Synthesis and crystal structure of (1,4,7,10-tetra-azacyclododecane-κ4N)(tetrasulfido-κ2S1,S4)manganese(II)

The title compound, [Mn(S-4)(C8H20N4)], was accidentally obtained by the hydrothermal reaction of Mn(ClO4)(2)center dot 6H(2)O, cyclen (cyclen = 1,4,7,10-tetraazacyclododecane) and Na3SbS4 center dot 9H(2)O in water at 413 K, indicating that polysulfide anions might represent intermediates in the synthesis of thiometallate compounds using Na3SbS4 center dot 9H(2)O as a reactant. X-ray powder diffraction proves that the sample is slightly contaminated with NaSb(OH)(6) and an unknown crystalline phase. The crystal investigated was twinned with a twofold rotation axis as the twin element, and therefore a twin refinement using data in HKLF-5 format was performed. The asymmetric unit of the title compound consists of one Mn-II cation, one [S-4](2-) anion and one cyclen ligand in general positions. The Mn-II cation is sixfold coordinated by two cis-S atoms of the [S-4](2-) anions, as well as four N atoms of the cyclen ligand within an irregular coordination. The complexes are linked via pairs of N-H center dot center dot center dot S hydrogen bonds into chains, which are further linked into layers by additional N-H center dot center dot center dot S hydrogen bonding. These layers are connected into a three-dimensional network by intermolecular N-H center dot center dot center dot S and C-H center dot center dot center dot S hydrogen bonding. It is noted that only one similar complex with Mn-II is reported in the literature.