Iodidobis(morpholine-4-carbodithioato-κ2 S,S′)(1,10-phenanthroline-κ2 N,N′)bismuth(III)

The title compound, [Bi(C4H8NOS2)2I(C12H8N2)], is monomeric, with the BiIII atom chelated by the two S atoms of two morpholine-4-carbodithioate ligands and the two N atoms of a 1,10-phenanthroline ligand. An iodide ligand completes the coordination sphere, with the seven-coordinate BiIII atom adopting a highly distorted monocapped octahedral geometry.

The title compound, [Bi(C 4 H 8 NOS 2 ) 2 I(C 12 H 8 N 2 )], is monomeric, with the Bi III atom chelated by the two S atoms of two morpholine-4-carbodithioate ligands and the two N atoms of a 1,10-phenanthroline ligand. An iodide ligand completes the coordination sphere, with the seven-coordinate Bi III atom adopting a highly distorted monocapped octahedral geometry.

Comment
Dithiocarbamates have been known as effective ligands for transition metal ions for many years. They can form chelates (Xu et al., 2001) or act as bridging ligands (Bardaji et al., 1994). However, the chemistry of main-group metal complexes with dithiocarbamates has been less extensively studied, and only a few reports describing bismuth(III) dithiocarbamate complexes have appeared (Yin et al., 2003). As a continuation of our interest in sulfur-containing ligands, we report here the synthesis and structure of the title compound, (I).
The title compound, (I), is monomeric, with the Bi atom chelated by the S atoms of two morpholine-4-carbodithioate ligands and the two N atoms of 1,10-phenanthroline. An iodido ligand completes the coordination environment of the seven coordinate Bi atom (Fig. 1). The Bi atom is in a capped octahedral environment, with atoms S3 and N3 in axial positions, and atoms S1, S2, S4 and I1 in the equatorial plane. The remaining N atom (N4) of the 1,10-phenanthroline ligand caps the S2/S4/N3 face of this octahedron, giving a highly distorted capped octahedral coordination geometry. One of the bidentate pyrrolidinyldithiocarbamate ligands forms a significantly longer Bi-S bond [Bi1-S4 = 2.962 (2) Å] than the others in the complex. This variation in coordination strength is also signalled by the fact that the C7-S4 bond is significantly shorter than the other C-S bonds, suggesting some delocalization in the system. In addition, the chelating phenanthroline ligand is bound to the Bi atom through both of its N atoms. The Bi1-N3 and Bi1-N4 distances fall in the same range as in other Bi/N complexes (Baraanyi et al., 1977).

Refinement
All H atoms were positioned geometrically and treated as riding on their parent atoms [C-H = 0.93 Å and U iso =1.2Ueq (C) for aromatic, C-H =0.97 Å and U iso = 1.2Ueq (C) for CH 2 H atoms].

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.