Two families of compounds have been prepared from the reaction of 3-X′-2-methylpyridine with CuX 2 (X, X′=Cl, Br) in the presence or absence of HX. Four salts, (3-X′-2-methylpyridinium) 2 CuX 4 were prepared, three of which crystallize in the orthorhombic space group Pbcn while the fourth (X=Br and X′=Cl) crystallizes in the monoclinic space group C2/c. All four neutral compounds of formula (3-X′-2-methylpyridine) 2 CuX 2 crystallize in the space group P1¯. Of these, three form weakly bridged chains via long Cu⋯X contacts, while the fourth (X=X′=Cl) forms centrosymmetric dimers. Most of the complexes exhibit only very weak antiferromagnetic interactions and can be modeled as weak uniform chains. Compound 4, (3-Cl-2-methylpyridinium) 2 CuBr 4 , shows behavior that models an isolated 2D-Heisenberg antiferromagnetic layer with J=−5.09(2)K, while compound 7, (3-Cl-2-methylpyridine) 2 CuCl 2 , crystallizes as a bichloride bridged centrosymmetric dimer with J=−29.31(6)K.