Crystal Structure of (Difluoro)methoxyoxo Iodine(V) IF₂(O)OCH₃

Abstract

(Difluoro)methoxyoxo iodine(V) (IF2(O)OCH3), the methyl ester of the unknown difluoro iodic acid (IF2(O)OH), was obtained by the reaction of methoxytrimethyl silane with iodine pentafluoride. IF2(O)OCH3 crystallizes orthorhombic in the space group Pbca with a = 7.605(1) A, b = 7.360(1) A, c = 15.017(1) A, and eight formula units per unit cell. The final R indices [I > 2 sigma(I)] are R1 = 0.0264 and wR2 = 0.0516. Additionally, IF2(O)OCH3 was characterized by its vibrational spectra and quantum mechanical calculations were performed.

An Accidental Discovery of a New Mixed-Valent Iodine Compound − Crystal Structure of Difluoroiodato(V) Iodine(III) Dichloride [Cl2IOI(O)F2]

“…3.038 (8) O (1)ϪI (1)ϪCl (2) (2)ϪI (2) [17,18] The angle between iodine and the two fluorine atoms is 172.2(4)°and shows a difference from the ideal value of 180°due to the steric activity of the lone pair. In Cl 2 IOI(O)F 2 there is an axial as well as an equatorial IϪCl bond, whose lengths of 2.343(4) and 2.352(5) Å are only slightly larger than the sum of the covalent radii (2.27 Å ).…”

Anhydrides of Real and Hypothetical [Hydroxy(R−O)iodo]benzenes

“…The I-centered angles approach the ideal 72°, where O3···I2−O2 is constrained to be small (45.36°) owing to tethering. A second example of an I atom with CN 9 and bicapped pentagonal-bipyramidal EDG is provided by the λ 5 -iodane IF 2 (O)OCH 3 ( 40 ; Figure ) . With one unshared pair of electrons and four secondary bonds (I1···O1′, 3.413 Å; I1···F2′, 2.876 Å; I1···F1′′, 3.278 Å; I1···O1′′′, 2.645 Å), a lightly puckered pentagonal plane is produced with an average atomic displacement of 0.102(49) Å, where I1 is displaced by 0.129 Å.…”

Untitled

“…Using similar methods the methyl ester of the unknown difluoroiodic acid, IF 2 (O)OH, was obtained by reaction of three equivalents of Me 3 SiOCH 3 with IF 5 . 43 The resulting pseudo-trigonal-bipyramidal based structure has the two fluorine atoms in apical positions and the large steric demand of the lone pair is observed through the significantly smaller than expected O-I-O angle of 101.4(2)°.…”