Syntheses and Crystal Structures of the First Row Transition Metals with 1,6-Bis(2＇-pyridyl)-2,5-dithiahexane

Six first row transition metal complexes with 1,6-bis（2′-pyridyl）-2,5-dithiahexane（Py;S;）, namely, MnPy;S;Cl;（1）, FePy;S;Cl;（2）, Co Py;S;Cl（3）, CoPy;S;（SCN）;（4）, NiPy;S;（SCN）;（5） and NiPy;S;（N;）;（6）, have been synthesized. A mixture of MCl;·x H;O（M = Mn, Co） in MeOH（FeCl;·4H;O in MeCN） and the stoichiometric amount of Py;S;was stirred for 4 h at room temperature, then these aiming products 1, 2 and 3 could be obtained by purification. A mixture of MPy;S;Cl;（M = Co, Ni） in MeOH and two equivalents of KSCN or NaN;was stirred for 4 h at room temperature. After that, complexes 4, 5 and 6 could be got by purifying. For 1, 2, 3, 4 and 5, the metal centers are hexa-coordinated in a similar distorted octahedral geometry and the crystal structures have the same space group Pbcn. The crystal structure of compound 6 belongs to monoclinic with space group P21/c. The coordinated atoms around M（Ⅱ） are two pyridyl N atoms(N（1） and N（2）), two thioether S atoms(S（1） and S（2）) and two chloride ions(Cl（1） and Cl（2）) in compounds 1, 2, and 3, but in 4, 5, and 6, two chloride ions(Cl（1） and Cl（2）) are replaced by another two N atoms from N;or NCS;.