SOLID-STATE STRUCTURE OF MONOTHIODIBENZOYLMETHANATO-PI-METHALLYLPALLADIUM(2)

The crystal and molecular structure of monothiodibenzoylmethanato-π-methallylpalladium(II) [(π-C4H7)Pd(S-DBM)] has been determined by a three-dimensional X-ray crystallographic analysis. The orange compound crystallizes in space group P2 1/c with unit cell dimensions a = 11.257(5), b = 8.432(3), c = 19.997 (8) Å, β = 119.31 (5)°, Z = 4. From 1402 independent observable reflections collected on a full-circle automated diffractometer, the structure was solved by use of conventional Patterson, Fourier, and least-squares refinement techniques. All atoms including hydrogen were located, and refinement converged at final values for the discrepancy indices R1 and R2 of 0.048 and 0.057, respectively. The coordination geometry of the palladium atom is defined by Pd-O and Pd-S bonds of 2.067 (6) and 2.291 (2) Å and by Pd-C distances of 2.08 (1), 2.15 (1), and 2.21 (1) Å to the three carbon atoms of the methallyl backbone. The long Pd-C bond length of 2.21 (1) Å is opposite the sulfur atom and may be ascribed to a trans effect. Despite this asymmetry in the palladium-methallyl attachment, the two olefinic C-C bond distances in the methallyl group, 1.40 (2) and 1.42 (2) Å, are essentially equivalent. The structure of the S-DBM chelate ring is shown to differ in several notable ways from its β-diketonate analogs. © 1969, American Chemical Society. All rights reserved.