Structure refinement and hydrogen bonding of ferrinatrite, Na3Fe(SO4)3⋅3H2O

  • Zhuming Yang
  • Gerald GiesterEmail author
Original Paper


The structure of trigonal ferrinatrite, Na3Fe(SO4)3⋅3H2O, from the Hongshan Cu-Au deposit, Eastern Tianshan, NW China was refined in space group P\( \overline{3} \) based on single crystal X-ray diffraction data [a = 15 .553(2), c = 8.6616(17 ) Å, V = 1814.4(5) Å3, Z = 6; R1 = 0.0535]. All hydrogen atoms were located by difference Fourier methods and refined with soft restrictions for distances, but with fixed thermal isotropic displacement parameters. The atomic arrangement in ferrinatrite is based on chains along [001] consisting of isolated FeO6-octahedra corner-linked with sulfate groups. All vertices of octahedra link to tetrahedra, and half the tetrahedron vertices link to octahedra. These chains are linked by interstitial Na-ions and H2O groups. All Na atoms are coordinated to four oxygen atoms of sulfate groups and to two oxygen atoms of H2O molecules within 2.33–2.71 Å; next oxygens are at distances of 2.85–3.00 Å. Among six hydrogen bonds, three acceptor O-atoms of sulfate groups belong to the nearest octahedral-tetrahedral chains, and three acceptor sulfate O-atoms from the neighboring chains, which further strengthen the linkages between octahedral-tetrahedral chains. The O–H···O distances are in the range 2.86–3.13 Å. The O–H stretching frequencies derived from structural data are in good consistence with the known Infrared spectra.


Ferrinatrite Hydrated sulfate Crystal structure Hydrogen-bonding system 



The authors acknowledge the help of Dr. Hao Xiang and Liang Tongling with the single-crystal structure measurement. The project was supported by the National Natural Science Foundation of China (No. 41272063).


  1. Brese NE, O’Keeffe M (1991) Bond-valence parameters for solids. Acta Cryst B47:192–197CrossRefGoogle Scholar
  2. Brown ID (1981) The bond-valence method: an empirical approach to chemical structure and bonding. In: O'Keeffe M, Navrotsky A (eds) Structure and bonding in crystals. Academic Press, New York, pp 1–30Google Scholar
  3. Brown ID (2002) The chemical bond in inorganic chemistry: the bond valence model. Oxford Scientific Publication, UKGoogle Scholar
  4. Cesbron F (1964) Contribution à la minéralogie des sulphates de fer hydratés. Bull Soc Minéral 87:125–143 (in French)Google Scholar
  5. Della Ventura G, Ventruti G, Bellatreccia F, Scordari F, Cestelli Guidi M (2013) FTIR transmission spectroscopy of sideronatrite, a sodium-iron hydrous sulfate. Mineral Mag 77(3):499–507CrossRefGoogle Scholar
  6. Dowty E (2016) Atoms V6.5.0 for atomic structure display. Shape Software, 521 Hidden 14 Valley Road, Kingsport, TN 37663 USAGoogle Scholar
  7. Ferraris G, Ivaldi G (1988) Bond valence vs. bond length in O···O hydrogen bonds. Acta Cryst B44:341–344CrossRefGoogle Scholar
  8. Graeber EJ, Rosenzweig A (1971) The crystal structures of yavapaiite, KFe(SO4)2, and goldichite, KFe(SO4)2.4H2O. Am Mineral 56:1917–1933Google Scholar
  9. Griffen DT, Ribbe PH (1979) Distortions in the tetrahedral oxyanions of crystalline substances. Neues Jahrb Mineral Abh 137:54–73Google Scholar
  10. Hawthorne FC, Krivovichev SV, Burns PC (2000) The crystal chemistry of sulfate minerals. In: Alpers CN, Jambor JL, Nordstrom BK (eds) Sulfate minerals: crystallography, geochemistry, and environmental significance. Rev Mineral Geochem l40:1–112Google Scholar
  11. Libowitzky E (1999) Correlation of O-H stretching frequencies and O-H···O hydrogen bond lengths in minerals. Monatsh Chem 130:1047–1059Google Scholar
  12. Mackintosh JB (1889) Notes on some native iron sulphates from Chili. Am J Sci 38:242–245CrossRefGoogle Scholar
  13. Majzlan J, Alpers CN, Koch CB, McCleskey RB, Myneni SCB, Neil JM (2011) Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California. Chem Geol 284:296–305CrossRefGoogle Scholar
  14. Mereiter K (1976) Die Kristallstruktur des Ferrinatrits, Na3Fe[SO4]3·3H2O. Tschermaks Mineral Petrogr Mitt 23:317–327 (in German)Google Scholar
  15. Mukhtarova NN, Rastsvetaeva RK, Ilyukhin VV, Belov NV (1979) Crystal structure of Na3In(SO4)3⋅3H2O. Dokl Akad Nauk SSSR 244:602–606Google Scholar
  16. Palmer KJ, Wong RY, Lee KS (1972) The crystal structure of ferric ammonium sulfate trihydrate, FeNH4(SO4)2·3H2O. Acta Cryst B28:236–241CrossRefGoogle Scholar
  17. Rouchon V, Badet H, Belhadj O, Bonnerot O, Lavedrine B, Michard JG, Miska S (2012) Raman and FTIR spectroscopy applied to the conservation report of paleontological collections: identification of Raman and FTIR signatures of several iron sulfate species such as ferrinatrite and sideronatrite. J Raman Spectrosc 43:1265–1274CrossRefGoogle Scholar
  18. Sabelli C, Santucci A (1987) Rare sulfate minerals from the Cetine mine, Tuscany, Italy. Neues Jahrb Mineral Mh 1987:171–182Google Scholar
  19. Scordari F, Ventruti G (2009) Sideronatrite, Na2Fe(SO4)2(OH)·3H2O: crystal structure of the orthorhombic polytype and OD character analysis. Am Mineral 94:1679–1686CrossRefGoogle Scholar
  20. Scordari F (1977) The crystal structure of ferrinatrite, Na3(H2O)3[Fe(SO4)3] and its relationship to Maus's salt, (H3O)2K2{K0.5(H2O)0.5}6[Fe3O(H2O)3(SO4)6](OH)2. Mineral Mag 41:375–383CrossRefGoogle Scholar
  21. Sheldrick GM (1997) SHELXL-97, program for the refinement of crystal structures. University of Göttingen, GermanyGoogle Scholar
  22. Ventruti G, Della Ventura G, Lacalamita M, Sbroscia M (2019) Crystal-chemistry and vibrational spectroscopy of ferrinatrite, Na3[Fe(SO4)3] ·3H2O, and its high-temperature decomposition. Phys Chem Miner. 46(2):119–131.
  23. Ventruti G, Scordari F, Della Ventura G, Bellatreccia F, Gualtieri AF, Lausi A (2013) The thermal stability of sideronatrite and its decomposition products in the system Na2O–Fe2O3–SO2–H2O. Phys Chem Miner 40:659–670CrossRefGoogle Scholar
  24. Ventruti G, Stasi F, Scordari F (2010) Metasideronatrite: crystal structure and its relation with sideronatrite. Am Mineral 95:329–334CrossRefGoogle Scholar
  25. Wildner M, Giester G (1991) Fe(II)Fe(III)2(SO4)4·2H2O: a new Fe(II)-Fe(III) compound. Synthesis and crystal structure. Z Krist 196:269–277CrossRefGoogle Scholar
  26. Xu YX (2007) Discovery of system sulfate minerals and formation mechanism of oxidation zone in Hongshan HS-epithermal Cu-Au deposit, Eastern Tianshan, and their significances. Dissertation, Institute of Geology and Geophysics, Chinese Academy of Sciences (in Chinese with English abstract)Google Scholar
  27. Xu YX, Qin KZ, Ding KS, Li JX, Miao Y, Fang TH, XU XW, Li DM, Luo XQ (2008) Geochronology evidence of Mesozoic metallogenesis and Cenozoic oxidation at Hongshan HS-epithermal Cu-Au deposit, Kalatage region, Eastern Tianshan, and its tectonic and paleoclimatic significances. Acta Petrol Sin 24:2371–2383 (in Chinese with English abstract)Google Scholar
  28. Yang ZM, Giester G, Ding KS, Li H (2015) Crystal structure of sideronatrite-2M, Na2Fe(SO4)2(OH)(H2O)3, a new polytype from Xitieshan lead-zincdeposit, Qinghai Province, China. Eur J Mineral 27:427–432CrossRefGoogle Scholar
  29. Yang ZM, Giester G (2016) Hydrogen-bonding system in amarillite, NaFe(SO4)2(H2O)6: the structure refinement. Eur J Mineral 28:953–958CrossRefGoogle Scholar
  30. Zhang MJ, Wang XB (1998) The Mössbauer spectra characteristics in weathering of sulfide deposits in drought district—a case study of Xitieshan lead-zinc deposit, Qinghai Province. Acta Sediment Sin 16(4):153–158 (in Chinese with English abstract)Google Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Institute of Geology and GeophysicsChinese Academy of SciencesBeijingChina
  2. 2.Institutions of Earth SciencesChinese Academy of SciencesBeijingChina
  3. 3.University of Chinese Academy of SciencesBeijingChina
  4. 4.Institut für Mineralogie und KristallographieUniversität WienWienAustria

Personalised recommendations