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Dihydrogen Phosphate and Hydrogen Sulphate of 1,4-Dimethyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium: Crystal Structures, Hydrogen Bonding and Infrared Spectra

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Abstract

The crystal structures of the title compounds consist of 1,4-dimethyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium cation [C8H18N2]2+ and [H2PO4]− or [HSO4]− anions. Both crystal structures are monoclinic, the structure of the dihydrogen phosphate (I) is non-centrosymmetric (P21) with a = 6.4090(2) Å, b = 13.6920(5) Å, c = 7.6140(3) Å, β = 94.620(2)°, V = 665.97(4) Å3, Z = 2; whereas the unit cell of the hydrogen sulphate (II) is centrosymmetric (P21/c) with a = 13.8460(2) Å, b = 12.6610(2) Å, c = 8.0360(2) Å, β = 99.5800(12)°, V = 1389.10(5) Å3, Z = 4. Both the structures are formed by the different bonding patterns of the anions interlinked by strong and moderate O–H···O hydrogen bonds. While the structure of (I) consists of a two-dimensional network of the hydrogen bonded dihydrogen phosphates, the infinite chains of the hydrogen bonded hydrogen sulphates are the basic building unit of the structure (II). In addition to the dominant electrostatic interaction the divalent cations stabilize themselves in the structures by forming several C–H···O hydrogen bonds to the oxygen atoms of the anions. The IR spectra of both the compounds are strongly affected by the hydrogen bonds whose influence on OH stretching vibrations is analysed by means of the DFT calculations in the solid state.

Graphical Abstract

The crystal structures of the 1,4-dimethyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium dihydrogen phosphate and hydrogen sulphate comprise strong and moderate O–H···O hydrogen bonds significantly influencing the high energy region of IR spectra.

The crystal structure of the dihydrogen phosphate of the title cation viewed along the a axis

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References

  1. Agmon N (1995) Chem Phys Lett 244:456

    Article  CAS  Google Scholar 

  2. Kreuer KD (1996) Chem Mater 8:610

    Article  CAS  Google Scholar 

  3. Baranov AI (2003) Crystallogr Rep 48:1012

    Article  CAS  Google Scholar 

  4. Smrčok Ľ, Havlíček D, Kaman O, Rundlöf H (2009) Z Kristallogr 224:174

    Article  Google Scholar 

  5. Chudoba V (2003) PhD thesis, Charles University in Prague, Czech Republic (In Czech)

  6. Belushkin AV, Adams MA, Hull S, Shuvalov LA (1995) Solid State Ion 77:91

    Article  CAS  Google Scholar 

  7. Chisholm CRI, Haile SM (1999) Acta Cryst B55:937

    CAS  Google Scholar 

  8. Wempe MF (2001) J Mol Struct 562:63

    Article  CAS  Google Scholar 

  9. Otwinowski Z, Minor W (1997) HKL Denzo and Scalepack Program Package. Nonius BV, Delft

  10. Blessing RH (1995) Acta Cryst A51:33

    CAS  Google Scholar 

  11. Altomare A, Burla MC, Camalli M, Cascarano G, Giacovazzo C, Guagliardi A, Polidori G (1994) J Appl Crystallogr 27:435

    Google Scholar 

  12. Sheldrick GM (1993) SHELX93, Program for crystal structure refinement. University of Gottingen, Germany

    Google Scholar 

  13. Spek AL (2002) PLATON. A multipurpose crystallographic tool. Utrecht University, Netherlands (www.cryst.ch-em.uu.nl/platon)

  14. Brandenburg K (2006) Diamond. Version 3.1e. Crystal Impact GbR, Bonn, Germany

  15. Kresse G, Hafner J (1993) Phys Rev B48:13115

    Google Scholar 

  16. Kresse G, Furthmüller J (1996) Phys Rev B54:11169

    Google Scholar 

  17. Kresse G, Furthmüller J (1996) Comp Mat Sci 6:15

    Article  CAS  Google Scholar 

  18. Blöchl PE (1994) Phys Rev B50:17953

    Google Scholar 

  19. Kresse G, Joubert J (1999) Phys Rev B59:1758

    Google Scholar 

  20. Kresse G, Hafner J (1994) J Phys Condens Matter 6:8245

    Article  CAS  Google Scholar 

  21. Teter MP, Payne MC, Allan DC (1989) Phys Rev B40:12255

    Google Scholar 

  22. Bylander DM, Kleinman L, Lee S (1990) Phys Rev B42:1394

    Google Scholar 

  23. Hafner J (2003) J Mol Struct 651–653:3

    Article  Google Scholar 

  24. Portmann S, Luthi HP (2000) Chimia 54:766

    CAS  Google Scholar 

  25. Nosé SJ (1984) J Chem Phys 81:511

    Article  Google Scholar 

  26. Ferrario M, Ryckaert JP (1985) Mol Phys 54:587

    Article  CAS  Google Scholar 

  27. Ramirez-Cuesta AJ (2004) Comp Phys Commun 157:226

    Article  CAS  Google Scholar 

  28. Jeffrey GA (1997) An introduction to hydrogen bonding. Oxford University Press, New York, p 222

    Google Scholar 

  29. Fergusson G, Glidewell C, Gregson RM, Meehan PR (1998) Acta Cryst B54:129

    Google Scholar 

  30. Amri M, Zouari N, Mhiri T, Pechev S, Gravereau P, Von Der Muhll R (2007) J Phys Chem Solids 68:1281

    Article  CAS  Google Scholar 

  31. Hemamalini M, Muthiah PT, Rychlewska U, Plutecka A (2005) Acta Cryst C61:o95

    CAS  Google Scholar 

  32. Drozd M, Baran J (2006) Spectrochim Acta A 64:867

    Article  CAS  Google Scholar 

  33. Sun XM, Qu Y (2005) Acta Cryst E61:m1360

    CAS  Google Scholar 

  34. Qu Y, Sun XM (2005) Acta Cryst E61:m2121

    CAS  Google Scholar 

  35. Wiebcke M, Emmer J, Felsche J, Hoebbel D, Engelhardt G (1994) Z Anorg Allg Chem 620:757

    Article  CAS  Google Scholar 

  36. Janzen DE, Ewbank PC, Mann KR (2005) Acta Cryst C61:o631

    CAS  Google Scholar 

  37. Bratos S (1975) J Chem Phys 63:3499

    Article  CAS  Google Scholar 

  38. Bratos S, Ratajczak H (1982) J Chem Phys 76:77

    Article  CAS  Google Scholar 

  39. Fillaux F, Marchon B, Novak A (1984) Chem Phys 86:127

    Article  CAS  Google Scholar 

  40. Fillaux F, Marchon B, Novak A (1989) Chem Phys 130:257

    Article  CAS  Google Scholar 

  41. Koleva V, Stefov V, Cahil A, Najdoski M, Šoptrajanov B, Engelen B, Lutz HD (2009) J Mol Struct 919:164

    Article  CAS  Google Scholar 

  42. Engelen B, Boldt K, Műller H, Unterderweide K (1997) J Mol Struct 436–437:247

    Article  Google Scholar 

  43. Baran J, Trzebiatowska M, Ratajczak H (2004) J Mol Struct 708:127

    Article  CAS  Google Scholar 

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Acknowledgments

Financial support by the Charles University in Prague, through the project GAUK 133508 and by the Long term research plan of the Ministry of Education of the Czech Republic through the project No. MSM 0021620857 is acknowledged. The work was partially supported by the Slovak Grant Agency VEGA under the contract No. 2/0150/09.

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Authors and Affiliations

  1. Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 8, 128 40, Prague 2, Czech Republic

    Ondřej Kaman, Ivana Císařová & David Havlíček

  2. Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, 845 36, Bratislava, Slovak Republic

    Ľubomír Smrčok

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  1. Ondřej Kaman
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  2. Ľubomír Smrčok
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Correspondence to Ondřej Kaman.

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Kaman, O., Smrčok, Ľ., Císařová, I. et al. Dihydrogen Phosphate and Hydrogen Sulphate of 1,4-Dimethyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium: Crystal Structures, Hydrogen Bonding and Infrared Spectra. J Chem Crystallogr 41, 1539–1546 (2011). https://doi.org/10.1007/s10870-011-0137-0

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