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- Lindsjö, Martin, et al.
(author)
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Novel Compounds Sn14In10P22I8 and Sn14In10P21.2I8 with Clathrate-I Structure: Synthesis and Crystal and Electronic Structure
- 2001
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In: Journal of Solid State Chemistry. - : Elsevier BV. - 0022-4596 .- 1095-726X. ; 161:2, s. 232-242
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Journal article (peer-reviewed)abstract
- Two new supramolecular pnictidehalides Sn10In14P22I8 (I) anti Sn14In10P21.2I8 (II) have been synthesized using a standard ampoule technique. Both compounds possess the clathrate I type of structure. I crystallizes in the cubic space group Pm (3) over barn (No. 223) with the unit cell parameter a = 11.0450(7) (Z = 1) while II reveals a complicated superstructure (space group P4(2)/m (No. 84), a = 24.745(3) Angstrom, c = 11.067(1) Angstrom, Z = 5) resulting from the partial ordering of vacancies at phosphorus sites. The crystal structures have been solved based on single-crystal X-ray diffraction data sets (omega -2 theta) scans, least-squares refinement against F-2) to R = 0.0376 (Sn10In14P22I8) and R = 0.0569 (Sn14In10P21.2I8). In both structures metal anti phosphorus atoms form a cationic clathrate I framework hosting iodine atoms in the cavities. The composition of both phases complies with the Zintl-Klemm formalism which justifies the existence of vacancies in the structure of II. The Sn-119 Mossbauer spectroscopy data together with the results of the band structure calculations suggest that the electron density on tin atoms is reduced in favor of bands, which lie just below the Fermi level and must define electronic properties of the compounds in question. The differences in the crystal and electronic structures of the cationic tin clathrates are discussed.
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- Kuznetsov, Alexei N., et al.
(author)
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Synthesis of main group polycations in molten and pseudo-molten GaBr3 media
- 2005
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In: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; :24, s. 4907-4913
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Journal article (peer-reviewed)abstract
- The prospects of synthesizing polycationic species using GaBr3 in benzene solution at room temperature have been investigated. The salts Bi-8[GaBr4](2), Sb-8[GaBr4](2) and Te-4- [Ga2Br7](2) have been isolated and characterized. The first two compounds are isotypic with Sb-8[GaCl4](2), crystallize in the space group Pna2(1), and feature square anti-prismatic E-8(2+) polycations (E = Sb, Bi). Unit-cell parameters for Bi-8[GaBr4](2) are a = 18.3014(10) angstrom, b = 10.3391(6) angstrom and c = 13.5763(7) angstrom, and for Sb-8[GaBr4](2); a = 18.096(2) angstrom, b = 10.1572(9) angstrom and c = 13.2168(10) angstrom. Te-4[Ga2Br7](2) crystallizes in the space group P2(1)/c with a = 10.1600(9) angstrom, b = 10.8314(9) angstrom, c = 13.8922(10) angstrom and beta = 99.182(7)degrees, and features a square-planar Te-4(2+) polycation. The compound Bi-5[GaBr4](3) has been synthesized from molten GaBr3 and characterized by using powder diffractometry in space group Fm-3c; a = 17.6263(8) angstrom. The structure model for this compound suggests the included Bi-5(3+) cations to be practically freely oriented within its cavities in the solid phase.
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