Crystal Structure of Bis(<i>O</i>-<i>n</i>-butyldithiocarbonato-<i>S</i>,<i>S</i>')(1,10-phenanthroline)-manganese(II)

Abstract

Xanthates comprise an important class of 1,1-dithiolate ligands with many applications ranging from flotation agents to radical polymerization. 1 Among the many structural investigations available for metal xanthates, 1 there is a clear deficiency with regard to the structural and synthetic characterization of manganese xanthates. The early syntheses of manganese(II) ethyl xanthates were accomplished in a nitrogen-filled glovebox. 2 Bivalent metal dithiocarbonates are known to form stable adducts with nitrogen donors which exhibit a variety of coordination geometries. 3 Coordination complexes of dithiocarbanto ligands with a variety of transition as well as non-transition metals have been reported, 4,5 owing to their wide applications in various fields, like metallurgy, rubber technology and medicines. Transition metal dithiocarbonates have also received special attention due to their rich structural diversity and potential biological activities. 6 As a part of our continuous research in this area, the title complex (I) was prepared in the crystalline form, and its various geometrical parameters were investigated. An analysis of the complex indicates that a fivemembered ring structure is acquired by the nitrogen donor giving the complex a distorted octahedral geometry. The chelating dithiocarbante ligand is represented by almost equivalent Mn-S bond distances.After 0.35 g of 1,10-phenanthroline (3.55 mmol) was added to an aqueous (100 mL) solution of MnSO4·H2O (0.3 g, 1.77 mmol) under stirring, the drop-wise addition of an aqueous solution (10 mL) of potassium salt of n-butyldithiocarbonate (0.667 g, 3.55 mmol) was performed. Yellow precipitates were X-ray Structure Analysis Online Crystal Structure of Bis(O-n-butyldithiocarbonato-S,S')(1,10-phenanthroline)-manganese(II)Gurvinder KOUR,* Akshit KUMAR,* Inderjeet KOUR,** Gurpreet KOUR,** Renu SACHAR,** Vivek K. GUPTA,* Rajnikant* † * X-ray Crystallography Laboratory, Post-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi-180 006, India **Department of Chemistry, University of Jammu, Jammu Tawi-180 006, IndiaThe title compound, bis(O-n-butyldithiocarbonato-S,S')(1,10-phenanthroline) manganese(II): Mn(S2COCH2CH2CH2CH3)2-(1,10-phenanthroline), crystallizes in the monoclinic space group C2/c with the following unit-cell parameters: a = 6.6626(3)Å, b = 18.9127(6)Å, c = 20.5778(10)Å, b = 97.773(4)˚, Z = 4. The crystal structure was solved by direct methods, and refined by full-matrix least-squares procedures to a final R-value of 0.0464 for 1892 observed reflections. In the title molecular complex, the butyl chain is disordered over two sets of sites, with occupancy ratios of 0.54(2): 0.46(2). The crystal structure is stabilized with the help of p-p interactions between neighbouring pyridine rings, with a centroid-to-centroid distance of 3.849 Å. The adduct is found to exhibit a distorted octahedral coordination geometry based on a N2S4 donor set with Mn 2+ located at the centre. formed immediately. The mixture was stirred for one hour, after...