Crystal structure of [N,N-bis(diphenylphosphorothioyl)amidato-κ2 S,S′]bis(triphenylphosphane-κP)copper(I) dichloromethane monosolvate

The title compound, [Cu(dppaS2)(PPh3)2], is a neutral mononuclear copper(I) complex bearing an N,N-bis(diphenylphosphorothioyl)amidate (dppaS2 −) ligand and two triphenylphosphane ligands. The structure of this complex was obtained by X-ray diffraction and supported by DFT calculations.


Chemical context
Copper(I) complexes have been studied actively because of the abundance of the metal ore and their interesting luminescent properties (Costa et al., 2012). The most well-explored copper(I) complexes are those bearing nitrogen and phosphorus donor atoms, which display strong emission and long-lived lifetime of the excited states (Czerwieniec et al., 2013). On the other hand, Cu I complexes bearing sulfur donor ligands have not been well studied in this respect. Several years ago, we reported some emissive copper(I) complexes bearing diphosphane disulfide (Dairiki et al., 2009). In addition, an interesting reaction was also reported in which a sulfur atom of the diphosphane disulfide ligand was transferred to another diphosphane ligand (Tsukuda et al., 2012). We describe here the crystal structure of a neutral copper(I) complex [Cu(dppaS 2 )(PPh 3 ) 2 ] bearing the anionic diphosphane disulfide ligand N,N-bis(diphenylphosphorothioyl)amidate (dppaS 2 À ) and two triphenylphosphane ligands.

Figure 2
The crystal structure constructed from chains by C-HÁ Á ÁC interactions (red dashed lines).
results compared with experimental values ( Table 2). The optimized structure in the singlet ground state is roughly consistent with crystal structure. The calculated Cu-S and Cu-P bond lengths are in agreement with the experimental value within 0.08 Å . The S-Cu-S and P-Cu-P bond angles, and the dihedral angle between the S/Cu/S and P/Cu/P planes obtained by DFT calculations and experimentally are in good agreement. The near right angle (87 ) of the dihedral angle shows that the tetrahedral geometry seems to be favorable for the complex.

Synthesis and crystallization
Under an argon atmosphere, 5 ml anhydrous dichloromethane were added with stirring to a mixture of N,N-bis(diphenylphosphorothioyl)amine (HdppaS 2 ) (135 mg, 0.3 mmol) and potassium tert-butoxide ( Rekowski et al., 2014). Single crystals suitable for X-ray diffraction were obtained during the synthetic procedure.

Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3. The non-hydrogen atoms were refined anisotropically. All H atoms were positioned geometrically and refined isotropically using the riding model with C-H = 0.99 Å and U iso (H) = 1.2U eq (C) for methylene groups, and 0.95 Å and U iso (H) = 1.2U eq (C) for aromatic groups.

[N,N-bis(diphenylphosphorothioyl)amidato-κ 2 S,S′]bis(triphenylphosphane-κP)copper(I)
where P = (F o 2 + 2F c 2 )/3 (Δ/σ) max = 0.001 Δρ max = 1.10 e Å −3 Δρ min = −0.46 e Å −3 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 was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F 2 . R-factor (gt) are based on F. The threshold expression of F 2 > 2.0 sigma(F 2 ) is used only for calculating Rfactor (gt).