[en] The compound Ba4Fe2I5S4 has been prepared at 1223-1123 K by the "U-assisted" reaction of FeS, BaS, S, and U with BaI2 as a flux. A more rational synthesis was also found; however, the presence of U appears to be essential for the formation of single crystals suitable for X-ray diffraction studies. Ba4Fe2I5S4 crystallizes in a new structure type with two formula units in space group 14/m of the tetragonal system. The structure consists of a Ba-I network penetrated by (1)(infinity) [Fe2S4] chains. Each Fe atom, which is located on a site with 4 symmetry, is tetrahedrally coordinated to four S atoms. The FeS4 tetrahedra edge-share to form linear (1)(infinity)[Fe2S4] chains in the [001] direction. The Fe-Fe interatomic distance in these chains is 2.5630(4) angstrom, only about 3 % longer than the shortest Fe-Fe distance in alpha-Fe metal. Charge balance dictates that the average formal oxidation state of Fe in these chains is +2.5. The Mossbauer spectra obtained at 85 and 270 K comprise a single quadrupole doublet that has hyperfine parameters consistent with an average Fe oxidation state of +2.5. The Mossbauer spectrum obtained at 4.2 K consists of a single magnetic sextet with a small hyperfine field of -15.5 T. This spectrum is also consistent with rapid electron delocalization and an average Fe oxidation state of +2.5. The molar magnetic susceptibility of Ba4Fe2I5S4, obtained between 3.4 and 300 K, qualitatively indicates the presence of weak pseudo-one-dimensional ferromagnetic exchange within a linear chain above 100 K and weak three-dimensional ordering between the chains at lower temperatures.
Disciplines :
Chemistry
Author, co-author :
Gray, Danielle L
Long, Gary J
Grandjean, Fernande ; Université de Liège - ULiège > Département de physique > Département de physique
Hermann, Raphaël ; Université de Liège - ULiège > Département de physique > Département de physique
Ibers, James A
Language :
English
Title :
Syntheses, structure, and a Mossbauer and magnetic study of Ba4Fe2I5S4
Publication date :
2008
Journal title :
Inorganic Chemistry
ISSN :
0020-1669
eISSN :
1520-510X
Publisher :
American Chemical Society, Washington, United States - District of Columbia
Grey, I. E.; Hong, H.; Steinfink, H. Inorg. Chem. 1971, 10, 340-343.
Swinnea, J. S.; Steinfink, H. J. Solid State Chem. 1980, 32, 329-334.
Hong, H. Y.; Steinfink, H. J. Solid State Chem. 1972, 5, 93-104.
Lemley, J. T.; Jenks, J. M.; Hoggins, J. T.; Eliezer, Z.; Steinfink, H. J. Solid State Chem. 1976, 16, 117-128.
Cohen, S.; Kimizuka, N.; Steinfink, H. J. Solid State Chem. 1980, 35, 181-186.
Grey, I. E. Ada Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. 1975, 31, 45-48.
Cohen, S.; Rendon-Diazmiron, L. E.; Steinfink, H. J. Solid State Chem. 1978, 25, 179-187.
Hoggins, J. T.; Steinfink, H. Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. 1977, 33, 673-678.
Reiff, W. M.; Grey, I. E.: Fan, A.; Eliezer, Z.; Steinfink, H. J. Solid State Chem. 1975, 13, 32-40.
SMART, version 5.054, Data Collection and SAINT-Plus, version 6.45a, Data Processing Software for the SMART System; Bruker Analytical X-Ray Instruments, Inc.: Madison, WI, 2003.
Sheldrick, G. M. SHELXTL, version 6.14; Bruker Analytical X-Ray Instruments, Inc.: Madison, WI, 2003.
Gelato, L. M.; Parthé, E. J. Appl. Crystallogr. 1987, 20, 139-143.
Gray, D. L.; Ibers, J. A. J. Alloys Compd. 2007, 440, 74-77.
Jette, E. R.; Foote, F. J. Chem. Phys. 1935, 3, 605-616.
Von, Seyerl, J.; Scheidsteger, O.; Berke, H.; Huttner, G. J. Organomet. Chem. 1986, 311, 85-89.
Gerlitzki, N.; Mudring, A.-V.; Meyer, G. Z. Anorg. Allg. Chem. 2005, 631, 381-384.
Hoggins, J. T.; Steinfink, H. Inorg. Chem. 1976, 15, 1682-1685.
Shenoy, G. K.; Wagner, F. E.; Kalvius, G. M. In Mössbauer Isomer Shifts; Shenoy, G. K., Wagner, F. E., Eds.; North-Holland Publishing Company: Amsterdam, The Netherlands, 1978; p 51.
Taft, C. A.; Braga, M. Phys. Rev. B 1980, 21, 5802-5807.
Lie, S. K.; Taft, C. A. Phys. Rev. B 1983, 28, 7308-7316.
Taft, C. A.; Raj, D.; Danon, J. J. Phys. Colloq. 1974, 6, 241-245.
Cooper, D. M.; Dickson, D. P. E.; Domingues, P. H.; Gupta, G. P.; Johnson, C. E.; Thomas, M. F.; Taft, C. A.; Walker, P. J. J. Magn. Magn. Mater. 1983, 36, 171-174.
Watson, R. E. Phys. Rev. 1960, 118, 1036-1045.
Zener, C. Phys. Rev. 1951, 82, 403-405.
Hatfield, W. E. In Solid State Chemistry: Techniques; Cheetham, A. K., Day, P., Eds.; Oxford University Press: New York, 1987.
