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

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Six first row transition metal complexes with 1,6-bis(2′-pyridyl)-2,5-dithiahexane(Py_2S_2), namely, MnPy_2S_2Cl_2(1), FePy_2S_2Cl_2(2), Co Py_2S_2Cl(3), CoPy_2S_2(SCN)_2(4), NiPy_2S_2(SCN)_2(5) and NiPy_2S_2(N_3)_2(6), have been synthesized. A mixture of MCl_2·x H_2O(M = Mn, Co) in MeOH(FeCl_2·4H_2O in MeCN) and the stoichiometric amount of Py_2S_2 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_2S_2Cl_2(M = Co, Ni) in MeOH and two equivalents of KSCN or NaN_3 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_3~– or NCS~–. Six first row transition metal complexes with 1,6-bis (2’-pyridyl) -2,5-dithiahexane (Py_2S_2), namely, MnPy_2S_2Cl_2 (1), FePy_2S_2Cl_2 (2), Co Py_2S_2Cl (3), CoPy_2S_2 (SCN) A mixture of MCl 2 · x H 2 O (M = Mn, Co) in MeOH (FeCl 2 · 4H 2 O in MeCN) _2 (4), NiPy_2S_2 (SCN) _2 (5) and NiPy_2S_2 (N_3) _2 and the stoichiometric amount of Py_2S_2 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_2S_2Cl_2 (M = Co, Ni) in MeOH and two equivalents of KSCN or NaN_3 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 of 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 but 4, 5 and 6 (2)) are replaced by another two N atoms from N_3 ~ - or NCS ~ -.
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