Module-Based Assembly of Copper(II) Chloranilate Compounds: Syntheses, Crystal Structures, and Magnetic Properties of {[Cu<sub>2</sub>(CA)(terpy)<sub>2</sub>][Cu(CA)<sub>2</sub>]}<i><sub>n</sub></i> and {[Cu<sub>2</sub>(CA)(terpy)<sub>2</sub>(dmso)<sub>2</sub>][Cu(CA)<sub>2</sub>(dmso)<sub>2</sub>](EtOH)}<i><sub>n</sub></i> (H<sub>2</sub>CA = Chloranilic Acid, terpy = 2,2‘:6‘,2‘ ‘-Terpyridine, dmso = Dimethyl Sulfoxide)
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Two new copper(II) compounds of chloranilate and 2,2‘:6‘,2‘ ‘-terpyridine have been synthesized, and the structures have been solved by the single-crystal X-ray diffraction method. The crystal structure of {[Cu2(CA)(terpy)2][Cu(CA)2]}n (1), where H2CA = chloranilic acid and terpy = 2,2‘:6‘,2‘ ‘-terpyridine, consists of two modules, the dimer unit [Cu2(CA)(terpy)2]2+ and the anionic mononuclear unit [Cu(CA)2]2-, forming an alternated chain. The chain is stabilized by semicoordinating and additional but efficient secondary bonding interactions. The crystal structure of {[Cu2(CA)(terpy)2(dmso)2][Cu(CA)2(dmso)2](EtOH)}n (2), where dmso = dimethyl sulfoxide, consists of solvent molecules and two discrete modules, the dimer unit [Cu2(CA)(terpy)2(dmso)2]2+ and the anionic mononuclear unit [Cu(CA)2(dmso)2]2-. The dimer units form a layer by secondary bonding interactions, and the monomer units and ethanol molecules are introduced between the layers. The magnetic properties of 1 and 2 have been investigated in the temperature range 2.0−300 K. A weak ferromagnetic interaction was observed in 1, Ja = 2.36 cm-1 and zJb = −0.68 cm-1 while no exchange coupling was observed in 2.
