Syntheses, Crystal Structures, Weak Interactions, and Magnetic Properties of Two Tetrachlorocuprate(II) Salts With Substituted Benzyl 4-Dimethylaminopyridinium

Abstract

Two new tetrachlorocuprate(II) salts, [BzDMAP]2[CuCl4](1) and [4FBzDMAP]2[CuCl4](2) ([BzDMAP]+ = 1-benzyl-4-dimethylaminopyridinium; [4FBzDMAP]+ = 1-(4′-fluorobenzyl)-4-dimethylaminopyridinium), have been prepared and characterized by elemental analysis, IR, MS, single-crystal X-ray diffraction and magnetic susceptibility. Compound 1 crystallizes in the monoclinic system with space group P21/n, while 2 crystallizes in the orthorhombic system with space group P212121. These two salts comprise one [CuCl4]2– anion and two cations, and the [CuCl4]2– anions exhibit distorted tetrahedral coordination geometry. The C˭H···Cl, C˭H···π hydrogen bonds and π···π stacking interactions in the crystal play important roles in the stacking and stabilization of the two salts, and give rise to a 3D network structure. Magnetic susceptibility measurements in the temperature range of 2–300 K show that both 1 and 2 exhibit a ferromagnetic coupling behavior.