Layered double hydroxide intercalated with p-methylbenzoate and p-bromobenzoate:: Molecular simulations and XRD analysis

Samples Of Mg4Al2 layered double hydroxide (LDH) intercalated with p-methylbenzoate and p-bromobenzoate anions were prepared by reconstruction of calcined LDH. The interlayer arrangement of guests was investigated by molecular modeling combined with X-ray powder diffraction and thermogravimetry. Molecular modeling was carried out in a Cerius(2) modeling environment. In both structures the guest anions adopt a nearly perpendicular arrangement of their long axis with respect to the host layers and they are anchored to the OH groups of the layers through COO- groups via electrostatic interactions. Molecular modeling revealed that both structures of the intercalates exhibit a certain disorder of guest anions in the interlayer space. In the case of LDH-p-methylbenzoate intercalate the anions tend to be situated in disordered rows, and the LDH-p-bromobenzoate intercalate exhibits a total disorientation of guest anions. A good agreement between calculated and measured Xray diffraction patterns and between experimental and calculated basal spacings was obtained. In the LDH-p-methylbenzoate intercalate d(exp) = 16.96 angstrom and d(calc) = 16.97 angstrom, and in the case of LDH-p-bromobenzoate intercalate d(exp) = 17.19 angstrom and d(calc) = 17.40 (c) 2007 Elsevier Inc. All rights reserved.