(1,10-Phenanthroline-κ2 N,N′)(triphenylphosphine-κP)silver(I) trifluoromethanesulfonate

The structure of the title complex, [Ag(C12H8N2)(C18H15P)]CF3SO3, is based on a distorted trigonal–planar N2P coordination of the AgI ion, provided by two N atoms of the bidentate phenanthroline ligand and one P atom of the triphenylphosphine ligand. The phenanthroline ligand and one phenyl ring of the triphenylphosphine ligand almost lie in one plane (maximum deviation = 0.014 Å from the best planes). The crystal structure may be stabilized by an intermolecular C—H⋯O hydrogen bond between the phenanthroline ligand and the O atom of the trifluoromethanesulfonate anion.

The structure of the title complex, [Ag(C 12 H 8 N 2 )(C 18 H 15 P)]-CF 3 SO 3 , is based on a distorted trigonal-planar N 2 P coordination of the Ag I ion, provided by two N atoms of the bidentate phenanthroline ligand and one P atom of the triphenylphosphine ligand. The phenanthroline ligand and one phenyl ring of the triphenylphosphine ligand almost lie in one plane (maximum deviation = 0.014 Å from the best planes). The crystal structure may be stabilized by an intermolecular C-HÁ Á ÁO hydrogen bond between the phenanthroline ligand and the O atom of the trifluoromethanesulfonate anion.
The molecular structure of the title complex is depicted in Fig.1. The coordination polyhedron of the silver atom adopts a distorted trigonal-planar geometry, formed by two nitrogen atoms of phen with Ag-N distances of 2.3469 (5) Å and 2.2797 (19) Å, and by one phosphorus atom of the PPh 3 ligand with a Ag-P distance of 2.292 (2) Å. The trifluoromethanesulfonate anion is present as a counter anion and, as expected, shows no direct coordination to the metal center, in contrast to the complex [AgBr(phen)(PPh 3 )] where the silver atom is coordinated to two nitrogen atoms of phen (Ag-N 2.376 (8) Å), one phosphorus atom of PPh 3 (Ag-P, 2.375 (3) Å) and in addition to one bromide anion (Jin et al., 1999), adopting a distorted tetrahedron as coordination polyhedron.
The molecular structure of the title complex shows little differences in comparison with the structures of compounds AgX:PPh 3 :L, where X = nitrate (Di Nicola et al., 2007), nitrite (Pettinari et al., 2007), acetate (Effendy et al., 2007a), perchlorate (Effendy et al., 2007b and trifluoroacetate (Awaleh et al., 2005a). Considering the large steric hindrance and the weak coordination ability (Awaleh et al., 2005b;Howells et al., 1977;Lawrance et al.,1986) of the trifluoromethanesulfonate anion, there is only one C-H···O hydrogen-bond between the phenanthroline ligand and the O atom of the anion with the distance O···H of 2.609Å and the angle C-H···O of 173°.
In the title complex, the P-Ag-N1, P-Ag-N2 and N1-Ag-N2 angles are 147.77 (6)°, 138.03 (6)° and 73.54 (8) ° with a sum of 359.54 °, which comfirms the trigonal-planar environment around the silver atom. In the silver nitrate complex, the P-Ag-N (132.66 (9)°, 131.76 (8)°) (Di Nicola et al., 2007) angles are similar. However, contributing to the role of the nitrate anion, the coordination environment of silver changes from distorted trigonal planar to tetrahedral. nitrite and acetate belong to the former type, whereas perchlorate, trifluoroacetate and trifluoromethanesulfonate can play a role in both of them because of large steric hindrance and the weak coordination ability.

S2. Experimental
A mixture of AgOTf, Ph 3 P and phen in the molar ratio of 1:1:1 in MeOH was stirred for 1 h at ambient temperature, then filtered. Subsequent slow evaporation of the filtrate resulted in the formation of colorless crystals of the title complex.
Crystals suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared. Analysis found (percentage): C 53.22, H 3.29, N 4.01; calculated: C 53.19, H 3.29, N 4.02.

S3. Refinement
All hydrogen atoms were located in the calculated sites and included in the final refinement in the riding model approximation with displacement parameters derived from the parent atoms to which they were bonded (U eq (H) = 1.2U eq (C)).  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.