METAL ION-AROMATIC COMPLEXES .7. CRYSTAL AND MOLECULAR STRUCTURE OF BIS(M-XYLENE) SILVER PERCHLORATE

The crystal and molecular structure of bis(m-xylene)silver(I) perchlorate has been determined by single-crystal X-ray diffraction from 672 counter intensities measured at ambient temperature. The crystals were found to be orthorhombic: a = 16.594 (8) Å, b = 8.861 (5) Å, c = 5.795 (3) Å space group P21221. The structure was refined by full-matrix least squares to a final conventional R factor of 0.050. The structure may be described as alternating tetrahedra of CIO4− ions and four coordinate Ag(I) sharing an oxygen vertex. The coordination tetrahedron of Ag(I) is composed of the two Ag-O interactions and two bonds to the π electrons of m-xylene rings. This tetrahedron is very flattened with an Ag-O distance of 2.49 ± 0.01 Å and O-Ag-O angle of 125.0 ± 0.8˚ together with an Ag-C distance of 2.45 ± 0.02 Å and C-Ag-C′ angle of 161.7 ± 0.8˚. The next shortest Ag-C distance is 2.61 ± 0.02 Å. Hence, the Ag(I) is asymmetrically located relative to the nearest C-C bond of the aromatic ring. The shortest Ag-C distance is ortho and para to the methyl ring substituents. The aromatic moiety is normal within experimental error. It is clear that the perchlorate group plays a significant role in stabilizing this metal ion-aromatic complex. © 1969, American Chemical Society. All rights reserved.