SYNTHESIS, ELECTRON-SPIN-RESONANCE SPECTROSCOPY, AND SHAPE-DETERMINING ANGLE ANALYSIS OF SUPERSTRUCTURED COPPER(II) SCHIFF-BASE COMPLEXES CONTAINING PERSISTENT VOIDS

Syntheses, electron spin resonance spectroscopy, X-ray structural determinations, and shape-determining angle analyses for the five-coordinate Schiff base complexes [Cu(Me2H2Me2malMeDPT)], [Cu{Me2(C3)Me2malMeDPT}], and [Cu{Me2(C6)Me2malMeDPT}] are reported. Syntheses of the superstructured complexes are accomplished by utilizing high-dilution techniques. Interpretation of the ESR spectra suggests that the complexes are five-coordinate with geometrices intermediate between TBP and SP. This interpretation is supported by the X-ray structure of each complex. [Cu(Me2H2Me2malMeDPT)] crystallizes in the monoclinic system (C2/c) with unit cell dimensions a = 17.746 (3) angstrom, b = 7.108 (1) angstrom, c = 17.278 (2) angstrom, beta = 121.68 (1)-degrees, and Z = 4. A total of 2046 reflections were collected, 1662 with I > 3-sigma(I). The structure was refined to weighted and unweighted R factors of 4.2 and 4.0%, respectively. [Cu{Me2(C3)Me2malMeDPT}] crystallizes in the orthorhombic system (Pbca) with unit cell dimensions a = 9.758 (1) angstrom, b = 35.922 (2) angstrom, and c = 17.899 (2) angstrom. With 2960 reflections having intensities greater than 3-sigma(I), the structure was refined to weighted and unweighted R factors of 6.0 and 5.2%, respectively. [Cu{Me2(C6)Me2malMeDPT}] crystallizes in the triclinic system (P1BAR) with unit cell dimensions a = 11.437 (1) angstrom, b = 13.374 (1) angstrom, c = 13.611 angstrom, alpha = 101.02 (1)-degrees, beta = 116.73 (1)-degrees, and gamma = 101.14 (1)degrees. Weighted and unweighted R factors are 4.1 and 4.3%, respectively, for 3991 reflections with I > 3-sigma(I).