Aqua(benzamidato-κN)bis[3,5-difluoro-2-(pyridin-2-yl)phenyl-κC 1]iridium(III) methanol monosolvate

In the title compound, [Ir(C11H6F2N)2(C7H6NO)(H2O)]·CH3OH, the IrIII ion adopts an octahedral geometry, and is coordinated by two 3,5-difluoro-2-(pyridin-2-yl)phenyl ligands, one molecule of water and one benzamidate anion. The two 2-(4,6-difluorophenyl)pyridyl ligands are arranged in a cis-C,C′ and trans-N,N′ fashion. Additionally, there is a bystanding methanol molecule outside the coordination sphere of the IrIII ion. In the crystal, molecules of the title compound are linked by O—H⋯O and O—H⋯N hydrogen bonds. One F atom of each ligand is equally disordered over two sites. The C atom of the solvent molecule is likewise disordered over two sites in a 0.589 (11):0.411 (11) ratio.

In the title compound, [Ir(C 11 H 6 F 2 N) 2 (C 7 H 6 NO)(H 2 O)]Á-CH 3 OH, the Ir III ion adopts an octahedral geometry, and is coordinated by two 3,5-difluoro-2-(pyridin-2-yl)phenyl ligands, one molecule of water and one benzamidate anion. The two 2-(4,6-difluorophenyl)pyridyl ligands are arranged in a cis-C,C 0 and trans-N,N 0 fashion. Additionally, there is a bystanding methanol molecule outside the coordination sphere of the Ir III ion. In the crystal, molecules of the title compound are linked by O-HÁ Á ÁO and O-HÁ Á ÁN hydrogen bonds. One F atom of each ligand is equally disordered over two sites. The C atom of the solvent molecule is likewise disordered over two sites in a 0.589 (11):0.411 (11) ratio.
We have synthesized several such bis(2-(4,6-difluorophenyl)pyridyl)iridium(III) κ 2 -amidate complexes, in all of which, there is a substitutent on the amide nitrogen atom . When benzamide lacking a substituent on the amide nitrogen atom was subjected to the reaction condition for the preparation of Ir(III) κ 2 -amidate complexes, an unexpected Ir(III) complex with a N-bound benzamidate ligand and an O-bound water ligand, i.e., the title compound, was obtained. As shown in Fig. 1, the iridium center adopts an octahedral geometry. The two 2-(4,6-difluorophenyl)pyridyl ligands are arranged in a cis-C, C′ and trans-N, N′ fashion, which have already been observed in some homoleptic meridional iridium(III) complexes (Tamayo et al., 2003) and also some heteroleptic iridium(III) complexes (Yang et al., 2007;You & Park, 2005;Zhang et al., 2011). The remaining two coordination sites were occupied by benzamidate nitro-

Experimental
Into a Schlenk tube containing chloro-bridged bis(2-(4,6-difluorophenyl)pyridyl) Ir(III) dimer (1 eq.), benzamide (2.5 eq.) and sodium methoxide (10 eq.) was added dichloromethane solvent under dinitrogen. The chloro-bridged Ir(III) dimer was obtained by reaction of IrCl 3 . 3H 2 O with 2-(4,6-difluorophenyl)pyridine ligand in ethoxyethanol solvent under dinitrogen atmosphere according to the general procedure reported by Nonoyama (1974). The mixture was stirred for 48 h at room temperature, resulting in the formation of an orange solution. The CH 2 Cl 2 solvent in the crude product mixture was then evaporated and the residue was then washed by dried ether. The crystal of the title compound was obtained by recrystallization of the solid in CH 2 Cl 2 /cyclohexane mixed solvent.

Refinement
Hydrogen atoms bound to carbon atoms were positioned geometrically with C-H = 0.93 Å or 0.96 Å and refined using a riding model, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C). Hydrogen atoms bound to nitrogen and oxygen atoms were OMe complex, which is supposed to be generated by transmetalation of chloro-bridged Ir(III) dimer with added sodium methoxide. Due to the disorder of the methanol molecule, the positions of hydrogen atoms on methanol are difficult to determine. Furthermore, this would lead to some disorder in the positions of fluorine atoms on the phenyl ring because there should be some interaction between the methanol hydrogen atoms with the fluorine atoms. This is believed to be the most probable structure of the title compound.

Figure 1
Molecular drawing of the title compound at 30% probability level. Hydrogen atoms are omitted for clarity. There are some disorder for the two fluorine atoms bound to C9 and C18 of phenyl rings.  Hydrogen bonding.