Carbonyl[tris(3,5-diphenylpyrazol-1-yl-κN 2)methane]copper(I) hexafluoridophosphate–dichloromethane–diethyl ether (4/3/1)

In the title compound, [Cu(C46H34N6)(CO)]PF6·0.75CH2Cl2·0.25C4H10O, the CuI atom is coordinated by three N atoms from the tridentate chelating tris(3,5-diphenylpyrazol-1-yl)methane ligand (average Cu—N distance = 2.055 Å) and the C atom from a carbon monoxide ligand in a distorted tetrahedral coordination geometry. The average N—Cu—N angle between adjacent pyrazole-ring-coordinated N atoms is 88.6°, while the average N—Cu—C angle between the pyrazole-bound N atom and the C atom of carbon monoxide is 126.3°. One of the 3-phenyl rings of the tris(pyrazolyl)methane ligand is disordered over two sites each with an occupancy factor of 0.50. The structure also exhibits disorder of the monosolvate that has been modeled with 0.75 CH2Cl2 and 0.25 Et2O occupancy.

In the title compound, [Cu(C 46 H 34 N 6 )(CO)]PF 6 Á0.75CH 2 Cl 2 Á-0.25C 4 H 10 O, the Cu I atom is coordinated by three N atoms from the tridentate chelating tris(3,5-diphenylpyrazol-1yl)methane ligand (average Cu-N distance = 2.055 Å ) and the C atom from a carbon monoxide ligand in a distorted tetrahedral coordination geometry. The average N-Cu-N angle between adjacent pyrazole-ring-coordinated N atoms is 88.6 , while the average N-Cu-C angle between the pyrazole-bound N atom and the C atom of carbon monoxide is 126.3 . One of the 3-phenyl rings of the tris(pyrazolyl)methane ligand is disordered over two sites each with an occupancy factor of 0.50. The structure also exhibits disorder of the monosolvate that has been modeled with 0.75 CH 2 Cl 2 and 0.25 Et 2 O occupancy.

Comment
In the course of studying the chemistry of tris(pyrazolyl)methane copper(I) complexes, we reacted several substituted tris(pyrazolyl)methane (Tpm) ligands with various copper(I) salts to form the corresponding [Cu(Tpm)] + complexes based on literature references. Once prepared, we tested the complexes for activity as catalysts, and we examined their reactivity with CO. The latter has been performed on several [Cu(Tpm)] + complexes including η 3 -tris(3,5-diphenylpyrazolyl)methane copper(I) perchlorate and has yielded the expected monocarbonyl adducts [Cu(Tpm)(CO)] + (Kujime et al., 2007). While the synthesis of [Cu( 3,5-Ph Tpm)]ClO 4 ([1]ClO 4 ) has been reported, its crystal structure has not been determined. As such, we prepared the hexafluoridophospate salt analogue (avoiding the potentially dangerous perchlorate salt) and report its crystal structure.
The crystal structure of [1]PF 6 , is shown in Figure 1. The Cu I atom is four-coordinate, bound by 3 N atoms from the tris(pyrazolyl)methane ligand and the C atom of carbon monoxide in a distorted tetrahedral coordination geometry. The average Cu-N bond distances (2.055 Å), Cu-C bond distance (1.796 (3) Å), and C-O bond distance (1.126 (3) Å) are within normal ranges as are the average N-Cu-N angles from adjacent pyrazolyl arms (88.6 Å), average N-Cu-C angles from bound pyrazolyl N atom to carbon monoxide C atom (126.3 Å), and the Cu-C-O bond angle (179.59 (3) Å) (Fujisawa et al., 2006).

Experimental
Ligand HC(3,5-Ph 2 py) 3 (0.100 g, 0.149 mmol) was added to tetrakis(acetonitrile)copper(I) hexafluoridophosphate (0.0557 g, 0.149 mmol) in methylene chloride (10 ml) under N 2 atmosphere in a 50 ml Schlenk flask. The mixture was stirred for 2 h then reacted with CO by bubbling CO (g) , prepared from the reaction of concentrated sulfuric acid and formic acid, through the solution for 10 min. The flask was left under CO atmosphere for 2 d. The flask was opened to N 2 atmosphere again and hexane (18 ml) was added to precipitate the product. The product was isolated by inverse filtration and dried under a stream of N 2 (112 mg, 0.123 mmol, 82.8%). FTIR analysis showed the expected strong νCO peak at 2098 cm -1.
Single crystals were obtained by vapor diffusion of diethyl ether into a concentrated CH 2 Cl 2 solution of [1]PF 6 at room temperature over several days.

Refinement
All hydrogen atoms were included at idealized positions and treated as riding to their parent atoms. The solvent in the lattice was modeled with a 75/25 disorder of dichloromethan/diethyl ether. The rotational disorder in the phenyl ring was modeled as a 50/50 disorder.  Fig. 1. Perspective view of complex [1]PF 6 . Displacement ellipsoids are drawn at the 30% probability level. H-atoms and disordered solvate molecules are omitted for clarity. Only one of the two conformations (50:50) of the disordered main molecule is depicted for clarity. The disorder is in the 3-phenyl ring of one of the the 3,5-diphenylpyrazole arms of the tris(pyrazolyl)methane ligand.

Special details
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.