No abstract

Mixing solutions of M2+ (M = Cu2+ or Zn2+) salts containing cyclam as ligand and an aqueous solution of Na3SbS4·9H2O led to crystallization of two new compounds within minutes: {[Cu(cyclam)]3[SbS4]2}n·20nH2O and {[Zn(cyclam)]3[SbS4]2}·8H2O.

The asymmetric unit of the title compound, {[Mn2Sb2S5(C15H11N3)2]·4H2O} n , consists of two crystallographically independent MnII ions, two unique terpyridine ligands, one [Sb2S5]4− anion and four solvent water molecules, all of which are located in general positions. The [Sb2S5]4− anion consists of two SbS3 units that share common corners. Each of the MnII ions is fivefold coordinated by two symmetry-related S atoms of [Sb2S5]4− anions and three N atoms of a terpyridine ligand within an irregular coordination. Each two anions are linked by two [Mn(terpyridine)]2+ cations into chains along the c-axis direction that consist of eight-membered Mn2Sb2S4 rings. These chains are further connected into a three-dimensional network by intermolecular O—H...O and O—H...S hydrogen bonds. The crystal investigated was twinned and therefore, a twin refinement using data in HKLF-5 [Sheldrick (2015). Acta Cryst. C71, 3–8] format was performed.

The title compound, [Mn(S4)(C8H20N4)], was accidentally obtained by the hydrothermal reaction of Mn(ClO4)2·6H2O, cyclen (cyclen = 1,4,7,10-tetraazacyclododecane) and Na3SbS4·9H2O in water at 413 K, indicating that polysulfide anions might represent intermediates in the synthesis of thiometallate compounds using Na3SbS4·9H2O 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 MnII cation, one [S4]2− anion and one cyclen ligand in general positions. The MnII cation is sixfold coordinated by two cis-S atoms of the [S4]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...S hydrogen bonds into chains, which are further linked into layers by additional N—H...S hydrogen bonding. These layers are connected into a three-dimensional network by intermolecular N—H...S and C—H...S hydrogen bonding. It is noted that only one similar complex with MnII is reported in the literature.

Reaction of Co(ClO4)2·6H2O with cyclam (cyclam = 1,4,8,11-tetraazacyclotetradecane) and Na3SbS4·9H2O (Schlippesches salt) in a mixture of acetonitrile and water leads to the formation of crystals of the title compound with the composition {[Co3(SbS4)2(C10H24N4)3]·2CH3CN·2H2O} n or {[(Co-cyclam)3(SbS4)2]·2(acetonitrile)·2H2O} n . The crystal structure of the title compound consists of three crystallographically independent [Co-cyclam]2+ cations, which are located on centers of inversion, one [SbS4]3− anion, one water and one acetonitrile molecule that occupy general positions. The acetonitrile molecule is disordered over two orientations and was refined using a split model. The CoII cations are coordinated by four N atoms of the cyclam ligand and two trans-S atoms of the tetrathioantimonate anion within slightly distorted octahedra. The unique [SbS4]3− anion is coordinated to all three crystallographically independent CoII cations and this unit, with its symmetry-related counterparts, forms rings composed of six Co-cyclam cations and six tetrathioantimonate anions that are further condensed into layers. These layers are perfectly stacked onto each other so that channels are formed in which acetontrile solvate molecules that are hydrogen bonded to the anions are embedded. The water solvate molecules are located between the layers and are connected to the cyclam ligands and the [SbS4]3− anions via intermolecular N—H...O and O—H...S hydrogen bonding.