Crystal Engineering of a Series of Arylammonium Copper(II) Malonates

We present a series of eight layered copper(II) malonates, each with a {[HA](2)[Cu(II)(mal)(2)(H(2)O)]}(n) A-B-A layer structure, where A is an ammonium cation and 13 is an anionic copper malonate layer (x = 1 or 2; A = benzylamine, 1; S-(alpha)-methylbenzylamine, 2; 4-methylbenzylamine, 3; 4-carboxybenzylamine, 4; 4-trifluoromethylbenzylamine, 5; 4-trifluoromethoxybenzylamine, 6; phenylethylamine, 7; and 4-fluorophenylethylamine, 8). The ammonium cations used are primary amines based around benzylamine and phenylethylamine and include several different functional groups. The different amines give a large array of interlayer interactions, including van der Wail Is packing, hydrogen bonding, C-H center dot center dot center dot pi, pi-center dot center dot center dot pi, H center dot center dot center dot F, and F center dot center dot center dot F. interactions. [Despite the various functionalities on the arylammonium groups, the different interlayer packing interactions, and the differing degrees of hydration in the [Cu(II)(mal)(2)(H(2)O)(x)](2-) group, the anionic layer structure remains the same, indicating a high stability of this layer and its potential for further engineering of the organic layer components.