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(H2O)x]}n A−B−A layer structure, where A is an ammonium cation and B is an anionic copper malonate layer (x = 1 or 2; A = benzylamine, 1; S-(α)-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 Waals packing, hydrogen bonding, C−H···π, π···π, H···F, and F···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(H2O)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.