Aqua­(benzamidato-κN)bis­[3,5-difluoro-2-(pyridin-2-yl)phenyl-κC1]iridium(III) methanol monosolvate

Zhang, S.; Wu, F.; Ding, Y.

doi:10.1107/S1600536812005922

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page m310

doi:10.1107/S1600536812005922

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Aqua(benzamidato-κN)bis[3,5-difluoro-2-(pyridin-2-yl)phenyl-κC¹]iridium(III) methanol monosolvate

Songlin Zhang,^a Feng Wu ^a and Yuqiang Ding ^a ^*

^aSchool of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu Province, People's Republic of China
^*Correspondence e-mail: yding@jiangnan.edu.cn

(Received 21 November 2011; accepted 10 February 2012; online 17 February 2012)

In the title compound, [Ir(C₁₁H₆F₂N)₂(C₇H₆NO)(H₂O)]·CH₃OH, 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′ and trans-N,N′ 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—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.

Related literature

For related cyclometallated Ir^III complexes containing a κ²-bound benzaminate anion, see: Yang et al. (2011 ); Wang et al. (2008 ); Zhang et al. (2011 ). For the coordination geometry of some homoleptic meridional and heteroleptic iridium(III) complexes, see: Tamayo et al. (2003 ); Yang et al. (2007 ); You & Park (2005 ); Zhang et al. (2011). For the general procedure of preparing a chloride-bridged Ir^III dimer, see: Nonoyama (1974 ).

Experimental

Crystal data

[Ir(C₁₁H₆F₂N)₂(C₇H₆NO)(H₂O)]·CH₄O
M_r = 742.74
Monoclinic, C 2/c
a = 29.544 (4) Å
b = 11.6258 (12) Å
c = 20.247 (3) Å
β = 129.391 (2)°
V = 5374.5 (12) Å³
Z = 8
Mo Kα radiation
μ = 5.04 mm⁻¹
T = 223 K
0.34 × 0.25 × 0.24 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.279, T_max = 0.378
14977 measured reflections
6122 independent reflections
5277 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.101
S = 1.09
6122 reflections
392 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.20 e Å⁻³
Δρ_min = −1.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2B⋯N3	0.85 (1)	2.54 (6)	3.029 (7)	117 (6)
O2—H2B⋯O1	0.85 (1)	1.74 (3)	2.560 (6)	161 (7)
O2—H2A⋯N1	0.85 (1)	2.45 (6)	2.960 (6)	119 (6)
O2—H2A⋯O1ⁱ	0.85 (1)	1.97 (4)	2.700 (7)	142 (6)
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

Data collection: CrystalClear (Rigaku, 2007 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812005922/br2185sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812005922/br2185Isup2.hkl

checkCIF report

Comment top

The title compound was obtained unexpectedly during our study on the preparation of bis(2-(4,6-difluorophenyl)pyridyl)iridium(III) κ²-benzamidate complex. Ancillary κ²-amidate ligands have been shown to have a great influence on the photophysical and electrochemical properties of cyclometalated Ir(III) complexes (Yang et al., 2011; Wang et al., 2008). We have synthesized several such bis(2-(4,6-difluorophenyl)pyridyl)iridium(III) κ²-amidate complexes, in all of which, there is a substitutent on the amide nitrogen atom (Zhang et al., 2011). When benzamide lacking a substituent on the amide nitrogen atom was subjected to the reaction condition for the preparation of Ir(III) κ²-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 nitrogen atom and water oxygen atom, respectively. The methanol molecule outside the coordination sphere of the Ir center should result from the deprotonation of the benzamide ligand by the intermediate Ir-OMe complex, which is generated by reaction of chloro-bridged Ir(III) dimer with sodium methoxide. However, there is still some uncertainties about the nature of the bystanding solvent molecule or how it is arranged. In the crystal, there should be intermolecular hydrogen bonds, such as O-H-O and N-H-O, as shown by Fig. 2.

Related literature top

For related cyclometallated Ir^III complexes containing a κ²-bound amidate ligand, see: Yang et al. (2011); Wang et al. (2008); Zhang et al. (2011). For the coordination geometry of some homoleptic meridional and heteroleptic iridium(III) complexes, see: Tamayo et al. (2003); Yang et al. (2007); You & Park (2005); Zhang et al. (2011). For the general procedure of preparing a chloro-bridged Ir^III dimer, see: Nonoyama (1974).

Experimental top

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 IrCl₃^.3H₂O 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 CH₂Cl₂ 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 CH₂Cl₂/cyclohexane mixed solvent.

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 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.
	Fig. 2. Hydrogen bonding.

Aqua(benzamidato-κN)bis[3,5-difluoro-2-(pyridin-2-yl)phenyl- κC¹]iridium(III) methanol monosolvate top

Crystal data top

[Ir(C₁₁H₆F₂N)₂(C₇H₆NO)(H₂O)]·CH₄O	F(000) = 2960
M_r = 742.74	D_x = 1.846 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -C 2yc	Cell parameters from 11541 reflections
a = 29.544 (4) Å	θ = 3.1–27.5°
b = 11.6258 (12) Å	µ = 5.04 mm⁻¹
c = 20.247 (3) Å	T = 223 K
β = 129.391 (2)°	Block, yellow
V = 5374.5 (12) Å³	0.34 × 0.25 × 0.24 mm
Z = 8

Data collection top

Rigaku Saturn diffractometer	6122 independent reflections
Radiation source: fine-focus sealed tube	5277 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 14.63 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −38→30
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −15→12
T_min = 0.279, T_max = 0.378	l = −21→26
14977 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0407P)² + 26.4741P] where P = (F_o² + 2F_c²)/3
6122 reflections	(Δ/σ)_max = 0.002
392 parameters	Δρ_max = 1.20 e Å⁻³
4 restraints	Δρ_min = −1.18 e Å⁻³

Crystal data top

[Ir(C₁₁H₆F₂N)₂(C₇H₆NO)(H₂O)]·CH₄O	V = 5374.5 (12) Å³
M_r = 742.74	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 29.544 (4) Å	µ = 5.04 mm⁻¹
b = 11.6258 (12) Å	T = 223 K
c = 20.247 (3) Å	0.34 × 0.25 × 0.24 mm
β = 129.391 (2)°

Data collection top

Rigaku Saturn diffractometer	6122 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	5277 reflections with I > 2σ(I)
T_min = 0.279, T_max = 0.378	R_int = 0.031
14977 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	4 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0407P)² + 26.4741P] where P = (F_o² + 2F_c²)/3
6122 reflections	Δρ_max = 1.20 e Å⁻³
392 parameters	Δρ_min = −1.18 e Å⁻³

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ir1	0.347048 (9)	0.650175 (18)	−0.014534 (14)	0.03168 (9)
F1	0.4503 (2)	1.0543 (4)	0.0772 (3)	0.0836 (15)
F2	0.3963 (8)	0.9191 (12)	−0.1797 (9)	0.054 (4)	0.50
F2A	0.4011 (16)	0.913 (3)	−0.175 (2)	0.170 (12)	0.50
F3	0.438 (3)	0.306 (5)	−0.067 (4)	0.073 (8)	0.50
F3A	0.451 (3)	0.326 (5)	−0.049 (4)	0.089 (12)	0.50
F4	0.5660 (2)	0.4827 (5)	0.2118 (4)	0.0969 (18)
O1	0.22923 (18)	0.5920 (4)	−0.0254 (3)	0.0452 (11)
O2	0.26439 (19)	0.7445 (4)	−0.0750 (3)	0.0416 (10)
H2A	0.279 (3)	0.774 (6)	−0.027 (2)	0.050*
H2B	0.249 (3)	0.688 (4)	−0.070 (5)	0.050*
N1	0.3828 (2)	0.7418 (4)	0.0941 (3)	0.0371 (11)
N2	0.3159 (2)	0.5635 (4)	−0.1235 (3)	0.0385 (11)
N3	0.3141 (2)	0.5160 (4)	0.0160 (3)	0.0368 (11)
H3	0.3352	0.4537	0.0359	0.044*
C1	0.3830 (3)	0.7075 (6)	0.1581 (4)	0.0487 (16)
H1	0.3678	0.6348	0.1550	0.058*
C2	0.4049 (3)	0.7770 (8)	0.2280 (5)	0.063 (2)
H2	0.4051	0.7507	0.2720	0.076*
C3	0.4262 (3)	0.8823 (8)	0.2333 (5)	0.063 (2)
H3A	0.4402	0.9305	0.2801	0.075*
C4	0.4271 (3)	0.9189 (6)	0.1684 (4)	0.0505 (17)
H4	0.4421	0.9918	0.1713	0.061*
C5	0.4058 (3)	0.8471 (5)	0.1000 (4)	0.0402 (14)
C6	0.4042 (3)	0.8707 (5)	0.0273 (4)	0.0382 (13)
C7	0.4257 (3)	0.9693 (6)	0.0165 (4)	0.0493 (16)
C8	0.4244 (3)	0.9879 (6)	−0.0520 (5)	0.0551 (18)
H8	0.4395	1.0551	−0.0575	0.066*
C9	0.3994 (3)	0.9010 (7)	−0.1115 (5)	0.0535 (18)
C10	0.3775 (3)	0.8013 (6)	−0.1057 (4)	0.0411 (14)
H10	0.3616	0.7445	−0.1482	0.049*
C11	0.3791 (2)	0.7851 (5)	−0.0359 (4)	0.0331 (12)
C12	0.2627 (3)	0.5836 (6)	−0.1998 (4)	0.0524 (17)
H12	0.2385	0.6403	−0.2034	0.063*
C13	0.2430 (4)	0.5236 (7)	−0.2718 (5)	0.070 (2)
H13	0.2058	0.5387	−0.3242	0.084*
C14	0.2788 (5)	0.4403 (8)	−0.2660 (6)	0.078 (3)
H14	0.2661	0.3972	−0.3143	0.093*
C15	0.3329 (4)	0.4215 (7)	−0.1894 (6)	0.069 (2)
H15	0.3578	0.3667	−0.1856	0.083*
C16	0.3516 (3)	0.4824 (6)	−0.1166 (5)	0.0498 (17)
C17	0.4074 (3)	0.4732 (6)	−0.0308 (5)	0.0468 (16)
C18	0.4528 (4)	0.3966 (7)	−0.0035 (6)	0.063 (2)
C19	0.5056 (4)	0.3973 (7)	0.0764 (7)	0.072 (3)
H19	0.5354	0.3450	0.0929	0.086*
C20	0.5129 (3)	0.4784 (7)	0.1314 (6)	0.065 (2)
C21	0.4706 (3)	0.5553 (6)	0.1116 (5)	0.0520 (17)
H21	0.4780	0.6080	0.1527	0.062*
C22	0.4169 (3)	0.5537 (5)	0.0303 (4)	0.0408 (14)
C23	0.2672 (2)	0.5124 (5)	0.0096 (4)	0.0353 (13)
C24	0.2570 (3)	0.4127 (5)	0.0461 (4)	0.0359 (13)
C25	0.2003 (3)	0.3869 (6)	0.0129 (5)	0.0505 (16)
H25	0.1690	0.4317	−0.0319	0.061*
C26	0.1894 (4)	0.2950 (7)	0.0454 (6)	0.065 (2)
H26	0.1507	0.2774	0.0221	0.078*
C27	0.2346 (4)	0.2312 (7)	0.1105 (6)	0.063 (2)
H27	0.2271	0.1691	0.1321	0.076*
C28	0.2916 (4)	0.2567 (7)	0.1455 (5)	0.062 (2)
H28	0.3227	0.2124	0.1908	0.075*
C29	0.3025 (3)	0.3481 (6)	0.1133 (5)	0.0506 (17)
H29	0.3413	0.3661	0.1376	0.061*
O3	0.44588 (19)	0.2099 (4)	0.2396 (3)	0.0543 (12)
C30	0.4370 (5)	0.2603 (9)	0.1702 (7)	0.0543 (12)	0.589 (11)
C30A	0.4817 (6)	0.2785 (10)	0.2269 (12)	0.0543 (12)	0.411 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir1	0.03266 (13)	0.03359 (13)	0.03432 (13)	0.00037 (10)	0.02386 (11)	0.00088 (10)
F1	0.097 (4)	0.068 (3)	0.087 (3)	−0.037 (3)	0.059 (3)	−0.021 (3)
F2	0.087 (10)	0.054 (6)	0.046 (6)	−0.033 (7)	0.054 (7)	−0.011 (5)
F2A	0.18 (3)	0.22 (3)	0.18 (2)	−0.02 (2)	0.15 (2)	0.03 (2)
F3	0.10 (2)	0.048 (10)	0.11 (2)	−0.003 (11)	0.09 (2)	−0.026 (12)
F3A	0.10 (2)	0.07 (2)	0.11 (2)	0.010 (16)	0.07 (2)	−0.021 (15)
F4	0.047 (3)	0.089 (4)	0.114 (4)	0.020 (3)	0.032 (3)	0.024 (3)
O1	0.038 (2)	0.042 (2)	0.063 (3)	0.004 (2)	0.035 (2)	0.006 (2)
O2	0.037 (2)	0.046 (3)	0.047 (2)	0.004 (2)	0.029 (2)	0.009 (2)
N1	0.033 (3)	0.044 (3)	0.034 (3)	0.002 (2)	0.021 (2)	−0.001 (2)
N2	0.045 (3)	0.039 (3)	0.043 (3)	−0.009 (2)	0.033 (3)	−0.001 (2)
N3	0.039 (3)	0.035 (3)	0.043 (3)	0.002 (2)	0.029 (2)	0.003 (2)
C1	0.053 (4)	0.059 (4)	0.040 (3)	−0.005 (3)	0.033 (3)	−0.002 (3)
C2	0.061 (5)	0.081 (6)	0.051 (4)	−0.013 (4)	0.037 (4)	−0.018 (4)
C3	0.051 (4)	0.089 (6)	0.046 (4)	−0.005 (4)	0.031 (4)	−0.023 (4)
C4	0.044 (4)	0.050 (4)	0.056 (4)	−0.007 (3)	0.031 (3)	−0.013 (3)
C5	0.030 (3)	0.045 (3)	0.040 (3)	0.005 (3)	0.020 (3)	−0.002 (3)
C6	0.033 (3)	0.039 (3)	0.039 (3)	0.002 (3)	0.021 (3)	−0.001 (3)
C7	0.040 (3)	0.046 (4)	0.054 (4)	−0.013 (3)	0.026 (3)	−0.010 (3)
C8	0.051 (4)	0.052 (4)	0.068 (5)	−0.011 (3)	0.040 (4)	0.002 (4)
C9	0.061 (4)	0.060 (4)	0.056 (4)	−0.010 (4)	0.045 (4)	0.005 (4)
C10	0.046 (4)	0.045 (3)	0.045 (3)	−0.003 (3)	0.035 (3)	0.004 (3)
C11	0.027 (3)	0.036 (3)	0.038 (3)	0.005 (2)	0.022 (3)	0.005 (3)
C12	0.057 (4)	0.055 (4)	0.043 (4)	−0.014 (4)	0.031 (4)	−0.003 (3)
C13	0.093 (6)	0.065 (5)	0.045 (4)	−0.033 (5)	0.041 (5)	−0.011 (4)
C14	0.121 (8)	0.071 (6)	0.065 (5)	−0.043 (6)	0.070 (6)	−0.036 (5)
C15	0.106 (7)	0.061 (5)	0.084 (6)	−0.014 (5)	0.082 (6)	−0.017 (5)
C16	0.072 (5)	0.042 (4)	0.068 (5)	−0.010 (3)	0.059 (4)	−0.007 (3)
C17	0.051 (4)	0.047 (4)	0.070 (4)	0.002 (3)	0.051 (4)	0.002 (3)
C18	0.081 (6)	0.045 (4)	0.108 (7)	0.003 (4)	0.081 (6)	−0.003 (5)
C19	0.057 (5)	0.058 (5)	0.113 (8)	0.023 (4)	0.060 (6)	0.024 (5)
C20	0.040 (4)	0.059 (5)	0.081 (6)	0.009 (4)	0.032 (4)	0.021 (4)
C21	0.040 (4)	0.050 (4)	0.065 (4)	−0.001 (3)	0.033 (4)	0.003 (4)
C22	0.040 (3)	0.037 (3)	0.062 (4)	0.000 (3)	0.040 (3)	0.005 (3)
C23	0.035 (3)	0.037 (3)	0.036 (3)	−0.007 (3)	0.024 (3)	−0.008 (3)
C24	0.047 (3)	0.032 (3)	0.041 (3)	−0.005 (3)	0.034 (3)	−0.003 (3)
C25	0.051 (4)	0.052 (4)	0.056 (4)	−0.007 (3)	0.037 (4)	−0.004 (3)
C26	0.090 (6)	0.051 (4)	0.091 (6)	−0.026 (5)	0.075 (6)	−0.017 (5)
C27	0.104 (7)	0.044 (4)	0.077 (5)	−0.013 (4)	0.073 (6)	−0.002 (4)
C28	0.087 (6)	0.057 (4)	0.057 (4)	0.007 (4)	0.053 (5)	0.013 (4)
C29	0.057 (4)	0.052 (4)	0.050 (4)	0.002 (3)	0.038 (4)	0.005 (3)
O3	0.036 (2)	0.031 (2)	0.092 (3)	0.0002 (17)	0.038 (2)	−0.017 (2)
C30	0.036 (2)	0.031 (2)	0.092 (3)	0.0002 (17)	0.038 (2)	−0.017 (2)
C30A	0.036 (2)	0.031 (2)	0.092 (3)	0.0002 (17)	0.038 (2)	−0.017 (2)

Geometric parameters (Å, º) top

Ir1—C22	1.991 (6)	C9—C10	1.367 (9)
Ir1—C11	2.016 (6)	C10—C11	1.397 (8)
Ir1—N1	2.035 (5)	C10—H10	0.9400
Ir1—N2	2.038 (5)	C12—C13	1.370 (10)
Ir1—N3	2.127 (5)	C12—H12	0.9400
Ir1—O2	2.207 (4)	C13—C14	1.383 (13)
F1—C7	1.371 (8)	C13—H13	0.9400
F2—C9	1.340 (15)	C14—C15	1.364 (13)
F2A—C9	1.33 (3)	C14—H14	0.9400
F3—C18	1.49 (4)	C15—C16	1.395 (10)
F3A—C18	1.21 (5)	C15—H15	0.9400
F4—C20	1.368 (9)	C16—C17	1.454 (10)
O1—C23	1.268 (7)	C17—C18	1.398 (10)
O2—H2A	0.854 (10)	C17—C22	1.429 (9)
O2—H2B	0.849 (10)	C18—C19	1.360 (12)
N1—C1	1.353 (8)	C19—C20	1.368 (12)
N1—C5	1.368 (8)	C19—H19	0.9400
N2—C12	1.353 (8)	C20—C21	1.374 (10)
N2—C16	1.353 (8)	C21—C22	1.383 (9)
N3—C23	1.309 (7)	C21—H21	0.9400
N3—H3	0.8700	C23—C24	1.504 (8)
C1—C2	1.382 (10)	C24—C29	1.379 (9)
C1—H1	0.9400	C24—C25	1.384 (9)
C2—C3	1.350 (12)	C25—C26	1.397 (10)
C2—H2	0.9400	C25—H25	0.9400
C3—C4	1.397 (10)	C26—C27	1.356 (12)
C3—H3A	0.9400	C26—H26	0.9400
C4—C5	1.380 (9)	C27—C28	1.382 (11)
C4—H4	0.9400	C27—H27	0.9400
C5—C6	1.470 (9)	C28—C29	1.388 (10)
C6—C7	1.392 (9)	C28—H28	0.9400
C6—C11	1.404 (8)	C29—H29	0.9400
C7—C8	1.379 (10)	O3—C30	1.387 (9)
C8—C9	1.374 (10)	O3—C30A	1.472 (9)
C8—H8	0.9400

C22—Ir1—C11	92.5 (2)	C10—C11—Ir1	127.1 (5)
C22—Ir1—N1	97.2 (2)	C6—C11—Ir1	113.8 (4)
C11—Ir1—N1	80.3 (2)	N2—C12—C13	121.9 (8)
C22—Ir1—N2	80.8 (2)	N2—C12—H12	119.1
C11—Ir1—N2	95.9 (2)	C13—C12—H12	119.1
N1—Ir1—N2	175.72 (19)	C12—C13—C14	118.7 (8)
C22—Ir1—N3	89.3 (2)	C12—C13—H13	120.6
C11—Ir1—N3	175.3 (2)	C14—C13—H13	120.6
N1—Ir1—N3	95.12 (19)	C15—C14—C13	119.4 (7)
N2—Ir1—N3	88.66 (18)	C15—C14—H14	120.3
C22—Ir1—O2	174.2 (2)	C13—C14—H14	120.3
C11—Ir1—O2	90.00 (19)	C14—C15—C16	120.8 (8)
N1—Ir1—O2	88.38 (18)	C14—C15—H15	119.6
N2—Ir1—O2	93.72 (19)	C16—C15—H15	119.6
N3—Ir1—O2	88.65 (17)	N2—C16—C15	119.0 (7)
Ir1—O2—H2A	90 (5)	N2—C16—C17	113.2 (6)
Ir1—O2—H2B	92 (5)	C15—C16—C17	127.8 (7)
H2A—O2—H2B	95 (7)	C18—C17—C22	117.6 (7)
C1—N1—C5	118.7 (5)	C18—C17—C16	126.5 (7)
C1—N1—Ir1	124.4 (4)	C22—C17—C16	115.9 (6)
C5—N1—Ir1	116.8 (4)	F3A—C18—C19	112 (3)
C12—N2—C16	120.2 (6)	F3A—C18—C17	124 (3)
C12—N2—Ir1	123.3 (5)	C19—C18—C17	123.7 (8)
C16—N2—Ir1	116.5 (4)	F3A—C18—F3	11 (5)
C23—N3—Ir1	130.2 (4)	C19—C18—F3	121 (3)
C23—N3—H3	114.9	C17—C18—F3	115 (3)
Ir1—N3—H3	114.9	C18—C19—C20	116.3 (7)
N1—C1—C2	121.5 (7)	C18—C19—H19	121.9
N1—C1—H1	119.3	C20—C19—H19	121.9
C2—C1—H1	119.3	C19—C20—F4	117.6 (7)
C3—C2—C1	120.3 (7)	C19—C20—C21	124.5 (8)
C3—C2—H2	119.9	F4—C20—C21	117.9 (8)
C1—C2—H2	119.9	C20—C21—C22	118.8 (7)
C2—C3—C4	119.2 (7)	C20—C21—H21	120.6
C2—C3—H3A	120.4	C22—C21—H21	120.6
C4—C3—H3A	120.4	C21—C22—C17	119.1 (6)
C5—C4—C3	119.4 (7)	C21—C22—Ir1	127.5 (5)
C5—C4—H4	120.3	C17—C22—Ir1	113.4 (5)
C3—C4—H4	120.3	O1—C23—N3	122.5 (5)
N1—C5—C4	120.9 (6)	O1—C23—C24	117.1 (5)
N1—C5—C6	112.4 (5)	N3—C23—C24	120.4 (5)
C4—C5—C6	126.7 (6)	C29—C24—C25	118.9 (6)
C7—C6—C11	118.1 (6)	C29—C24—C23	122.1 (6)
C7—C6—C5	125.6 (6)	C25—C24—C23	119.0 (6)
C11—C6—C5	116.3 (5)	C24—C25—C26	120.5 (7)
F1—C7—C8	116.6 (6)	C24—C25—H25	119.8
F1—C7—C6	119.2 (6)	C26—C25—H25	119.8
C8—C7—C6	124.1 (6)	C27—C26—C25	119.8 (8)
C9—C8—C7	115.0 (6)	C27—C26—H26	120.1
C9—C8—H8	122.5	C25—C26—H26	120.1
C7—C8—H8	122.5	C26—C27—C28	120.6 (7)
F2A—C9—F2	6 (2)	C26—C27—H27	119.7
F2A—C9—C10	118.9 (16)	C28—C27—H27	119.7
F2—C9—C10	119.5 (8)	C27—C28—C29	119.7 (8)
F2A—C9—C8	116.3 (16)	C27—C28—H28	120.2
F2—C9—C8	115.9 (8)	C29—C28—H28	120.2
C10—C9—C8	124.6 (7)	C24—C29—C28	120.5 (7)
C9—C10—C11	119.1 (6)	C24—C29—H29	119.7
C9—C10—H10	120.4	C28—C29—H29	119.7
C11—C10—H10	120.4	C30—O3—C30A	44.6 (8)
C10—C11—C6	119.0 (5)	C30Aⁱ—C30A—O3	111 (2)

C22—Ir1—N1—C1	−86.8 (5)	O2—Ir1—N1—C1	91.6 (5)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···N3	0.85 (1)	2.54 (6)	3.029 (7)	117 (6)
O2—H2B···O1	0.85 (1)	1.74 (3)	2.560 (6)	161 (7)
O2—H2A···N1	0.85 (1)	2.45 (6)	2.960 (6)	119 (6)
O2—H2A···O1ⁱⁱ	0.85 (1)	1.97 (4)	2.700 (7)	142 (6)

Symmetry code: (ii) −x+1/2, −y+3/2, −z.

Experimental details

Crystal data
Chemical formula	[Ir(C₁₁H₆F₂N)₂(C₇H₆NO)(H₂O)]·CH₄O
M_r	742.74
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	223
a, b, c (Å)	29.544 (4), 11.6258 (12), 20.247 (3)
β (°)	129.391 (2)
V (Å³)	5374.5 (12)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	5.04
Crystal size (mm)	0.34 × 0.25 × 0.24

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.279, 0.378
No. of measured, independent and observed [I > 2σ(I)] reflections	14977, 6122, 5277
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.101, 1.09
No. of reflections	6122
No. of parameters	392
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0407P)² + 26.4741P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.20, −1.18

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···N3	0.849 (10)	2.54 (6)	3.029 (7)	117 (6)
O2—H2B···O1	0.849 (10)	1.74 (3)	2.560 (6)	161 (7)
O2—H2A···N1	0.854 (10)	2.45 (6)	2.960 (6)	119 (6)
O2—H2A···O1ⁱ	0.854 (10)	1.97 (4)	2.700 (7)	142 (6)

Symmetry code: (i) −x+1/2, −y+3/2, −z.

Acknowledgements

The authors thank the National Natural Science Foundation of China (NNSFC grant No. 20971058) and the Fundamental Research Funds for the Central Universities (grant No. JUSRP 11105) for financial support.

References

Jacobson, R. (1998). REQAB. Private communication to Rigaku Corporation, Tokyo, Japan. Google Scholar
Nonoyama, M. (1974). Bull. Chem. Soc. Jpn, 47, 767–768. CrossRef CAS Web of Science Google Scholar
Rigaku (2007). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tamayo, A. B., Alleyne, B. D., Djurovich, P. I., Lamansky, S. L., Tsyba, I., Ho, N. N., Bau, R. & Thompson, M. E. (2003). J. Am. Chem. Soc. 125, 7377–7387. Web of Science CSD CrossRef PubMed CAS Google Scholar
Wang, W., Zhu, T., Chen, G., Li, C., Di, H., Ren, C. & Ding, Y. (2008). Synth. Met. 158, 1022–1027. Web of Science CrossRef CAS Google Scholar
Yang, C. H., Cheng, Y. M., Chi, Y., Hsu, C. J., Fang, F. C., Wong, K. T., Chou, P. T., Chang, C. H., Tsai, M. H. & Wu, C. C. (2007). Angew. Chem. Int. Ed. 46, 2418–2421. Web of Science CSD CrossRef CAS Google Scholar
Yang, W., Fu, H., Song, Q., Zhang, M. & Ding, Y. (2011). Organometallics, 30, 77–83. Web of Science CSD CrossRef CAS Google Scholar
You, Y. & Park, S. Y. (2005). J. Am. Chem. Soc. 127, 12438–12439. Web of Science CrossRef PubMed CAS Google Scholar
Zhang, S., Wu, F., Yang, W. & Ding, Y. (2011). Inorg. Chem. Commun. 14, 1414–1417. Web of Science CSD CrossRef CAS Google Scholar

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