Novel Compounds Sn10In14P22I8 and Sn14In10P21.2I8 with Clathrate I Structure: Synthesis and Crystal and Electronic Structure

Two new supramolecular pnictidehalides Sn10In14P22I8 (I) and 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 n (No. 223) with the unit cell parameter a=11.0450(7) ? (Z=1) while II reveals a complicated superstructure (space group P42/m (No. 84), a=24.745(3) ?, c=11.067(1) ?, 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–2theta scans, leastsquares refinement against F2) to R=0.0376 (Sn10In14P22I8) and R=0.0569 (Sn14In10P21.2I8). In both structures metal and 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 119Sn M?ssbauer 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.