Supplement 1. Comparison of the Square Pyramidal ClF5, BrF5, IF5, and XeF5+,
and the ICl5 and IBr5 Structures.

ClF5 (B3LYP/aug-cc-pV5Z)
  • Cl - Feq 1.687 Å
  • Cl - Fax 1.610 Å
  • Fax-Cl-Feq 86.3o
 BrF5 (B3LYP/aug-cc-pV5Z)
  • Br - Feq 1.789 Å
  • Br - Fax 1.720 Å
  • Fax-Br-Feq 84.9o
 IF5 (B3LYP/aug-cc-pV5Z-pp)
  • I - Feq 1.906 Å
  • I - Fax 1.841 Å
  • Fax-I-Feq 83.0o
Literature Valuesa for ClF5
  • Cl - Feq 1.67(2) Å
  • Cl - Fax 1.57(1) Å
  • Fax-Cl-Feq 86(2)o
 Literature Valuesa for BrF5
  • Br - Feq 1.768(2) Å
  • Br - Fax 1.697(4) Å
  • Fax-Br-Feq 85.1(4)o
 Literature Valuesa for IF5
  • I - Feq 1.871(2) Å
  • I - Fax 1.814(6) Å
  • Fax-I-Feq 83.0(3)o
XeF5+ (B3LYP/aug-cc-pV5Z-pp)
  • Xe - Feq 1.863 Å
  • Xe - Fax 1.829 Å
  • Fax-Xe-Feq 83.4 o
 ICl5 (B3LYP/pVTZ)
  • I - Cleq 2.475 Å
  • I - Clax 2.401 Å
  • Clax-I-Cleq 88.4o
 IBr5 (B3LYP/pVTZ)
  • I - Breq 2.677 Å
  • I - Brax 2.575 Å
  • Brax-I-Breq 90.3o
Literature Valuesa for XeF5+
  • Xe - Feq 1.85 Å
  • Xe - Fax 1.81 Å
  • Fax-Xe-Feq 79 o
  • Crystallizes with F bridges
 --
a. R. J. Gillesie, E. A. Robinson, Inorg. Chem., 1992, 31,, 1960-1963, and
R. J. Gillsepie, I. Hargittai, The VSEPR Model of Molecular Geometry, 1991 Allyn and Bacon, Boston, MA, USA, p. 151-7
We found no structural data for ICl5 and IBr5 to compare with our computational values.