Advertisement

How do halogen atoms influence the competition between all-trans and hairpin conformers of unbranched alkanes?

  • Olga V. GrinevaEmail author
Original Research
  • 11 Downloads

Abstract

Influence of fluorine, chlorine, and bromine atoms on conformational preferences of free non-rigid molecules is analyzed on the basis of quantum chemical calculations. Thirty-six compounds are considered: 35 with the general formula X(CH2)nY (where X = Y = CH3, F, Cl, Br or X = F, Cl, Br, Y = CH3 and even n from 8 to 16) and n-octane. According to the previous computational and experimental results obtained by other researches, free n-alkane molecules with the number of carbon atoms (nC) greater than approximately 16–18 prefer to form hairpin conformers (where the chain is folded in two) instead of fully extended (all-trans) conformers that are more favorable for the compounds with lower nC. For halogenated n-alkanes, such investigation is made for the first time. Calculations at the ωB97X-D/6–31++G(d,p) level of theory were performed for all compounds and at the MP2/6–31++G(d,p) level for n-alkanes, 1,n-difluoro-, 1,n-dichloroalkanes with n from 8 to 16, 1,8-dibromooctane and 1,9-fluoro-, 1,9-chloro-, 1,9-bromononane. Conclusions about influence of X, Y, or n on conformational preferences drawn from the calculations on the different theoretical levels are in qualitative agreement. The most prominent distinctions are revealed for tetradecane and 1,14-dichlorotetradecane. It is found that differences in the electronic (ΔEel) and electronic plus zero-point (ΔE0) energies between the hairpin and all-trans conformers have similar tendencies by variations of X, Y, or n. When the ΔEel and ΔE0 values for the particular compound are close to zero and have opposite signs, the distance between X and Y equal to ~ 4.0 Å or less is an indicator for the preference of the hairpin conformer. The most strong effect on the advantageousness of the hairpin conformers is caused by two bromine atoms placing at the ends of molecules: for all considered 1,n-dibromoalkanes, the hairpin conformers are more favorable than the all-trans ones.

Keywords

Flexible molecules Intramolecular contacts Noncovalent interactions DFT calculations MP2 calculations 

Notes

Compliance with ethical standards

Conflict of interest

The author declares that she has no conflict of interest.

Supplementary material

11224_2019_1281_MOESM1_ESM.pdf (361 kb)
ESM 1 (PDF 361 kb)

References

  1. 1.
    Sakurai T, Sundaralingam M, Jeffrey GA (1963) A nuclear quadrupole resonance and X-ray study of the crystal structure of 2,5-Dichloroaniline. Acta Cryst 16:354–363CrossRefGoogle Scholar
  2. 2.
    Wheeler GL, Colson SD (1976) Intermolecular interactions in polymorphic p-dichlorobenzene crystals: the α, β, and γ phases at 100°K. J Chem Phys 65:1227–1235CrossRefGoogle Scholar
  3. 3.
    Sarma JARP, Desiraju GR (1986) The role of Cl...Cl and C–H...O interactions in the crystal engineering of 4-Å short-axis structures. Acc Chem Res 19:222–228CrossRefGoogle Scholar
  4. 4.
    Grineva OV, Zorkii PM (1998) Intermolecular interaction energy in crystals of some chlorine-containing organic compounds. Russ J Phys Chem 72:622–628Google Scholar
  5. 5.
    Grineva OV, Zorkii PM (2000) Aggregation of halogen atoms in haloorganic crystals with low halogen contents. Russ J Phys Chem 74:1758–1764Google Scholar
  6. 6.
    Grineva OV, Zorkii PM (2001) Isostructural and nonisostructural compounds in series of halogenated organic crystal substances. Structure of Hal-aggregates. J Struct Chem 42:16–23CrossRefGoogle Scholar
  7. 7.
    Nayak SK, Reddy MK, Row TNG, Chopra D (2011) Role of hetero-halogen (F···X, X = Cl, Br, and I) or homo-halogen (X···X, X = F, Cl, Br, and I) interactions in substituted Benzanilides. Cryst Growth Des 11:1578–1596CrossRefGoogle Scholar
  8. 8.
    Foi A, Correa RS, Ellena J, Doctorovich F, Di Salvo F (2014) Halogen···halogen contacts for the stabilization of a new polymorph of 9,10-dichloroanthracene. J Mol Struct 1059:1–7CrossRefGoogle Scholar
  9. 9.
    Cavallo G, Metrangolo P, Milani R, Pilati T, Priimagi A, Resnati G, Terraneo G (2016) The halogen bond. Chem Rev 116:2478–2601CrossRefGoogle Scholar
  10. 10.
    Desiraju GR, Sarma JARP (1986) The chloro-methyl exchange rule and its violations in the packing of organic molecular solids. Proc Indian Acad Sci (Chem Sci) 96:599–605CrossRefGoogle Scholar
  11. 11.
    Edwards MR, Jones W, Motherwell WDS, Shields GP (2001) Crystal engineering and chloro-methyl interchange - a CSD analysis. Mol Cryst Liq Cryst 356:337–353CrossRefGoogle Scholar
  12. 12.
    Nath NK, Nangia A (2012) Isomorphous crystals by chloro-methyl exchange in polymorphic fuchsones. Cryst Growth Des 12:5411–5425CrossRefGoogle Scholar
  13. 13.
    Grineva OV (2009) Conformations and intermolecular contacts of 4-and 4,4′-substituted biphenyl molecules in crystals. J Struct Chem 50:727–734CrossRefGoogle Scholar
  14. 14.
    Leon CDA, Echeverria GA, Piro OE, Ulic SE, Jios JL, Paci MB, Arguello GA (2016) The role of halogen C-X1···X2-C contact on the preferred conformation of 2-perhalomethylchromones in solid state. Chem Phys 472:142–155CrossRefGoogle Scholar
  15. 15.
    Haruna K, Alenaizan AA, Al-Saadi AA (2016) Density functional theory study of the substituent effect on the structure, conformation and vibrational spectra in halosubstituted anilines. RSC Adv 6:67794–67804CrossRefGoogle Scholar
  16. 16.
    Goodman JM (1997) What is the longest unbranched alkane with a linear global minimum conformation? J Chem Inf Comput Sci 37:876–878CrossRefGoogle Scholar
  17. 17.
    Lüttschwager NOB, Wassermann TN, Mata RA, Suhm MA (2013) The last globally stable extended alkane. Angew Chem Int Ed 52:463–466CrossRefGoogle Scholar
  18. 18.
    Byrd JN, Bartlett RJ, Montgomery Jr JA (2014) At what chain length do unbranched alkanes prefer folded conformations? J Phys Chem A 118:1706–1712CrossRefGoogle Scholar
  19. 19.
    Liakos DG, Neese F (2015) Domain based pair natural orbital coupled cluster studies on linear and folded alkane chains. J Chem Theory Comput 11:2137–2143CrossRefGoogle Scholar
  20. 20.
    Zefirov YV, Porai-Koshits MA (1980) Mean-statistical value of the van der Waals radius of the fluorine atom. J Struct Chem 21:526–530CrossRefGoogle Scholar
  21. 21.
    Zefirov YV, Zorkii PM (1974) Statistical mean values of the van der Waals radii of organogenic elements. J Struct Chem 15:102–105CrossRefGoogle Scholar
  22. 22.
    Zefirov YV, Porai-Koshits MA (1986) Geometry of halogen-halogen specific interactions in organic crystals. J Struct Chem 27:239–244CrossRefGoogle Scholar
  23. 23.
    Groom CR, Bruno IJ, Lightfoot MP, Ward SC (2016) The Cambridge structural database. Acta Crystallogr Sect B Struct Sci Cryst Eng Mat 72:171–179CrossRefGoogle Scholar
  24. 24.
    Chai JD, Head-Gordon M (2008) Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections. Phys Chem Chem Phys 10:6615–6620CrossRefGoogle Scholar
  25. 25.
    DiLabio GA, Otero-de-la-Roza A (2016) In: Parrill AL, Lipkowitz KB (eds) Reviews in Computational Chemistry, vol 29. Wiley, Hoboken, pp 1–97Google Scholar
  26. 26.
    Burns LA, Vázquez-Mayagoitia Á, Sumpter BG, Sherrill CD (2011) Density-functional approaches to noncovalent interactions: a comparison of dispersion corrections (DFT-D), exchange-hole dipole moment (XDM) theory, and specialized functionals. J Chem Phys 134:084107CrossRefGoogle Scholar
  27. 27.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA et al (2009) Gaussian 09, revision D.01. Gaussian, Inc., Wallingford, CTGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Chemistry Department of Moscow M.V. Lomonosov State UniversityMoscowRussia

Personalised recommendations