, Volume 60, Issue 5, pp 514–520 | Cite as

Complexes of An(VI) with Cyclobutanecarboxylic Acid Anions and Outer-Sphere Alkali Metal Cations

  • M. S. Grigor’ev
  • I. A. CharushnikovaEmail author
  • A. M. Fedoseev


New complexes of hexavalent actinides with cyclobutanecarboxylic acid (Hcbc) anions, Na4[NpO2· (cbc)3]4·H2O (I), K[NpO2(cbc)3] (II), Cs[NpO2(cbc)3] (III), and Cs[PuO2(cbc)3] (IV), cbc = C4H7(COO), were synthesized and studied by single crystal X-ray diffraction. The structures of I–IV are based on the anionic complexes [AnO2(cbc)3] surrounded by alkali metal cations. The AnO 2 2+ cation in the anionic complex is bonded with three chelating C4H7COO anions, and the coordination polyhedron (CP) of An is a hexagonal bipyramid with the O atoms of the AnO 2 2+ cations in apical positions. The coordination number (CN) of the alkali metal cations in the structures of II–IV is the same and equal to 6; the coordination surrounding of the K+ and Cs+ cations is constituted by the O atoms of six C4H7COO anions. The crystal structures of IIIV are examples of cubic 3-connected networks (10,3) built of alkali metal and actinide cations. In the structure of I, there are four kinds of crystallographically different NpO 2 2+ and Na+ cations. The coordination surrounding of the NpO 2 2+ cations differs only in the conformational characteristics of the C4H7COO ligands. Four independent Na+ cations differ from each other in the structure of the coordination surrounding. The CPs of the Na(1) and Na(4) atoms can be described as distorted octahedra (CN 6); that of Na(3), as a trigonal prism (CN 6); and that of Na(2), as a tetragonal pyramid (CN 5) with one of the basal vertices occupied by the Ow(1) atom of a water molecule. In the structure of I, the configuration of the network formed by the Na and Np cations differs from the cubic 3-connected network found in the structures of IIIV.


neptunium(VI) plutonium(VI) cyclobutanecarboxylic acid synthesis crystal structure 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Navaza, A., Charpin, P., Vigner, D., and Heger, G., Acta Crystallogr., Sect. C, 1991, vol. 47, no. 9, pp. 1842–1845.CrossRefGoogle Scholar
  2. 2.
    Alcock, N.W., Roberts, M.M., and Brown, D., J. Chem. Soc., Dalton Trans., 1982, no. 1, pp. 33–36.CrossRefGoogle Scholar
  3. 3.
    Charushnikova, I.A., Krot, N.N., and Starikova, Z.A., Radiochemistry, 2007, vol. 49, no. 6, pp. 565–570.CrossRefGoogle Scholar
  4. 4.
    Grigoriev, M.S. and Fedosseev, A.M., Acta Crystallogr., Sect. C, 2011, vol. 67, no. 6, pp. 205–207.CrossRefGoogle Scholar
  5. 5.
    Serezhkina, L.B., Vologzhanina, A.V., Klepov, V.V., and Serezhkin, V.N., Crystallogr. Rep., 2010, vol. 55, no. 5, pp. 773–779.CrossRefGoogle Scholar
  6. 6.
    Serezhkina, L.B., Vologzhanina, A.V., Klepov, V.V., and Serezhkin, V.N., Crystallogr. Rep., 2011, vol. 56, no. 2, pp. 265–269.CrossRefGoogle Scholar
  7. 7.
    Serezhkina, L.B., Vologzhanina, A.V., Karasev, M.O., et al., Russ. J. Inorg. Chem., 2015, vol. 60, no. 1, pp. 38–45.CrossRefGoogle Scholar
  8. 8.
    Serezhkina, L.B., Peresypkina, E.V., Virovets, A.V., and Klepov, V.V., Crystallogr. Rep., 2010, vol. 55, no. 2, pp. 221–223.CrossRefGoogle Scholar
  9. 9.
    Burkov, V.I., Mistryukov, V.E., Mikhailov, Yu.N., and Chulkanova, E.B., Russ. J. Inorg. Chem., 1997, vol. 42, no. 3, pp. 327–331.Google Scholar
  10. 10.
    Serezhkina, L.B., Peresypkina, E.V., Virovets, A.V., et al., Radiochemistry, 2013, vol. 55, no. 1, pp. 31–35.CrossRefGoogle Scholar
  11. 11.
    Serezhkin, V.N., Grigoriev, M.S., Abdulmyanov, F.R., et al., Inorg. Chem., 2016, vol. 55, no. 16, pp. 7688–7693.CrossRefGoogle Scholar
  12. 12.
    Sheldrick, G.M., SADABS, Madison, Wisconsin (USA): Bruker AXS, 2008.Google Scholar
  13. 13.
    Sheldrick, G.M., Acta Crystallogr., Sect. A, 2008, vol. 64, no. 1, pp. 112–122.CrossRefGoogle Scholar
  14. 14.
    Sheldrick, G.M., Acta Crystallogr., Sect. C, 2015, vol. 71, no. 1, pp. 3–8.CrossRefGoogle Scholar
  15. 15.
    Wells, A.F., Structural Inorganic Chemistry, Oxford: Clarendon, 1986. Translated under the title Strukturnaya neorganicheskaya khimiya, Moscow: Mir, 1987, vol. 1.Google Scholar

Copyright information

© Pleiades Publishing, Inc. 2018

Authors and Affiliations

  • M. S. Grigor’ev
    • 1
  • I. A. Charushnikova
    • 1
    Email author
  • A. M. Fedoseev
    • 1
  1. 1.Frumkin Institute of Physical Chemistry and ElectrochemistryRussian Academy of SciencesMoscowRussia

Personalised recommendations