Single-crystal X-ray diffraction and spectroscopic studies on humboldtine and lindbergite: weak Jahn–Teller effect of Fe2+ ion

  • Takuya EchigoEmail author
  • Mitsuyoshi Kimata
Original Paper


The single-crystal of humboldtine [Fe2+(C2O4) · 2H2O] was first synthesized and the crystal structure has been refined. Single-crystal X-ray diffraction data were collected using an imaging-plate diffractometer system and graphite-monochromatized MoKα radiation. The crystal structure of humboldtine was refined to an agreement index (R1) of 3.22% calculated for 595 unique observed reflections. The mineral crystallizes in the monoclinic system, space group C2/c, with unit cell dimensions of a = 12.011 (11), b = 5.557 (5), c = 9.920 (9) Å, β = 128.53 (3)˚, V = 518.0 (8) Å3, and Z = 4. In this crystal structure, the alternation of oxalate anions [(C2O4)2−] and Fe2+ ions forms one-dimensional chain structure parallel to [010]; water molecules (H2O)0 create hydrogen bonds to link the chains, where (H2O)0 is essentially part of the crystal structure. The water molecules with the two lone electron pairs (LEPs) on their oxygen atom are tied obliquely to the chains, because the one lone electron pair is considered to participate in the chemical bonds with Fe2+ ions. Humboldtine including hydrogen bonds is isotypic with lindbergite [Mn2+(C2O4) · 2H2O]. The donor–acceptor separations of the hydrogen bonds in humboldtine are slightly shorter than those in lindbergite, which suggests that the hydrogen bonds in the former are stronger than those in the latter. The infrared and Raman spectra of single-crystals of humboldtine and lindbergite confirmed the differences in hydrogen-bond geometry. In addition, Fe2+–O stretching band of humboldtine was split and broadened in the observed Raman spectrum, owing to the Jahn–Teller effect of Fe2+ ion. These interpretations were also discussed in terms of bond-valence theory.


Humboldtine Lindbergite Crystal structure Bond-valence theory Jahn–Teller effect Hydrogen bond 



This investigation was supported by Research Fellowships of the Japan Society for the Promotion of Science for Young Scientists (project no. 17-7332). Single-crystal X-ray data collection was performed at the Chemical Analysis Division, Research Facility Center for Science and Technology, University of Tsukuba. Helpful comments by Dr. Daniel Atencio and an anonymous reviewer led to improvements in the manuscript. We are indebted to Dr. Milan Rieder for handling of this manuscript.


  1. Adams DM, Morris DM (1968) Vibrational spectra of halides and complex halides. Part IV. Some tetrahalogenothallates and the effects of d-electronic structure on the frequencies of hexachlorometallates. J Chem Soc A 20:694–695CrossRefGoogle Scholar
  2. Altomare A, Burla M, Camalli M, Cascarano G, Giacovazzo C, Guagliardi A, Moliterni A, Polidori G, Spagna R (1999) SIR97: a new tool for crystal structure determination and refinement. J Appl Crystallogr 32:115–119CrossRefGoogle Scholar
  3. Atencio D, Coutinho JMV, Graeser S, Matioli PA, Menezes F, Luiz AD (2004) Lindbergite, a new Mn oxalate dihydrate from Boca Rica mine, Galileia, Minas Gerais, Brazil, and other occurrences. Am Mineral 89:1087–1091Google Scholar
  4. Bellamy LJ, Owen AJ (1969) A simple relationship between the infrared stretching frequencies and the hydrogen bond distances in crystals. Spectrochim Acta A25:329–333Google Scholar
  5. Benarafa A, Kacimi M, Gharbage S, Millet JMM, Ziyad M (2000) Structural and spectroscopic properties of calcium-iron Ca9Fe(PO4)7 phosphate. Mater Res Bull 35:2047–2055CrossRefGoogle Scholar
  6. Bersuker IB, Vekhter BG (1962) Splitting of infrared absorption and Raman spectra in octahedral complexes of transitional metals as a result of internal asymmetry. Izv Akad Nauk Mold 10:11–17Google Scholar
  7. Beurskens PT, Admiraal G, Beurskens G, Bosman WP, de Gelder R, Israel R, Smits JMM (1999) The DIRDIF-99 program system. Technical Report of the Crystallography Laboratory, University of NijmegenGoogle Scholar
  8. 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 II. Academic Press, New York, pp 1–30Google Scholar
  9. Brown ID (1996) VALENCE: a program for calculating bond valences. J Appl Crystallogr 29:479–480CrossRefGoogle Scholar
  10. Brown ID (2002) The chemical bond in inorganic chemistry, the bond valence model. IUCr monographs on crystallography 12. International Union of Crystallography, Oxford Science Publications, OxfordGoogle Scholar
  11. Burns RG (1993) Mineralogical applications of crystal field theory, 2nd eds. Cambridge University Press, CambridgeGoogle Scholar
  12. Calatayud ML, Castro I, Sletten J, Lloret F, Julve M (2000) Syntheses, crystal structures and magnetic properties of chromato-, sulfato-, and oxalato-bridged dinuclear copper(II) complexes. Inorg Chim Acta 300–302:846–854CrossRefGoogle Scholar
  13. Caric S (1959) The structure of humboldtine (FeC2O4·2H2O). Bull Soc Fr Miner Cristallogr 82:50–56Google Scholar
  14. Castillo O, Luque A, Julve M, Lloret F, Román P (2001) One-dimensional oxalato-bridged copper(II) complexes with 3-hydroxypyridine and 2-amino-4-methylpyridine. Inorg Chim Acta 315:9–17CrossRefGoogle Scholar
  15. Cotton FA, Meyers MD (1960) Magnetic and spectral properties of the spin-free 3d6 systems iron(II) and cobalt(III) in cobalt(III) hexafluoride ion: probable observation of dynamic Jahn–Teller effects. J Amer Chem Soc 82:5023–5026CrossRefGoogle Scholar
  16. CrystalMaker Software (2007) CrystalMaker—CrystalMaker Software. Bicester, OxfordshireGoogle Scholar
  17. Deyrieux R, Peneloux A (1969) Divalent metal oxalates. I. Crystal structure of two allotropic forms of dihydrated ferrous oxalate. Bull Soc Chim Fr 8:2675–2681Google Scholar
  18. Deyrieux R, Berro C, Peneloux A (1973) Oxalates of some divalent metals. III. Crystal structure of dihydrated manganese, cobalt, nickel, and zinc oxalates. Polymorphism of dihydrated cobalt and nickel oxalates. Bull Soc Chim Fr 1:25–34Google Scholar
  19. Dubernat J, Pezerat H (1974) Stacking faults in the dihydrated oxalates of divalent metals of the magnesium series (magnesium, manganese, iron, cobalt, nickel, zinc). J Appl Crystallogr 7:387–393CrossRefGoogle Scholar
  20. Dunitz JD, Orgel LE (1957) Electronic properties of transition-metal oxide I: distortions from cubic symmetry. J Phys Chem Solids 3:20–29CrossRefGoogle Scholar
  21. Fritsch V, Hemberger J, Büttgen N, Scheidt EW, Krug von Nidda HA, Loidol A, Tsurkan V (2004) Spin and orbital frustration in MnSc2S4 and FeSc2S4. Phys Rev Lett 92(11):116401-1–116401-4CrossRefGoogle Scholar
  22. Frost RL (2004) Raman spectroscopy of natural oxalates. Anal Chim Acta 517:207–214CrossRefGoogle Scholar
  23. Gaines RV, Skinner HCW, Foord EE, Mason B, Rosenzweig A (1997) Dana’s new mineralogy: the system of mineralogy of James Dwight Dana and Edward Salisbury Dana, 8th edn. John Wiley, New YorkGoogle Scholar
  24. Garavelli C (1955) Discovery of oxalite among the secondary minerals of the Capo Calamita layer. Rend Soc Miner Ital 11:176–181Google Scholar
  25. Gillespie RJ (1971) Molecular geometry. Van Nostrand Reinhold, New YorkGoogle Scholar
  26. Gillespie RJ, Hargittai I (1991) The VSEPR model of molecular geometry. Allyn and Bacon, BostonGoogle Scholar
  27. Hawthorne FC (1992a) The role of OH and H2O in oxide and oxysalt minerals. Z Kristallogr 201:183–206Google Scholar
  28. Hawthorne FC (1992b) Bond topology, bond valence and structure stability. In: Price GD, Ross NL (eds) The stability of minerals. Wiley series in advances in environmental science and technology 29, Chapman and Hall, London, pp 25–87Google Scholar
  29. Hawthorne FC (1997) Structural aspects of oxide and oxysalt minerals. In :Merlino S (ed) EMU notes in mineralogy, vol. 1: modular aspects of minerals, Eötvös University Press, Budapest, pp 373–429Google Scholar
  30. Higashi T (1995) Abscor—empirical absorption correction based on Fourier series approximation. Rigaku Corporation, TokyoGoogle Scholar
  31. Jahn HA, Teller E (1937) Stability of polyatomic molecules in degenerate electronis states I: orbital degeneracy. Proc R Soc A 161:220–235CrossRefGoogle Scholar
  32. Kitagawa S, Okubo T, Kawata S, Kondo M, Katada M, Kobayashi H (1995) An oxalate-linked copper(II) coordination polymer, [Cu2(oxalate)2(pyrazine)3]n, constructed with two different copper units: X-ray crystallographic and electronic structures. Inorg Chem 34:4790–4796CrossRefGoogle Scholar
  33. Lagier JP, Pezerat H, Dubernat J (1969) Magnesium, manganese, iron, cobalt, nickel, and zinc oxalate dihydrates. Evolution towards the best ordered form of compounds presenting stacking faults. Rev Chim Miner 6:1081–1093Google Scholar
  34. Libowitzky E (1999) Correlation of O–H stretching frequencies and O–H···O hydrogen bond lengths in minerals. Monatsh Chem 130:1047–1059Google Scholar
  35. Manasse E (1911) Oxalite (Humboldtine) from cape D’Arco (Elba). Rend Accad Lincei 19:138–145Google Scholar
  36. Matioli PA, Atencio D, Coutinho JMV, Menezes Filho LAD (1997) Humboldtina de Santa Maria de Itabira, Minas Gerais: primeira ocorrência brasileira e primeira ocorrência mundial em fraturas de pegmatito. An Acad Bras Cienc 69:431–432Google Scholar
  37. Mazzi F, Garavelli C (1957) Structure of oxalite, FeC2O4·2H2O. Period Miner 26:269–305Google Scholar
  38. Mazzi F, Garavelli CL (1959) Corrections of the structure of humboldtine (oxalite). Period Mineral 28:243–248Google Scholar
  39. Mikenda W (1986) Stretching frequency versus bond distance correlation of O–D(H)–Y (Y = N, O, S, Sc, Cl, Br, I) hydrogen bonds in solid hydrates. J Mol Struct 147:1–15CrossRefGoogle Scholar
  40. Moore EA (2004) Metal-ligand bonding. Royal Society of Chemistry, CambridgeGoogle Scholar
  41. Nakamoto K (1997) Infrared and Raman spectra of inorganic and coordination compounds part A: theory and applications in inorganic chemistry. Wiley-Interscience, New YorkGoogle Scholar
  42. Nakamoto K, Margoshes M, Rundle RE (1955) Stretching frequencies as a function of distances in hydrogen bonds. J Am Chem Soc 77:6480–6486CrossRefGoogle Scholar
  43. Novak A (1974) Hydrogen bonding in solids: correlation of spectroscopic and crystallographic data. Struct Bond 18:177–216CrossRefGoogle Scholar
  44. Orgel LE, Dunitz JD (1957) Stereochemistry of cupric compounds. Nature 179:462–465CrossRefGoogle Scholar
  45. Pezerat H, Dubernat J, Lagier JP (1968) Structure of magnesium, manganese, iron, cobalt, nickel, and zinc oxalate dihydrates. Existence of stacking faults. C R Acad Sci Paris Ser C 288:1357–1360Google Scholar
  46. Renner B, Lehmann G (1986) Correlation of angular and bond length distortions in TO4 units in crystals. Z Kristallogr 175:43–59Google Scholar
  47. Shannon RD (1976) Revised effective ionic radii and synthetic studies of interatomic distances in harides and chalcogenides. Acta Crystallogr A 32:751–767CrossRefGoogle Scholar
  48. Sheldrick GM (1997) SHELXL97. Program for refinement of crystal structures. University of Göttingen, GöttingenGoogle Scholar
  49. Silverstein RM, Bassler GC, Morrill TC (1991) Spectrometric identification of organic compounds, 5th edn. John Wiley, New YorkGoogle Scholar
  50. Śledzińska I, Murasik A, Piotrowski M (1986) Neutron diffraction study of crystal and magnetic structures of α-FeC2O4·2D2O. Physica B 138:315–322CrossRefGoogle Scholar
  51. Śledzińska I, Murasik A, Fischer P (1987) Magnetic ordering of the linear chain system manganese oxalate dehydrate investigated by means of neutron diffraction and bulk magnetic measurements. J Phys C 20:2247–2259CrossRefGoogle Scholar
  52. Smith E, Dent G (2005) Modern Raman spectroscopy: a practical approach. John Wiley, New YorkGoogle Scholar
  53. Soleimannejad J, Aghabozorg H, Hooshmand S, Ghadermazi M, Gharamaleki JA (2007) The monoclinic polymorph of catena-poly [[diaquamanganese(II)]-μ-oxalate-κ4O1,O2:O1′.O2′] Acta Crystallogr E 63:m2389–m2390CrossRefGoogle Scholar
  54. Stiefel EI, Brown GF (1972) Detailed nature of the six-coordinate polyhedra in tris (bidentate ligand) complexes. Inorg Chem 11:434–436CrossRefGoogle Scholar
  55. Wilson MJ, Jones D (1984) The occurrence and significance of manganese oxalate in Pertusaria corallina (Lichenes). Pedobiologia 26:373–379Google Scholar

Copyright information

© Springer-Verlag 2008

Authors and Affiliations

  1. 1.Earth Evolution Sciences, Life and Environmental SciencesUniversity of TsukubaTsukubaJapan
  2. 2.Japan International Research Center for Agricultural SciencesTsukubaJapan

Personalised recommendations