Abstract
The solid solution of the general formula Sn24−x In x P19.2+0.2x Br8 (x ≤ 10) was synthesized in the Sn-In-P-Br system, and its crystal structure was determined for the composition with x = 7.8. This solid solution crystallizes in the cubic system, the space group Pm \(\bar 3\) n, and has a type-I clathrate structure, in which the clathrate framework is composed of tin, indium, and phosphorus atoms, whereas bromine atoms occupy two types of guest positions. The unit cell parameter a increases with increasing indium content, two linear regions with different increments being observed in the a(x) plot. The crystal structure of the solid solution is characterized by a complicated disorder manifested in the partial occupancy of three closely spaced positions by tin and indium atoms. The application of the Zintl formalism to the rationalization of the composition of the solid solution is discussed, and its structure is compared with the iodide analogs of similar composition but showing differences in structural details.
Similar content being viewed by others
References
T. M. Tritt, H. Bottner, L. Chen, MRS Bull., 2008, 33, 366.
N. Armaroli, V. Balzani, Angew. Chem., Int. Ed., 2007, 46, 52.
Thermoelectrics Handbook Macro to Nano, Ed. D. M. Rowe, CRC, Boca Raton (FL), 2006.
G. F. Snyder, E. S. Toberer, Nature Mater., 2008, 7, 105.
G. S. Nolas, J. Sharp, H. J. Goldsmid, Thermoelectrics: Basic Principles and New Materials Developments, Springer, New York, 2001.
A. V. Shevelkov, Usp. Khim., 2008, 77, 3 [Russ. Chem. Rev. (Engl. Transl.), 2008, 77].
M. A. White, Properties of Materials, Oxford University Press, New York, 1999.
K. A. Kovnir, A. V. Shevelkov, Usp. Khim., 2004, 73, 999 [Russ. Chem. Rev. (Engl. Transl.), 2004, 73].
A. F. Wells, Structural Inorganic Chemistry, 5th ed., Oxford University Press, London, 1984.
S. Bobev, S. C. Sevov, J. Solid State Chem., 2000, 153, 92.
J. V. Zaikina, K. A. Kovnir, A. V. Sobolev, I. A. Presniakov, Yu. Prots, M. Baitinger, W. Schnelle, A. V. Olenev, O. I. Lebedev, G. Van Tendeloo, Yu. Grin, A. V. Shevelkov, Chem. Eur. J., 2007, 13, 5090.
M. M. Shatruk, K. A. Kovnir, A. V. Shevelkov, I. A. Presniakov, B. A. Popovkin, Inorg. Chem., 1999, 38, 3455.
M. M. Shatruk, K. A. Kovnir, A. V. Shevelkov, B. A. Popovkin, Zh. Neorg. Khim., 2000, 45, 203 [Russ. J. Inorg. Chem. (Engl. Transl.), 2000, 45].
M. M. Shatruk, K. A. Kovnir, M. Lindsjö, I. A. Presniakov, L. A. Kloo, A. V. Shevelkov, J. Solid State Chem., 2001, 161, 233.
L. N. Reshetova, J. V. Zaikina, A. V. Shevelkov, K. A. Kovnir, M. Lindsjö, L. Kloo, Z. anorg. allg. Chem., 2002, 628, 2145.
K. A. Kovnir, J. V. Zaikina, L. N. Reshetova, A. V. Olenev, E. V. Dikarev, A. V. Shevelkov, Inorg. Chem., 2004, 43, 3230.
K. A. Kovnir, M. M. Shatruk, L. N. Reshetova, I. A. Presniakov, E. V. Dikarev, M. Baitinger, F. Haarmann, W. Schnelle, M. Baenitz, Yu. Grin, A. V. Shevelkov, Solid State Sci., 2005, 7, 957.
K. A. Kovnir, A. V. Sobolev, I. A. Presniakov, O. I. Lebedev, G. Van Tendeloo, W. Schnelle, Yu. Grin, A. V. Shevelkov, Inorg. Chem., 2005, 44, 8786.
K. Kishimoto, S. Arimura, T. Koyanagi, Appl. Phys. Lett., 2006, 88, 222115.
A. V. Yakimchuk, Yu. V. Zaikina, L. N. Reshetova, L. I. Ryabova, D. R. Khokhlov, A. V. Shevelkov, Fiz. Nizkikh Temperatur, 2007, 33, 369 [Low Temperature Physics (Engl. Transl.), ], 2007, 33.
J. V. Zaikina, W. Schnelle, K. A. Kovnir, A. V. Olenev, Yu. Grin, A. V. Shevelkov, Solid State Sci., 2007, 9, 664.
J. V. Zaikina, T. Mori, K. Kovnir, D. Teschner, A. Senyshyn, U. Schwarz, Yu. Grin, A. V. Shevelkov, Chem. Eur. J., 2010, 16, 12582.
M. Falmbigl, P. F. Rogl, E. Bauer, M. Kriegisch, H. Müller, S. Paschen, Mater. Res. Soc. Symp. Proc., 2009, 1166, 3.
S. Stefanoski, L. N. Reshetova, A. V. Shevelkov, G. S. Nolas, J. Electr. Mater., 2009, 38, 985.
G. J. Miller, in Chemistry, Structure, and Bonding of Zintl Phases and Ions, Ed. S. M. Kauzlarich, VCH, New York, 1996, p. 1.
A. V. Shevelkov, M. M. Shatruk, Izv. Akad. Nauk, Ser. Khim., 2001, 321 [Russ. Chem. Bull., Int. Ed., 2001, 50, 337].
H.-G. von Schnering, W. Hönle, Chem. Rev., 1988, 88, 243.
Yu. V. Karyakin, I. I. Angelov, Chistye khimicheskie veshchestva [Pure Chemical Substances], Khimiya, Moscow, 1974, 408 pp. (in Russian).
G. M. Sheldrik, SHELXS-97, Program for Crystal Structure Solution, University of Göttingen, Göttingen, Germany, 1997.
G. M. Sheldrik, SHELXL-97, Program for Crystal Structure Refinement, University of Göttingen, Göttingen, Germany, 1997.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 28—32, January, 2012.
Rights and permissions
About this article
Cite this article
Reshetova, L.N., Shevelkov, A.V. Synthesis and clathrate-type crystal structure of a solid solution in the Sn-In-P-Br system. Russ Chem Bull 61, 28–32 (2012). https://doi.org/10.1007/s11172-012-0004-y
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11172-012-0004-y