The crystal and molecular structure of chlorocarbonyl(sulfur dioxide)bis(triphenylphosphine)iridium, IrCl(CO)(SO2)(P-(C8H5)5)2, has been determined from three-dimensional X-ray data. The material crystallizes in space group C2h5-P21/c of the monoclinic system, with four molecules in a cell of dimensions a = 12.11, 6 = 16.79, c = 17.09 A, β = 103.0°. The individual monomeric units are well separated, the closest Ir-Ir distance being greater than 8 A. The coordination geometry around the Ir is that of a tetragonal pyramid, with CO, CI, and trans P atoms in the base and the S of the SO2 group at the apex. The O (of the CO), CI, and two P atoms are coplanar; the Ir lies 0.21 A above this plane toward the S. The basal interatomic distances are normal. However, the Ir-S bond length of 2.49 A is very long and the Ir, S, and two O atoms of the SO2 group are not coplanar. Rather the Ir-S vector makes an angle of 32° with the normal to the SO2 plane. The dimensions of the SO2 group are not significantly different from those found in solid SO2. The basic geometry of the SO2 complex differs markedly from that of the analogous O2 complex, Ir(O2)Cl(CO)(P(C6H5)3)2, in which the Ir is in a trigonal bipyramidal configuration with trans P atoms at the apices.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry