Three molecular solids, [2RBzIQl] 2 [Cu(mnt) 2 ] (mnt 2− =maleonitriledithiolate; [2RBzIQl] + =1-(2′-R-benzyl) isoquinolinium, R=F(1), Cl(2) and Br(3)), have been prepared and systemically investigated. The crystal structural analysis reveals that three molecular metals crystallize in the monoclinic with space group P2 1 /c, and the [2RBzIQl] + cations stack into an one-dimensional column through CH⋯π, π⋯π and CH⋯X (X=F or Cl) interactions while the [Cu(mnt) 2 ] 2− anions in 1 and 2 form a dimer by the side-to-side S⋯S, N⋯N and S⋯N interactions. The anions (A) and cations (C) are arranged alternatively into one 1D column for 1 and 2 and two 1D columns for 3 with a ⋯ACCACCA⋯ sequence though CH⋯S, CH⋯π, CH⋯N or/and CH⋯Cu hydrogen bonds, and weak X⋯N (X=F, Cl), Br⋯S, Cu⋯N or/and π⋯π interactions. The magnetic susceptibilities measured in the temperature range 2.0–300K reveal that 1 shows an antiferromagnetic behavior, while 2 and 3 exhibit a change of magnetic exchange from weak ferromagnetic to antiferromagnetic around 48K upon the temperature is lowered.