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) 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 (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.