Skip to main content
SpringerLink
Log in

Tripod molecules build molecular networks and open-dimer capsules by weak interactions

  • Articles
  • Published:
Science China Chemistry Aims and scope Submit manuscript

Abstract

Three tripod molecules, tris(2-methoxy-5-nitrobenzyl)phosphine oxide (1), tris(2-butoxy-3-methyl-5-nitrobenzyl)phosphine oxide (2), and tris(3-nitrobenzyl)amine (TNBA), were synthesized and crystallized. The structures of 1, 2, and their comparison (TNBA) were determined by X-ray crystallography. It is noteworthy that compound 1 interacted with adjacent molecules via π-π stacking and C-H⋯π interactions to yield an open supramolecular network with the porosity P in 8.9%, whereas compound 2 gathered closely to form an open-dimer capsule by sixfold N-O⋯π and triple C-H⋯O interactions, which showed a rare example of a stable in, out-invertomer of phosphine inversion existing in open-dimers. A series of columns were built and arranged side by side by these weak interactions. By contrast, TNBA crystallized to form a 2D network maintained by C-H⋯O and C-H⋯π interactions. It seems minor changes of the chemical structure may cause large differences in the crystal structure and interactions in crystal engineering.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Basavoju S, Aitipamula S, Desiraju GR. Host-guest and network structures of some tetraphenylmethane derivatives. CrystEngComm, 2004, 6(25): 120–125

    Article  CAS  Google Scholar 

  2. Bai ZS, Chen SS, Zhang ZH, Chen MS, Liu GX, Sun WY. Two novel interpenetrated zinc(II) and cadmium(II) coordination polymers based on 4-imidazole-benzoate: Syntheses, crystal structures and properties. Sci China Ser B: Chem, 2009, 52(4): 459–464

    Article  CAS  Google Scholar 

  3. Ou GC, Jiang L, Feng XL, Lu TB. Synthesis and structures of two supramolecular complexes constructed via hydrogen bond linking. Sci China Ser B: Chem, 2009, 52(4): 465–470

    Article  CAS  Google Scholar 

  4. Li X, Li H, Yu SY, Li YZ. Anion coordination complex [ClÌPt-(bpt)4]Cl (bpt=N,N′-bis(3-pyridylmethyl)-2-thiourea). Sci China Ser B: Chem, 2009, 52(4): 471–474

    Article  CAS  Google Scholar 

  5. Xiao X, Zhang YQ, Zhu QJ, Xue SF, Tao Z. Host-guest complexes of a water soluble cucurbit[6]uril derivative with some dications of 1, ω-alkyldipyridines: 1H NMR and X-ray structures. Sci China Ser B: Chem, 2009, 52(4): 475–482

    Article  CAS  Google Scholar 

  6. Laliberté D, Maris T, Wuest JD. Molecular networks built from weakly interacting nitro-substituted pentaerythrityl tetraaryl ethers. CrystEngComm, 2005, 7(24): 158–160

    Article  CAS  Google Scholar 

  7. Huang LL, Massa L, Karle J. Calculated interactions of a nitro group with aromatic rings of crystalline picryl bromide. Proc Natl Acad Sci USA, 2008, 105: 13720–13723

    Article  CAS  Google Scholar 

  8. Desiraju GR. The C-H⋯O Hydrogen Bond: Structural Implications and Supramolecular Design. Acc Chem Res, 1996, 29: 441–449

    Article  CAS  Google Scholar 

  9. Sutor DJ. Evidence for the existence of C-H⋯O hydrogen bonds in crystals. J Chem Soc, 1963, 1105–1110

  10. Houk KN, Menzer S, Newton SP, Raymo FM, Stoddart JF, Williams DJ. [C-H⋯O] Interactions as a control element in supramolecular complexes: experimental and theoretical evaluation of receptor affinities for the binding of bipyridinium-based guests by catenated hosts. J Am Chem Soc, 1999, 121: 1479–1487

    Article  CAS  Google Scholar 

  11. Raymo FM, Bartberger MD, Houk KN, Stoddart JF. The magnitude of [C-H⋯O] hydrogen bonding in molecular and supramolecular assembles. J Am Chem Soc, 2001, 123: 9264–9267

    Article  CAS  Google Scholar 

  12. Thaimattam R, Feng X, Sarma JARP, Mak TCW, Desiraju GR. Inclusion compounds of tetrakis(4-nitrophenyl)methane: C-H⋯O networks, pseudopolymorphism, and structural transformations. J Am Chem Soc, 2001, 123: 4432–4445

    Article  CAS  Google Scholar 

  13. Braga D, Grepioni F, Novoa JJ, Inter-anion C-H⋯O hydrogen bond like interactions: the breakdown of the strength-length analogy. Chem Commun, 1998, 1959–1960

  14. Macchi P, Iversen BB, Sironi A, Chakoumakos BC, Larsen FK. Interanionic O-H⋯O interactions: The charge density point of view. Angew Chem Int Ed, 2000, 39: 2719–2722

    Article  CAS  Google Scholar 

  15. Madhavi NNL, Katz AK, Carrell HL, Nangia A, Desiraju GR. Evidence for the characterisation of the C-H⋯π interaction as a weak hydrogen bond: toluene and chlorobenzene solvates of 2,3,7,8-tetraphenyl-1,9,10-anthyridine. Chem Commun, 1997, 1953–1954

  16. Biradha K, Zaworotko MJ. A Supramolecular analogue of cyclohexane sustained by aromatic C-H⋯π interactions: Complexes of 1,3,5-trihydroxybenzene with substituted pyridines. J Am Chem Soc, 1998, 120: 6431–6432

    Article  CAS  Google Scholar 

  17. Lindeman SV, Kosynkin D, Kochi JK. Unusually short (C-H⋯π) hydrogen bonds for effective supramolecular (aromatic/aromatic) organization in edge-to-face motifs. J Am Chem Soc, 1998, 120: 13268–13269

    Article  CAS  Google Scholar 

  18. Harder S. Can C-H⋯C(π) bonding be classified as hydrogen bonding? A systematic investigation of C-H⋯C(π) bonding to cyclopentadienyl anions. Chem Eur J, 1999, 5: 1852–1861

    Article  CAS  Google Scholar 

  19. Desiraju GR. Hydrogen bridges in crystal engineering: interactions without borders. Acc Chem Res, 2002, 35: 565–573

    Article  CAS  Google Scholar 

  20. Desiraju GR, Steiner T. The Weak Hydrogen Bond in Structural Chemistry and Biology. Oxford: Oxford University Press, 1999

    Google Scholar 

  21. Hunter CA, Lawson KR, Perkins J, Urch CJ. Aromatic interactions. J Chem Soc, Perkin Trans 2. 2001, 651–669

    Google Scholar 

  22. Demers E, Maris T, Cabana J, Fournier JH, Wuest JD. Weakly bonded molecular networks built from tetranitro- and tetracyanospirobifluorenes. Cryst Growth Des, 2005, 5(3): 1237–1245

    Article  CAS  Google Scholar 

  23. SMART, version 5. Madison, Wisconsin: Bruker AXS Inc. 2002

  24. Sheldrick GM. SADABS, Program for Empirical Absorption Correction of Area Detector Data. University of Gottingen, Göttingen, Germany, 1996

    Google Scholar 

  25. Sheldrick GM. A short history of SHELX. Acta Cryst, 2008, A64: 112–122

    CAS  Google Scholar 

  26. The percentage of volume accessible to guests was estimated by the PLATON program. See: Spek AL. PLATON, A Multipurpose Crystallographic Tool. Utrecht, the Netherlands: Utrecht University, 2001. van der Sluis P, Spek AL. BYPASS: an effective method for the refinement of crystal structures containing disordered solvent regions. Acta Cryst, 1990, A46: 194–201

    Google Scholar 

  27. Alder RW, Butts CP, Orpen AG, Read D. J Chem Soc, Perkin Trans 2, 2001, 288–295

    Google Scholar 

  28. Friedrichsen BP, Whitlock HW. Concave functionality: Intracavity phosphine oxide as a locus of complexation. J Am Chem Soc, 1989, 111: 9132–9134

    Article  CAS  Google Scholar 

  29. Friedrichsen BP, Powell DR, Whitlock HW. Sterically encumbered functional groups: An investigation of endo versus exo phosphoryl complexation using 1H and 31P NMR. J Am Chem Soc, 1990, 112: 8931–8941

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Key Laboratory of Mesoscopic Chemistry, Ministry of Education, Nanjing University, Nanjing, 210093, China

    Jun Han, Chao Deng, Ru Fang & LeYong Wang

  2. State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 210093, China

    YiZhi Li & Yi Pan

  3. School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China

    Jun Han, Chao Deng, Ru Fang & LeYong Wang

Authors
  1. Jun Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Chao Deng
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ru Fang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. YiZhi Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. LeYong Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yi Pan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to LeYong Wang or Yi Pan.

Additional information

This work was supported by the National Natural Science Foundation of China (Grant Nos. 20602017 & 20932004), the National Basic Research Program of China (Grant No. 2007CB925103), and the Natural Science Foundation of Jiangsu (Grant No. BK2008259).

Rights and permissions

Reprints and permissions

About this article

Cite this article

Han, J., Deng, C., Fang, R. et al. Tripod molecules build molecular networks and open-dimer capsules by weak interactions. Sci. China Chem. 53, 851–857 (2010). https://doi.org/10.1007/s11426-010-0119-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11426-010-0119-7

Keywords

Search

Navigation