Synthesis, Crystal Structure and Magnetic Properties of Two Ribbon-shaped Chalcogenidometalate Complexes(Butyl-Sn)4S8M2(TEPA)2(M = Mn, Ni)

Under solvothermal conditions,two ribbon-shaped chalcogenidometalate coordination compounds(butyl-Sn)SM(TEPA)(M=Mn(1),Ni(2),TEPA=tetraethylenepentamine),have been synthesized and characterized by elemental analysis,energy dispersive X-ray,infrared/ultraviolet-visible spectroscopy,thermogravimetric analysis,single-crystal and powder X-ray diffraction.Complexes 1 and 2 crystallize in the triclinic space group P1 with a=13.999(3),b=14.658(4),c=16.150(4) A,a=68.78(3)°,β=69.12(3)°,γ=72.07(3)°,V=2825.0(14) A~3,Z=2,M=1448.28,μ=2.503 mm,F(000)=1444,GOOF=1.001,R=0.0629 and wR=0.1286 for 12855 observed reflections with I> 2σ(I) for 1;and a=11.029(3),b=11.858(2),c=11.888(3) A,a=87.27(2)°,β=69.10(2)°,γ=83.63(2)°,V=1443.6(6) A~3,Z=1,M=1455.78,μ=2.660 mm,F(000)=728,GOOF=1.017,R=0.0464 and wR=0.1185 for 9267 observed reflections with I> 2σ(I) for 2,respectively.Both 1 and 2 are composed of linear hexamer {SnM}(M=Mn for 1,and Ni for 2) with 8 μ-Sbridges and 2 TEPA terminal ligands.Despite the quite large inter-paramagnetic-cation spacing(dMn-S-Sn-S-Sn-S-Sn-S-Sn-S-Mn=13.485 A,dNi-S-Sn-S-Sn-S-Sn-S-Sn-S-Ni=14.078 A),two samples exhibit distinct ferromagnetic-like behaviors with the intradimer coupling constant(J) and Weiss(θ) values up to 6.8 cmand 8.5 K for 1 and 17.2 cmand 21.1 K for 2 calculated from the temperature dependence of the magnetic susceptibility.