New insights into the crystal chemistry of agardite-(Ce): refinement of the crystal structure, hydrogen bonding, and epitaxial intergrowths with the Sb-analogue of auriacusite

  • Sergey M. Aksenov
  • Nikita V. Chukanov
  • Jörg Göttlicher
  • Steffen Möckel
  • Dmitriy Varlamov
  • Konstantin V. Van
  • Ramiza K. Rastsvetaeva
Original Paper
  • 42 Downloads

Abstract

Agardite-(Ce) from Clara Mine, Schwarzwald, Germany, has been investigated by means of electron microprobe analysis, single-crystal X-ray analysis, XANES spectroscopy and IR spectroscopy. Hexagonal unit-cell parameters are: a = 13.598(6), c = 5.954(3) Å; V = 953.5(2) Å3; space group P63/m. The structure has been solved and refined to final R1 = 3.87%, wR2 = 5.02 for 786 I > 3σ(I). Hydrogen atoms have been localized. The crystal-chemical formula is (Z = 2): A(1)(Ce0.82Ca0.14Sr0.04)Σ1.00A(2)(Ca0.03Ce0.02)Σ0.05 [Cu5.75(Fe3+, Mn)0.20]Σ5.95 [T(1)(AsO4)2.96T(2)(SbO4)0.04)]Σ3.00 (OH)5.96O0.04·3H2O. Hydrogen bonding in agardite-series minerals has been characterized for the first time. IR spectra of agardite-(Ce) and agardite-(Nd) from Lavrion used for comparison, as well as structural data indicate the presence of isolated H+ cations that do not form strong covalent bonds with coordinating O atoms. Agardite-(Ce) from Clara Mine forms epitaxial growths with the Sb-analogue of auriacusite. The latter mineral was characterized by EDS analyses; its typical empirical formulae are \({\text{Ca}}_{0.0 6} {\text{Ce}}_{0.0 4} {\text{Fe}}^{ 3+ }{}_{ 1.0 6} {\text{Cu}}_{0. 8 9}\)[(SbO4)0.58(AsO4)0.38(SiO4)0.04]Σ1.00(O,OH) and \({\text{Ca}}_{0.0 7 5} {\text{Ce}}_{0.0 4} {\text{Fe}}^{ 3+ }{}_{0. 9 3} {\text{Cu}}_{0. 9 7}\)[(SbO4)0.59(AsO4)0.35(SiO4)0.06]Σ1.00(O,OH). The formation of uniaxial growths of the Sb-analogue of auriacusite and agardite-(Ce) is caused by the close values of their c parameters (for auriacusite s.s. c  =  5.9501(5) Å). Three-valence state of iron and five-valence of antimony in both minerals has been validated by means of Fe K- and Sb L2,3-edge XANES spectroscopy.

Keywords

Agardite-(Ce) Agardite-(Nd) Crystal structure Hydrogen bonding IR spectrum Clara Mine Lavrion 

Supplementary material

269_2017_899_MOESM1_ESM.docx (47 kb)
Supplementary material 1 (DOCX 46 kb)

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Copyright information

© Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  • Sergey M. Aksenov
    • 1
    • 2
    • 3
  • Nikita V. Chukanov
    • 4
  • Jörg Göttlicher
    • 5
  • Steffen Möckel
    • 6
  • Dmitriy Varlamov
    • 4
    • 7
  • Konstantin V. Van
    • 7
  • Ramiza K. Rastsvetaeva
    • 3
  1. 1.Faculty of GeologySt Petersburg State UniversitySt PetersburgRussia
  2. 2.Nesmeyanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussia
  3. 3.FSRC “Crystallography and Photonics”Russian Academy of SciencesMoscowRussia
  4. 4.Institute of Problems of Chemical PhysicsRussian Academy of SciencesChernogolovka, Moscow RegionRussia
  5. 5.Karlsruhe Institute of Technology, Institute for Photon Science and Synchrotron Radiation (IPS)Eggenstein-LeopoldshafenGermany
  6. 6.Alpha-Geophysik in SachsenBurkersdorfGermany
  7. 7.Institute of Experimental MineralogyRussian Academy of SciencesChernogolovka, Moscow RegionRussia

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