Bis(N,N-diethyldithiocarbamato)(1,10-phenanthroline)cobalt(III) tetrafluoridoborate

The cationic complex in the structure of the title compound, [Co(Et2NCS2)2(C12H8N2)]BF4, has a CoIII atom with a distorted octahedral coordination formed by four S atoms of two diethyldithiocarbamate and two N atoms of 1,10-phenanthroline ligands. The crystal structure features head-to-tail stacking of the phenanthroline ligands. The tetrafluoridoborate anions are positioned in the channels between the cation stacks running along the a axis, and form weak C—H⋯F interactions.

The cationic complex in the structure of the title compound, [Co(Et 2 NCS 2 ) 2 (C 12 H 8 N 2 )]BF 4 , has a Co III atom with a distorted octahedral coordination formed by four S atoms of two diethyldithiocarbamate and two N atoms of 1,10phenanthroline ligands. The crystal structure features headto-tail stacking of the phenanthroline ligands. The tetrafluoridoborate anions are positioned in the channels between the cation stacks running along the a axis, and form weak C-HÁ Á ÁF interactions.
The molecular structure of (I) is shown in Fig. 1. The Co atom has a distorted octahedral coordination formed by four S atoms of two dithiocarbamate and two N atoms of 1,10-phenanthroline ligands ( Table 1).
The crystal packing of the title compound ( Fig. 2) features head-to-tail cationic complexes assembled in the crystal via stacking of the phenanthroline ligands in an alternating mode (interplanar distance is 3.57 Å). The tetrafluoroborate anions are located in the channels between the cation stacks running along the a axis of the structure and are held in position by many C-H···F interactions between phenanthroline C-H bonds and the F atoms of the tetrafluoroborate anion, (Table 2).

S2. Experimental
The complex(I) was prepared by reaction of equimolar amounts of [Co 2 ((C 2 H 5 ) 2 NCS 2 ) 5 ]BF 4 (Hendrickson et al., 1975) and 1,10-phenanthroline in dichloromethane solution at room temperature following the same procedure to that reported for the synthesis of the analogous dimethyldithiocarbamate complex (Hodgson et al., 2008). Crystals were grown from a dichloromethane solution.

S3. Refinement
Hydrogen atoms were placed in calculated positions and refined using the riding model [C-H 0.93-0.97 Å), with U iso (H) = 1.2 U eq (C) for aromatic and methylene groups and 1.5U eq (C) for methyl groups. In the case of the methyl groups, protons were rotated to fit the H-atom positions to the observed electron density. SHELXL97 retraints SIMU and DELU (Sheldrick, 2008) were applied to the thermal parameters for the fluorine atoms of the tetrafluoroborate anions.   The crystal packing of the title compound viewed along the a axis showing stacking of phenanthroline ligands as well as the channels between cation stacks occupied by the BF 4ions. Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.