Hexakis(μ3-2-hydroxynaphthalene-1-carboxaldehyde thiosemicarbazonato-κ3 N 2:S:S)hexasilver(I) N,N-dimethylformamide tetrasolvate

In the title compound, [Ag6(C12H10N3OS)6]·4C3H7NO, the hexanuclear complex molecule lies about an inversion center. The six Ag atoms form a distorted octahedron, with Ag⋯Ag distances in the range 2.933 (1)–3.401 (1) Å. Each Ag atom is surrounded by one N atom and two thiolate S atoms from two deprotonated 2-hydroxy-1-naphthaldehyde thiosemicarbazone ligands. Each ligand coordinates three Ag atoms via a bridging thiolate S atom and a monodentate N atom, thus two Ag3S3 hexagonal rings are linked together. Two dimethylformamide solvent molecules are located in four sets of sites with half-occupancy and form O⋯H—N hydrogen bonds to the complex molecule. Intramolecular O—H⋯N hydrogen bonds are also present. The discrete hexanuclear clusters are further linked through π–π interactions into layers parallel to (001), the shortest distance between the centroids of aromatic rings being 3.698 (2) Å.

In the title compound, [Ag 6 (C 12 H 10 N 3 OS) 6 ]Á4C 3 H 7 NO, the hexanuclear complex molecule lies about an inversion center. The six Ag atoms form a distorted octahedron, with AgÁ Á ÁAg distances in the range 2.933 (1)-3.401 (1) Å . Each Ag atom is surrounded by one N atom and two thiolate S atoms from two deprotonated 2-hydroxy-1-naphthaldehyde thiosemicarbazone ligands. Each ligand coordinates three Ag atoms via a bridging thiolate S atom and a monodentate N atom, thus two Ag 3 S 3 hexagonal rings are linked together. Two dimethylformamide solvent molecules are located in four sets of sites with half-occupancy and form OÁ Á ÁH-N hydrogen bonds to the complex molecule. Intramolecular O-HÁ Á ÁN hydrogen bonds are also present. The discrete hexanuclear clusters are further linked throughinteractions into layers parallel to (001), the shortest distance between the centroids of aromatic rings being 3.698 (2) Å .
compounds (Sun, 2011;Xu et al., 2011), we describe here the structure of the title compound.
The structure of the title compound is shown in Fig. 1. It contains an Ag 6 hexanuclear cluster with the Ag···Ag distances varying from 2.93 Å to 3.40 Å (Fig. 2), which is shorter than the sum of van der Waals radii of two silver atoms (3.44 Å) (Han et al., 2004). In the cluster, each Ag(I) ion is surrounded by one nitrogen atom and two thiolate sulfur atoms from two deprotonated ligands L 5 . Each ligand coordinates to three Ag(I) ions using a bridged thiolate sulfur atom and a monodentate nitrogen atom, from which two Ag 3 S 3 hexagonal rings are linked together to give the overall Ferris wheel structure.
There are intramolecular hydrogen bonds of O-H···N type. Besides this, solvent DMF molecules are linked to the hexanuclear cluster via O···H-N hydrogen bonds.

Refinement
In the compound, all the DMF molecules were found to be disordered, and the s.o.f. for the four disordered molecules were fixed at 0.5. All of the non-hydrogen atoms were refined with anisotropic thermal displacement parameters.

Figure 1
The structure of title compound showing the atom-numbering scheme with H atoms omitted for clarity. Displacement Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.