Tetrachlorocuprate(II) hybrids of the three anisidine
isomers (ortho-,meta-, andpara-, or 2-, 3-, and 4-methoxyaniline, respectively) were
prepared and
studied in the solid state via X-ray diffraction and magnetization
measurements. Depending on the position of the methoxy group of the
organic cation, and subsequently, the overall cation geometry, a layered,
defective layered, and the structure comprising discrete tetrachlorocuprate(II)
units were obtained for thepara-,meta-, andortho-anisidinium hybrids, respectively.
In the case of layered and defective layered structures, this affords
quasi-2D-layered magnets, demonstrating a complex interplay of strong
and weak magnetic interactions that lead to the long-range ferromagnetic
(FM) order. In the case of the structure with discrete CuCl42–ions, a peculiar antiferromagnetic (AFM) behavior
was revealed. The structural and electronic origins of magnetism are
discussed in detail. To supplement it, the method for calculation
of dimensionality of the inorganic framework as a function of interaction
length was developed. The same was used to discriminate betweenn-dimensional and “almost”n-dimensional frameworks, to estimate the organic cation geometry
limits for layered halometallates, and to provide additional reasoning
behind the observed relation between cation geometry and framework
dimensionality, as well as their relation to differences in magnetic
behavior.