Synthesis and Crystal Structure of Manganese(II) Complexes with 2-Acetylpyridine Methyldithiocarbazate

The aerobic reaction of 2-(acetylpyridine)-S-methyldithiocarbazate (acpy-mdtcH) and 2-(acetylpyridine)-N-phenylthiosemicarbazate(acpy-phTscH) with manganese(Ⅱ) acetate affords Mn(acpy-mdtc)2 and Mn(acpyphTsc)2, respectively. The spectroscopic data and X-ray structure of Mn(acpy-mdtc)2 are reported. Crystal data for Mn(acpy-mdtc)2; C18H20N6S4Mn, mol wt 503.58, monoclinic crystal system(P21/c) a=12.240(5) Å, b= 10.918(l) Å, c=17.651(3) Å, β=105.93(2), and V=2268(l) Å3, Z=4, 5071 data collected with 0°< 2θ < 52.64°, 2995 data with I > 3σ(I), R= 0.046, Rw= 0.065. The ligands act as tridentate NNS donors. The two Mn-S distances are not equal, and respectively 2.512(2) Å and 2.541(2) Å. The average Mn-N (azomethine) length, 2.242(5) Å, is slightly shorter than the average Mn-N (pyridyl) length, 2.262(5) Å. The coordination environment about MN(Ⅱ) center deviates considerably from octahedral geometry. The manganese(Ⅱ)-manganese(Ⅰ) and manganese(Ⅰ)-manganese(0) reduction potentials of Mn(acpy-mdtc)2 are ∼-l.71 and ∼-l.98 V while those of Mn(acpy-phTsc)2 are ∼-l.87 and ∼-2.11 V vs. Ag/Ag+ in dimethyl sulfoxide, respectively.