Crystal structure, spectroscopic and thermal properties of [Zn(Lap)2(DMF)(H2O)] and isomorphous [M(Lap)2]n (M: Cd, Mn) complexes

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.