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Stereochemistry of Neptunium in Oxygen-Containing Compounds

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Abstract

Coordination of Np(III–VII) atoms in the crystal structures of all the oxygen-containing compounds characterized with the R-factor lower than 0.1 was analyzed with the aid of Voronoi–Dirichlet polyhedra (VDPs). Nine types of NpO n coordination polyhedra (6 ≤ n ≤ 12) are realized. The most characteristic of them are trigonal dodecahedra [Np(IV)], penta- and hexagonal bipyramids [Np(V) and Np(VI)], and octahedra [Np(VII)] based on square NpO4– cores. For Np atoms of a fixed oxidation state, the volume of their VDPs in the NpO n complexes is virtually independent of the coordination number n. The VDP parameters can be used for determining the valence state of the Np atoms, finding compounds with the maximal nonlinearity of the NpO2+ and NpO22+ dioxocations, and revealing errors in the crystal structure data. Anion–anion interactions involving NpO4– and OH– ions are an important structure-forming factor in Np(VII) compounds. In sublattices consisting of Np atoms only (Np sublattices), the rule of 14 neighbors is fulfilled. Compounds in which binding Np···Np 5f interactions in crystal structures are possible were revealed by analysis of the VDPs of the atoms in the Np sublattices. In such compounds, the metal atoms form bent Np=O–Np bridging fragments and the NpVO7 bipyramids are combined in dimers sharing a common axial edge, with the Np atoms of the dimers being also bound via two carboxylate bridges.

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References

  1. Inorganic Crystal Structure Database, Gmelin-Institut für Anorganische Chemie & FIC Karlsruhe, 2016.

  2. Cambridge Structural Database System, Cambridge Crystallographic Data Centre, 2016.

  3. Krot, N.N. and Grigor’ev, M.S., Russ. Chem. Rev., 2004, vol. 73, no. 1, pp. 89–100.

    Article  CAS  Google Scholar 

  4. Serezhkin, V.N., Sidorenko, G.V., Pushkin, D.V., and Serezhkina, L.B., Radiochemistry, 2014, vol. 56, no. 2, pp. 115–133.

    Article  CAS  Google Scholar 

  5. Haire, R.G., J. Alloys Compd., 2007, vols. 444–445, pp. 63–71.

    Article  Google Scholar 

  6. Moore, K.T. and Van der Laan, G., Rev. Modern Phys., 2009, vol. 81, no. 1, pp. 235–298.

    Article  CAS  Google Scholar 

  7. Serezhkin, V.N., Savchenkov, A.V., Pushkin, D.V., and Serezhkina, L.B., Radiochemistry, 2016, vol. 58, no. 6, pp. 561–570.

    Article  CAS  Google Scholar 

  8. Serezhkin, V.N., Savchenkov, A.V., and Serezhkina, L.B., Radiochemistry, 2017, vol. 59, no. 1, pp. 26–34.

    Article  CAS  Google Scholar 

  9. Korol’kov, D.V. and Skorobogatov, G.A., Teoreticheskaya khimiya (Theoretical Chemistry), St. Petersburg: Sankt-Peterb. Gos. Univ., 2005.

    Google Scholar 

  10. Serezhkin, V.N., Mikhailov, Yu.N., and Buslaev, Yu.A., Russ. J. Inorg. Chem., 1997, vol. 42, no. 12, pp. 1871–1910.

    Google Scholar 

  11. Serezhkin, V.N. and Urusov, V.S., Crystallogr. Rep., 2017, vol. 62, no. 1, pp. 50–59.

    Article  CAS  Google Scholar 

  12. Serezhkin, V.N., Savchenkov, A.V., and Serezhkina, L.B., Russ. J. Inorg. Chem., 2017, vol. 62, no. 5, pp. 633–638.

    Article  Google Scholar 

  13. Serezhkin, V.N., Medvedkov, Ya.A., Serezhkina, L.B., and Pushkin, D.V., Russ. J. Phys. Chem. A, 2015, vol. 89, no. 6, pp. 1018–1027.

    Article  CAS  Google Scholar 

  14. Charushnikova, I.A., Krot, N.N., and Starikova, Z.A., Radiochemistry, 2000, vol. 42, no. 5, pp. 434–438.

    CAS  Google Scholar 

  15. Morss, L.R., Appelman, E.H., Gerz, R.R., and Martin-Rovet, D., J. Alloys Compd., 1994, vol. 203, pp. 289–295.

    Article  CAS  Google Scholar 

  16. Forbes, T.Z., Burns, P.C., Skanthakumar, S., and Soderholm, L., J. Am. Chem. Soc., 2007, vol. 129, pp. 2760–2761.

    Article  CAS  Google Scholar 

  17. Bolvin, H., Wahlgren, U., Gropen, O., and Marsden, C., J. Phys. Chem. A, 2001, vol. 105, no. 46, pp. 10 570–10 576.

    Article  Google Scholar 

  18. Charushnikova, I.A., Perminov, V.P., and Katser, S.B., Radiochemistry, 1995, vol. 37, no. 6, pp. 454–458.

    Google Scholar 

  19. Budantseva, N.A. and Fedoseev, A.M., Radiokhimiya, 1993, vol. 35, no. 1, pp. 29–38.

    Google Scholar 

  20. Andreev, G.B., Antipin, M.Yu., Budantseva, N.A., and Krot, N.N., Russ. J. Coord. Chem., 2005, vol. 31, no. 11, pp. 800–803.

    Article  CAS  Google Scholar 

  21. Serezhkin, V.N. and Serezhkina, L.B., Vestn. Samarsk. Gos. Univ., Estestv.-Nauchn. Ser., 2017, no. 4 (44), pp. 129–152.

    Google Scholar 

  22. Almond, P.M., Sykora, R.E., Skanthakumar, S., et al., Inorg. Chem., 2004, vol. 43, pp. 958–963.

    Article  CAS  Google Scholar 

  23. Wang, S., Diwu, J., Alekseev, E.V., et al., Inorg. Chem., 2012, vol. 51, no. 13, pp. 7016–7018.

    Article  CAS  Google Scholar 

  24. Wang, S., Alekseev, E.V., Depmeier, W., and Albrecht-Schmitt, T.E., Chem. Commun., 2010, vol. 46, no. 22, pp. 3955–3957.

    Article  CAS  Google Scholar 

  25. Smith, A.L., Hen, A., Raison, P.E., et al., Inorg. Chem., 2015, vol. 54, no. 9, pp. 4556–4564.

    Article  CAS  Google Scholar 

  26. Conway, J. and Sloane, N.J.A., Sphere Packings, Lattices, and Groups, New York: Springer, 1988.

    Book  Google Scholar 

  27. Grigor’ev, M.S., Yanovskii, A.I., Krot, N.N., and Struchkov, Yu.T., Radiokhimiya, 1987, vol. 29, no. 6, pp. 574–579.

    Google Scholar 

  28. Grigor’ev, M.S., Gulev, B.F., and Krot, N.N., Radiokhimiya, 1986, vol. 28, no. 6, pp. 690–694.

    Google Scholar 

  29. Serezhkin, V.N. and Buslaev, Yu.A., Russ. J. Inorg. Chem., 1997, vol. 42, no. 7, pp. 1064–1071.

    Google Scholar 

  30. Serezhkin, V.N., Serezhkina, L.B., Pushkin, D.V., et al., Dokl. Chem., 2001, vol. 379, nos. 4–6, pp. 212–215.

    Article  Google Scholar 

  31. Pushkin, D.V., Serezhkin, V.N., Karasev, M.O., and Kravchenko, E.A., Russ. J. Inorg. Chem., 2010, vol. 55, no. 4, pp. 523–529.

    Article  CAS  Google Scholar 

  32. Serezhkin, V.N., Karasev, M.O., and Serezhkina, L.B., Radiochemistry, 2013, vol. 55, no. 2, pp. 137–146.

    Article  CAS  Google Scholar 

  33. Budantseva, I.A., Grigor’ev, M.S., Mishkevich, V.I., and Fedoseev, A.M., Radiochemistry, 2011, vol. 53, no. 6, pp. 576–581.

    Article  CAS  Google Scholar 

  34. Burns, J.H., Baldwin, W.H., and Stokely, J.R., Inorg. Chem., 1973, vol. 12, no. 2, pp. 466–469.

    Article  CAS  Google Scholar 

  35. Serezhkin, V.N., Structural Chemistry of Inorganic Actinide Compounds, Krivovichev, S.V., Burns, P.C., and Tananaev, I.G., Eds., Amsterdam: Elsevier, 2007, pp. 31–65.

  36. Serezhkin, V.N., Krivolapova, M.A., and Serezhkina, L.B., Russ. J. Coord. Chem., 1998, vol. 24, no. 1, pp. 59–66.

    CAS  Google Scholar 

  37. Krot, N.N., Charushnikova, I.A., and Perminov, V.P., Radiochemistry, 2015, vol. 57, no. 5, pp. 451–458.

    Article  CAS  Google Scholar 

  38. Serezhkin, V.N., Verevkin, A.G., Pushkin, D.V., and Serezhkina, L.B., Russ. J. Coord. Chem., 2008, vol. 34, no. 3, pp. 225–232.

    Article  CAS  Google Scholar 

  39. Serezhkin, V.N., Serezhkina, L.B., and Pushkin, D.V., J. Struct. Chem., 2009, vol. 50, supplement, pp. S14–S21.

    Article  CAS  Google Scholar 

  40. Serezhkin, V.N., Vologzhanina, A.V., Pushkin, D.V., et al., Crystallogr. Rep., 2017, vol. 62, no. 5, pp. 725–733.

    Article  CAS  Google Scholar 

  41. Cousson, A., Dabos, S., Abazli, H., et al., J. Less-Common Met., 1984, vol. 99, no. 2, pp. 233–240.

    Article  CAS  Google Scholar 

  42. Vlaisavljevich, B., Mirό, P., Ma, D., et al., Chem. Eur. J., 2013, vol. 19, no. 9, pp. 2937–2941.

    Article  CAS  Google Scholar 

  43. Grigoriev, M.S., Krot, N.N., Bessonov, A.A., and Suponitsky, K.Y., Acta Crystallogr., Sect. E, 2007, vol. 63, pp. m561–m562.

    Google Scholar 

  44. Grigor’ev, M.S., Baturin, N.A., Fedoseev, A.M., and Budantseva, N.A., Koord. Khim., 1994, vol. 20, pp. 552–556.

    Google Scholar 

  45. Jin, G., Skanthakumar, S., and Soderholm, L., Inorg. Chem., 2011, vol. 50, no. 13, pp. 6297–6303.

    Article  CAS  Google Scholar 

  46. Grigor’ev, M.S., Charushnikova, I.A., Krot, N.N., et al., Radiokhimiya, 1993, vol. 35, no. 1, pp. 31–36.

    Google Scholar 

  47. Grigor’ev, M.S., Yanovskii, A.I., Struchkov, Yu.T., et al., Radiokhimiya, 1989, vol. 31, no. 1, pp. 37–44.

    Google Scholar 

  48. Jin, G., Skanthakumar, S., and Soderholm, L., Inorg. Chem., 2011, vol. 50, no. 11, pp. 5203–5214.

    Article  CAS  Google Scholar 

  49. Nocton, G., Horeglad, P., Pecaut, J., and Mazzanti, M., J. Am. Chem. Soc., 2008, vol. 130, no. 49, pp. 16 633–16 645.

    Article  Google Scholar 

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  1. Samara University, ul. Akademika Pavlova 1, Samara, 443011, Russia

    V. N. Serezhkin & L. B. Serezhkina

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  1. V. N. Serezhkin
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  2. L. B. Serezhkina
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Correspondence to V. N. Serezhkin.

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Original Russian Text © V.N. Serezhkin, L.B. Serezhkina, 2018, published in Radiokhimiya, 2018, Vol. 60, No. 1, pp. 3–13.

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Serezhkin, V.N., Serezhkina, L.B. Stereochemistry of Neptunium in Oxygen-Containing Compounds. Radiochemistry 60, 1–12 (2018). https://doi.org/10.1134/S1066362218010010

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