CRYSTAL AND MOLECULAR-STRUCTURE AND RAMAN AND I-127 MOSSBAUER-SPECTRA OF IODINE(III) BIS(FLUOROSULFATE) IODIDE, I(OSO2F)2I

Iodine is oxidized by peroxodisulfuryl difluoride,S2O6F2, to give I(OSOdifluoride,S2O6F2, to give I(OSO2F)2I. Crystals FVjI. Crystals are orthorhombic, space group P212121with a=5.511 (1) Å, b=12.054 (2) Å, c=13.573 (3) Å, V=901.8 (3) Å3, and=3.33 g cm-3for Z=4. The structure was solved by means of Patterson functions and refined by least squares to final agreement indices of R1>=0.0353 and R2>=0.0374 for 1600 independent reflections. There are three primary bonds to the central iodine, I(1), (I(1)-OSO2F=2.086 (7) and 2.258(7) Å; I(1)—I(2)=2.676 (1) Å), which create a distorted T-shaped AX3E2 geometry. The second iodine, I(2), has a primary bond to I(1) and a strong intermolecular secondary I(2)-O bond of length 2.655 (8) Å to one of the fluorosulfate groups that is colinear with the primary bond, giving an AXYE3geometry about I(2). The Raman spectrum of the solid and the 127I Mössbauer spectrum are in full agreement with the structure found. © 1990, American Chemical Society. All rights reserved.