Abstract
The solid state structure of the lapacholate (Lap−) complexes with Zn(II), Cd(II) and Mn(II) were determined by X-ray diffraction methods. [Zn(Lap)2(DMF)(H2O)] crystallizes in the triclinic space group P1¯ with a=10.5051(4), b=12.8020(4), c=13.0394(4)Å, α=60.418(2), β=83.904(2), γ=86.206(2)°, and Z=2 molecules per unit cell. The isomorphous complexes [M(Lap)2]n (M: Cd, Mn) crystallize in the tetragonal space group P43212 with a=b=13.5770(6)Å, c=14.5730(6)Å (Cd), and a=b=13.3539(4), c=14.7148(4)Å (Mn), and Z=4. In [Zn(Lap)2(DMF)(H2O)] the Zn(II) ion is in a distorted octahedral environment coordinated to two different and nearly perpendicular Lap− molecules acting as bidentate ligands through their adjacent carbonyl and phenol oxygen atoms. The remaining two cis-coordination sites are occupied by water and DMF molecules. [M(Lap)2]n (M: Cd, Mn) isomorphous complexes are also octahedral and present a supra-molecular arrangement in the lattice. There is only one independent Lap− molecule that coordinates the metal through all three ligand binding sites, giving rise to a 3-D structure of [M(Lap)2]n complexes that extends throughout the crystal lattice.The lapachol binding to metal is also revealed by the IR spectra. In fact, the carbonyl CO stretching frequency is appreciable red-shifted in the complexes as compared to uncoordinated lapachol ligand. As expected, the IR and UV–Vis spectra of the isomorphous pair of complexes closely resemble to each other.Up to above 300°C there are significant differences in the TGA of the Zn complex when compared with the isomorphous pair: while the former shows the loss of the secondary ligands (water and DMF), the latter exhibits a plateau signaling the lesser labile character of the lapacholate ligand.
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