Syntheses, crystal structures and magnetic properties of three new molecular solids based on bis(maleonitriledithiolate)copper(II) anion and ortho-position substituted benzyl isoquinolinium cations.

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 P 2 1 / c , and the [2RBzIQl] + cations stack into an one-dimensional column through C H⋯π, π⋯π and C H⋯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 ⋯A CC A CC A⋯ sequence though C H⋯S, C H⋯π, C H⋯N or/and C H⋯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 2.0–300 K reveal that 1 shows an antiferromagnetic behavior, while 2 and 3 exhibit a change of magnetic exchange from weak ferromagnetic to antiferromagnetic around 48 K upon the temperature is lowered. [ABSTRACT FROM AUTHOR]