Two [Ni(dmit)_2]~- Compounds Showing Layered and Chain Alignments: Crystal Structures and Magnetic P

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Two metal-dithiolene compounds with a formula of[4-ClBz-l-APy][Ni(dmit)_2](1)and[4-NO_2Bz-l-APy][Ni(dmit)_2](2,4-ClBz-1-APy = 1-N-(4’-chlorobenzyl)pyridinium,4-NO_2Bz-1-APy = l-N-(4’-nitrobenzyl)pyridinium,dmit~(2-)= 1,3-dithiole-2-thione-4,5-dithiolate) were synthesized and characterized.Two compounds crystallize in triclinic space group P1 and P1,respectively,but with different cell parameters and packing structures.The[Ni(dmit)_2]~- anions and cations of 1 form mixed column stacks along the a axis and alternately layered alignments in the crystal of 2,which are parallel to the crystallographic(110) plane.Two compounds show a similar magnetic behavior,the magnetic exchange natures are mainly antiferromagnetic,and the magnetic susceptibility data can be fitted to the simple Curie-Weiss law.For 1 and 2,the fitted Curie constants are much less than the spin-only value expected for an S =1/2 system,and the fitted Weiss constants marking magnetic interaction are also very smaller.This fact implies that the weak CurrieWeiss-type paramagnetism is not the intrinsic characteristics of two compounds. Two metal-dithiolene compounds with a formula of [4-ClBz-1-APy] [Ni (dmit) _2] (1) and [4-NO_2Bz-1-APy] [Ni (dmit) 4-NO2Bz-1-APy = lN- (4’-nitrobenzyl) pyridinium, dmit ~ (1 -) = 1,3-dithiole-2 -thione-4,5-dithiolate were synthesized and characterized. Two compounds crystallize in triclinic space group P1 and P1, respectively, but with different cell parameters and packing structures. [Ni (dmit) _2] ~ - anions and cations of 1 form mixed column stacks along the a axis and alternate layer alignments in the crystal of 2, which are parallel to the crystallographic (110) plane. Two compounds show a similar magnetic behavior, the magnetic exchange natures are mainly antiferromagnetic, and magnetic susceptibility the data can be fitted to the simple Curie-Weiss law. For 1 and 2, the fitted Curie constants are much less than the spin-only value expected for an S = 1/2 system, and the fitted Weiss constants marking magnetic interaction are also very smaller.This fac t implies that the weak CurrieWeiss-type paramagnetism is not the intrinsic characteristics of two compounds.
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