[Cu(H4C3N2S)Cl2](n), an unprecedented diazole-bridged one-dimensional copper halide: synthesis, structure, and magnetic properties.
The simultaneous desulfurization of 2-mercapto-5-methyl-1,3,4-thiadiazole with CuCl(2) x 2H(2)O via mutual diffusion in solvents results in the isolation of air-stable dark-green crystals of [Cu(H(4)C(3)N(2)S)Cl(2)](n) (approximately 65% yield). The structure is characterized by a unique one-dimensional copper chain bridged by diazine N-N single bonds rather than halogens, in sharp contrast with the halide bridging mode in conventional copper halide coordination polymers. Each Cu(II) ion shows a square planar coordination geometry featuring a strong Jahn-Teller distortion, as also supported by EPR data. The phase follows a Curie-Weiss paramagnetic behavior over 6-300 K. However, the intrachain antiferromagnetic interaction is evident (-2J = 21.1 cm(-1)). Such magnetic coupling is related to the interplay between the Cu(II)-d(x2-y2) and diazine N-N p-orbitals.
Song
Jun-Ling
JL
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China.
Dong
Zhen-Chao
ZC
Zeng
Hui-Yi
HY
Zhou
Wen-Bo
WB
Naka
Takashi
T
Wei
Qiang
Q
Mao
Jiang-Gao
JG
Guo
Guo-Cong
GC
Huang
Jin-Shun
JS