumar K, Mugesh G, Guru Row TN (2015) Unusually short chalcogen bonds involving organoselenium: insights into the Se–N bond cleavage mechanism of the antioxidant ebselen and analogues. Chem Eur J 21(18):6793–6800. https://doi.org/10.1002/chem.201405998

  14. 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 13:643–650. https://doi.org/10.1007/s00894-007-0176-9

    Article  CAS  PubMed  Google Scholar 

  15. Metrangolo P, Resnati G (2001) Halogen bonding: a paradigm in supramolecular chemistry. Chem A Eur J 7:2511–2519. https://doi.org/10.1002/1521-3765(20010618)7:12<2511::AID-CHEM25110>3.0.CO;2-T

    Article  CAS  Google Scholar 

  16. Bouchmella K, Boury B, Dutremez SG, van der Lee A (2007) Molecular assemblies from Imidazolyl-containing haloalkenes and haloalkynes: competition between halogen and hydrogen bonding. Chem A Eur J 13:6130–6138

    Article  CAS  Google Scholar 

  17. An X, Zhuo H, Wang Y, Li Q (2013) Competition between hydrogen bonds and halogen bonds in complexes of formamidine and hypohalous acids. J Mol Model 19:4529–4535. https://doi.org/10.1007/s00894-013-1969-7

    Article  CAS  PubMed  Google Scholar 

  18. Metrangolo P, Murray JS, Pilati T et al (2011) The fluorine atom as a halogen bond donor, viz. a positive site. CrystEngComm 13:6593–6596. https://doi.org/10.1039/c1ce05554b

    Article  CAS  Google Scholar 

  19. Asiabar BM, Esrafili MD, Mohammadian-Sabet F et al (2014) An ab initio study on the concerted interaction between chalcogen and pnicogen bonds. J Mol Model 20. https://doi.org/10.1007/s00894-014-2545-5

  20. Scheiner S (2011) Can two trivalent N atoms engage in a direct N⋯N noncovalent interaction? Chem Phys Lett 514:32–35. https://doi.org/10.1016/j.cplett.2011.08.028

    Article  CAS  Google Scholar 

  21. Adhikari U, Scheiner S (2012) Sensitivity of pnicogen, chalcogen, halogen and H-bonds to angular distortions. Chem Phys Lett 532:31–35. https://doi.org/10.1016/j.cplett.2012.02.064

    Article  CAS  Google Scholar 

  22. Zahn S, Frank R, Hey-Hawkins E, Kirchner B (2011) Pnicogen bonds: a new molecular linker? Chem - A Eur J 17:6034–6038. https://doi.org/10.1002/chem.201002146

    Article  CAS  Google Scholar 

  23. Vickaryous WJ, Healey ER, Berryman OB, Johnson DW (2005) Synthesis and characterization of two isomeric, self-assembled arsenic-thiolate macrocycles. Inorg Chem 44:9247–9252. https://doi.org/10.1021/ic050954w

    Article  CAS  PubMed  Google Scholar 

  24. Saparov B, He H, Zhang X et al (2010) Synthesis, crystallographic and theoretical studies of the new Zintl phases Ba2Cd2Pn3 (Pn = As, Sb), and the solid solutions (Ba1-xSrx)2Cd2Sb 3 and Ba2Cd2(Sb1-xAs x)3. Dalton Trans 39:1063–1070. https://doi.org/10.1039/b914305j

    Article  CAS  PubMed  Google Scholar 

  25. Guan L, Mo Y (2014) Electron transfer in pnicogen bonds. J Phys Chem A 118:8911–8921. https://doi.org/10.1021/jp500775m

    Article  CAS  PubMed  Google Scholar 

  26. Scheiner S (2013) The pnicogen bond: its relation to hydrogen, halogen, and other Noncovalent Bonds. Acc Chem Res 46:280–288. https://doi.org/10.1021/ar3001316

    Article  CAS  PubMed  Google Scholar 

  27. Murray JS, Lane P, Politzer P (2007) A predicted new type of directional noncovalent interaction. Int J Quantum Chem 107:2286–2292. https://doi.org/10.1002/qua.21352

    Article  CAS  Google Scholar 

  28. Molina MJ, Rowland FS (1974) Stratospheric sink for chlorofluoromethanes: chlorine atom-catalysed destruction of ozone. Nature. 249:810–812. https://doi.org/10.1038/249810a0

    Article  CAS  Google Scholar 

  29. Thomas EL (1979) Myeloperoxidase, hydrogen peroxide, chloride antimicrobial system: nitrogen-chlorine derivatives of bacterial components in bactericidal action against Escherichia coli. Infect Immun 23:522–531. https://doi.org/10.1128/iai.23.2.522-

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  30. Abu-Soud HM, Maitra D, Byun J, Souza CEA, Banerjee J, Saed GM, Pennathur S (2012) The reaction of HOCl and cyanocobalamin: corrin destruction and the liberation of cyanogen chloride. Free Radic Biol Med 52(3):616–625. https://doi.org/10.1016/j.freeradbiomed.2011.10.496

  31. Li Q, Xu X, Liu T, Jing B, Li W, Cheng J, Sun J (2010) Competition between hydrogen bond and halogen bond in complexes of formaldehyde with hypohalous acids. Phys Chem Chem Phys 12(25):6837–6843. https://doi.org/10.1039/B926355A

  32. Zabaradsti A, Kakanejadifard A, Ghasemian M (2012) Theoretical study of molecular interactions of phosphorus ylide with hypohalous acids HOF. HOCl HOBr Comput Theor Chem 989:1–6. https://doi.org/10.1016/j.comptc.2012.02.017

    Article  CAS  Google Scholar 

  33. Wolf ME, Zhang B, Turney JM, Schaefer HF (2019) A comparison between hydrogen and halogen bonding: the hypohalous acid–water dimers, HOX⋯H 2 O (X = F, Cl, Br). Phys Chem Chem Phys 21:6160–6170. https://doi.org/10.1039/C9CP004

    Article  CAS  PubMed  Google Scholar 

  34. Zabardasti A, Kakanejadifard A, Goudarziafshar H et al (2013) Theoretical study of hydrogen and halogen bond interactions of methylphosphines with hypohalous acids. Comput Theor Chem 1014:1–7. https://doi.org/10.1016/j.comptc.2013.03.008

    Article  CAS  Google Scholar 

  35. Blanco F, Alkorta I, Solimannejad M, Elguero J (2009) Theoretical study of the 1:1 complexes between carbon monoxide and hypohalous acids. J Phys Chem A 113:3237–3244. https://doi.org/10.1021/jp810462h

    Article  CAS  PubMed  Google Scholar 

  36. Zabardasti A, Tyula YA, Goudarziafshar H (2017) Interplay between n∙∙∙h, n∙∙∙x and π∙∙∙x interactions in the complex pairing of pyrazine with hypohalous acids: a nbo and qtaim (quantum theory of atoms in molecules) analysis. Bull Chem Soc Ethiop 31:241–252. https://doi.org/10.4314/bcse.v31i2.6

    Article  CAS  Google Scholar 

  37. Frisch MJEA, Trucks G, Schlegel HB, Scuseria G, Robb M, Cheeseman J, Nakatsuji H (2009) Gaussian 09, Revision a. 02, 200, Gaussian. Inc., Wallingford, CT, P 271

  38. Møller C, Plesset MS (1934) Note on an approximation treatment for many-electron systems. Phys Rev 46:618–622. https://doi.org/10.1103/PhysRev.46.618

    Article  Google Scholar 

  39. 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 19:553–566. https://doi.org/10.1080/00268977000101561

    Article  CAS  Google Scholar 

  40. Bulat, F.A., Toro-Labbé, A., Brinck, T., Murray, J.S., Politzer, P.: Quantitative analysis of molecular surfaces: areas, volumes, electrostatic potentials and average local ionization energies. J Mol Model 16, 1679–1691 (2010). 10.1007/s0

  41. Иванов (1988) A.E. Reed, L.A. Curtiss, F. Weinhold, Intermolecular interactions from a natural bond orbital, donor - acceptor viewpoint, Chem. Rev. 88 (1988) 899–926. Птицы 1:12–17

  42. Keith TA (2012) AIMAll (Version 12.09.23). TK Gristmill Software, Overland Park KS

    Google Scholar 

  43. Lu T, Chen F (2012) Multiwfn: a multifunctional wavefunction analyzer. J Comput Chem 33:580–592

    Article  PubMed  Google Scholar 

  44. Humphrey W, Dalke A, Schulten K (1996) Humphrey, W., Dalke, A. and Schulten, K., “VMD - Visual Molecular Dynamics”. J Mol Graph 14:33–38

    Article  CAS  PubMed  Google Scholar 

  45. Li Q, Zhu H, Zhuo H, Yang X, Li W, Cheng, J (2014) Complexes between hypohalous acids and phosphine derivatives. Pnicogen bond versus halogen bond versus hydrogen bond. Spectrochim Acta A Mol Biomol Spectrosc 132:271–277 https://doi.org/10.1016/j.saa.2014.05.001

  46. Koch U, Popelier PLA (1995) Characterization of C-H-O hydrogen bonds on the basis of the charge density. J Phys Chem 99:9747–9754. https://doi.org/10.1021/j100024a016

    Article  CAS  Google Scholar 

  47. Boldeskul IE, Tsymbal IF, Ryltsev EV et al (1997) Reversal of the usual spectral shift of haloforms in some hydrogen-bonded complexes. J Mol Struct 436–437:167–171. https://doi.org/10.1016/S0022-2860(97)00137-3

    Article  Google Scholar 

  48. Allerhand A, Von Rague SP (1963) A survey of C-H groups as proton donors in hydrogen bonding. J Am Chem Soc 85:1715–1723. https://doi.org/10.1021/ja00895a002

    Article  CAS  Google Scholar 

  49. Delanoye SN, Herrebout WA, van der Veken BJ (2002) Blue shifting hydrogen bonding in the complexes of chlorofluoro haloforms with Acetone- d 6 and Oxirane- d 4. J Am Chem Soc 124:11854–11855. https://doi.org/10.1021/ja027610e

    Article  CAS  PubMed  Google Scholar 

  50. Bent HA (1961) An appraisal of valence-bond structures and hybridization in compounds of the first-row elements. Chem Rev 61:275–311. https://doi.org/10.1021/cr60211a005

    Article  CAS  Google Scholar 

  51. Moradkhani M, Naghipour A, Tyula YA, Abbasi S (2023) Competition of hydrogen, tetrel, and halogen bonds in COCl2-HOX (X=F, Cl, Br, I) complexes. J Mol Graph Model 122:108–482. https://doi.org/10.1016/j.jmgm.2023.108482

    Article  CAS  PubMed  Google Scholar 

  52. Moradkhani M, Naghipour A, Tyula YA (2023) Investigation of structural, spectral, and electronic properties of complexes resulting from the interaction of acetonitrile and hypohalous acids. Struct Chem. https://doi.org/10.1007/s11224-023-02243-8

  53. Espinosa E, Molins E, Lecomte C (1998) Hydrogen bond strengths revealed by topological analyses of experimentally observed electron densities. Chem Phys Lett 285:170–173. https://doi.org/10.1016/S0009-2614(98)00036-0

    Article  CAS  Google Scholar 

  54. Lu Y-X, Zou J-W, Wang Y-H et al (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 111:10781–10788. https://doi.org/10.1021/jp0740954

    Article  CAS  PubMed  Google Scholar 

  55. Khan P, Jamshaid M, Tabassum S et al (2021) Exploring the interaction of ionic liquids with Al12N12 and Al12P12 nanocages for better electrode-electrolyte materials in super capacitors. J Mol Liq 344:117–828. https://doi.org/10.1016/j.molliq.2021.117828

    Article  CAS  Google Scholar 

  56. Singh H (2023) A DFT insight into structure, NBO, NCI, QTAIM, vibrational, and NLO properties of cationic amino acid ionic liquid [Pro-H]+BF4−. Struct Chem. https://doi.org/10.1007/s11224-023-02195-z

Download references

Funding

The authors declare that no funds, grants, or other support were received during the preparation of this manuscript.

Author information

Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Ilam University, Ilam, 69315-516, Iran

    Mohammadmehdi Moradkhani, Ali Naghipour & Yunes Abbasi Tyula

Authors
  1. Mohammadmehdi Moradkhani
    View author publications

    Search author on:PubMed Google Scholar

  2. Ali Naghipour
    View author publications

    Search author on:PubMed Google Scholar

  3. Yunes Abbasi Tyula
    View author publications

    Search author on:PubMed Google Scholar

Contributions

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Mohammadmehdi Moradkhani: Writing – original draft, Formal analysis, Software, Investigation, Methodology, Conceptualization, Writing – review & editing. Ali Naghipour: Validation, Supervision, Project administration. Yunes Abbasi Tyula: Writing – original draft, Investigation, Formal analysis, Methodology, Writing – review & editing.

Corresponding authors

Correspondence to Ali Naghipour or Yunes Abbasi Tyula.

Ethics declarations

Ethics approval

Not applicable.

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

ESM 1

Figure S1: Correlation between bond angles and then interaction energy(SE0) in complexes of the groups I,II and III respectively. Figure S2: Correlation between the Interaction energy SE0(kcal/mol) and potential energy density V(r) (a.u) for XB and HB complexes. Figure S3:Relationship between absolute values of the stabilization energy(SE0 kcal/mol)and electron density (ρC a.u). Figure S4:Relationship between the second-order perturbation energy (E(2) kcal/mol) and electron density (ρC a.u). (DOCX 151 kb)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Moradkhani, M., Naghipour, A. & Tyula, Y.A. Ab initio investigation of the competition of pnicogen, halogen, and hydrogen bonds resulting from the interactions between cyanophosphine and hypohalous acids. J Mol Model 30, 15 (2024). https://doi.org/10.1007/s00894-023-05809-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00894-023-05809-9

Keywords

Profiles

  1. Mohammadmehdi Moradkhani View author profile
  2. Ali Naghipour View author profile