Mono- and bis-tolyl­terpyridine iridium(III) complexes

The first structure report of trichlorido[4'-(p-tolyl)-2,2':6',2''-terpyridine]iridium(III) dimethyl sulfoxide solvate, [IrCl₃(C₂₂H₁₇N₃)]·C₂H₆OS, (I), is presented, along with a higher-symmetry setting of previously reported bis­[4'-(p-tolyl)-2,2':6',2''-terpyridine]iridium(III) tris­(hexa­fluorido­phosphate) acetonitrile disolvate, [Ir(C₂₂H₁₇N₃)₂](PF₆)₃·2C₂H₃N, (II) [Yoshikawa, Yamabe, Kanehisa, Kai, Takashima & Tsukahara (2007). Eur. J. Inorg. Chem. pp. 1911-1919]. For (I), the data were collected with synchrotron radiation and the dimethyl sulfoxide solvent mol­ecule is disordered over three positions, one of which is an inversion center. The previously reported structure of (II) is presented in the more appropriate C2/c space group. The iridium complex and one PF₆^- anion lie on twofold axes in this structure, making half of the mol­ecule unique.

S1. Comment

To our knowledge, before the publication of this paper only seven structures of terpyridine iridium(III) complexes were present in the Cambridge Structural Database (CSD, Version 5.30 of May 2009; Allen, 2002). The lack of both mono- and bis-terpyridine-based iridium(III) structures may be due in part to the inertness of the metal center or the difficulty of making tricationic iridium(III) species in considerable yield (Cusanelli et al., 1996; Collin et al., 1999). In an attempt to synthesize a tricationic bis-ttpy (ttpy is tolylterpyridine?) species, we were able to isolate the neutral trichloride species. Here we present the structures of both trichlorido[4'-(p-tolyl)-2,2':6',2''-terpyridine]iridium(III) dimethyl sulfoxide solvate, (I), and bis[4'-(p-tolyl)-2,2':6',2''-terpyridine]iridium(III) tris(hexafluorophosphate) acetonitrile disolvate, (II).

Structure (I), Ir(ttpy)Cl₃.DMSO (DMSO is dimethysulfoxide), is shown in Fig. 1. The DMSO solvent molecule is disordered over three positions, one of which is 1. The tolyl group at the 4'-position of the terpyridine ligand is positionally disordered over two positions [0.64 (4):0.37 (4)]. The plane formed by the Ir metal center and the atoms of the three chelating rings (N1/C1–C5, N2/C6–C10 and N3/C11–C13 [C15?]) of the ttpy ligand is planar, with an r.m.s. deviation of 0.0673 Å. This plane is twisted by 89.84 (5)° relative to the plane formed by the Ir atom and the three Cl ligands, which has an r.m.s. deviation of 0.0054 Å. Due to the bite angle of the ttpy ligand, the bond distance from Ir1 to the central atom N2 is 1.947 (4) Å, which is significantly shorter than those for the two outer atoms, N1 and N3, of 2.037 (5) and 2.041 (4) Å, respectively. The chloride ligand (Cl2) trans to the central N atom of the ttpy ligand exhibits the longest bond distance of the three chlorides [Ir1—Cl2 = 2.3856 (13) Å]. All of the Ir—N and Ir—Cl bond distances in (I) fall within the expected ranges based on a CSD search.

The data for structure (II), [Ir(ttpy)₂](PF₆)₃.2CH₃CN, were collected initially to aid in the identification of the products from a reaction between Ir(ttpy)Cl₃ and ttpy. While the collection temperature for (II) was lower, at 173 K, the initial unit-cell parameters and cell volume were similar to a room-temperature structure reported by Yoshikawa et al. (2007) for the same compound (CSD refcode YIDGAU). The previously reported structure was solved in space group Cc. However, closer examination of the bond distances within this structure led us to believe that the structure had been solved in the incorrect space group.

A comparison of the chemically equivalent bond distances between the two independent ttpy ligands in structure YIDGAU revealed many that were more than five standard deviations apart. This result was surprising considering the inherent D_2d symmetry of the molecule. Marsh (1997) reports that the space group Cc is often misassigned when a two-fold axis has been overlooked. It appears that many structures in Cc are often revised to be C2/c after this missing symmetry element is found (Herbstein & Marsh, 1998; Marsh, 1997). Furthermore, this space group change leads to more reasonable bond lengths and angles within the structure. The ADDSYM routine in PLATON (Spek, 2009) was conducted on the YIDGAU CIF and conclusively found missing symmetry in the structure. The addition of 1 and two-fold symmetry to the structure leads to a solution in space group C2/c. Solving the structure of (II) in the centrosymmetric space group C2/c gave comparable bond lengths and angles to those reported for a bis(2,2':6',2''-terpyridine)iridium(III) structure (CSD refcode FOHQAU; Collin et al., 1999), leading us to believe that C2/c is indeed the correct space group setting for (II).

In (II), one P atom (P1) is not on a special postion, while the second (P2) lies on a two-fold axis. The Ir atom also lies on this two-fold axis, making half of the cation unique. The acetonitrile solvent molecule is located on a general position as well (Fig. 2). Bond distances from the N atoms to the Ir atom are 2.052 (6) (N1), 1.966 (6) (N2) and 2.047 (6) Å (N3), following the similar long–short–long pattern found in the mono-ttpy derivative, (I), and are within the expected range for Ir—N bond distances. The Ir atom and the atoms of the three chelating rings of the ttpy ligand are planar, with an r.m.s. deviation from the plane of 0.0457 Å.

S2. Experimental

Ir(ttpy)Cl₃ was synthesized following the method of Collin et al. (1999) and single crystals of (I) were grown from slow cooling of a hot solution in DMSO. X-ray data were collected at the APS synchrotron sector 15-ID-C at Argonne National Laboratory, due to the extremely small size of at least one of the crystal dimensions.

[Ir(ttpy)₂](PF₆)₃ was synthesized according to the method of Collin et al. (1999) and crystals of (II) were grown by slow evaporation of a solution in acetonitrile after separation of the compound with dichloromethane and acetone on a neutral alumina column.

S3. Refinement

In structure (I), the DMSO molecule was modeled over three positions whose site-occupation factors were restrained to sum to 1.00 [actual occupation factors of the three orientations = 0.500 (3), 0.328 (3) and 0.173 (2)]. Similarity restraints were applied to the chemically equivalent bond lengths and angles across the three orientations, while the distances between the S and O atoms and between the S and C atoms were restrained to 1.678 (5) and 1.862 (5) Å, respectively. The atomic displacement parameters of the corresponding atom in each of the three orientations were constrained to be identical. The tolyl substituent was also disordered over two orientations, with C16 serving as the anchor atom. The atomic displacement parameters of corresponding atoms in the two orientations were also constrained to be identical, while (**author to appropriately correct and complete the next bit **) similarity restraints were applied to the chemically equivalent bond lengths and angles.

In structure (II), a direct methods solution was attempted, but did not yield the correct position of the heavy atom. When a Patterson map solution was used, the correct position of the Ir atom was chosen as that on the 2 [text incomplete?]. Refinement of the remaining atoms proceeded without incident. No disorder was modeled within this structure.

In both structures, all aromatic H atoms were placed in ideal positions and refined as riding, with C—H = 0.95 Å and with U_iso(H) = 1.2U_eq(C). Methyl H atoms were placed in ideal positions and refined as riding, with C—H = 0.98 Å and with U_iso(H) = 1.5U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2008) for (I); SMART (Bruker, 2003) for (II). Cell refinement: APEX2 (Bruker, 2008) for (I); SAINT (Bruker, 2003) for (II). For both compounds, data reduction: SAINT (Bruker, 2003); 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: [Please provide missing details].

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been removed for clarity. Within the Ir-containing molecule, solid bonds represent the main disorder component. DMSO modeling is also shown and the molecule represented with dashed bonds is over the inversion center.
	Fig. 2. The symmetry-generated molecule of (II). Displacement ellipsoids are drawn at the 50% probability level. H atoms have been removed for clarity and only selected atoms have been labeled. [Please include sufficient C-atom labels to enable unambiguous assignment]

(I) trichlorido[4'-(p-tolyl)-2,2':6',2''-terpyridine]iridium(III) dimethyl sulfoxide solvate

Crystal data

[IrCl3(C22H17N3)]·C2H6OS	F(000) = 1360
Mr = 700.06	Dx = 1.868 Mg m^−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.41328 Å
a = 10.377 (2) Å	Cell parameters from 9999 reflections
b = 23.166 (5) Å	θ = 2.3–20.0°
c = 10.370 (2) Å	µ = 3.08 mm^−1
β = 93.22 (3)°	T = 100 K
V = 2488.9 (9) Å^3	Needle, yellow
Z = 4	0.08 × 0.01 × 0.01 mm

Data collection

Bruker SMART APEXII diffractometer	7484 independent reflections
Radiation source: APS15-ID-B	6292 reflections with I > 2σ(I)
Double-diamond monochromator	Rint = 0.045
ϕ and ω scans	θmax = 17.2°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	h = −14→14
Tmin = 0.791, Tmax = 0.985	k = −33→33
68215 measured reflections	l = −12→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0375P)^2 + 14.1866P] where P = (Fo^2 + 2Fc^2)/3
7484 reflections	(Δ/σ)max = 0.002
346 parameters	Δρmax = 3.32 e Å^−3
61 restraints	Δρmin = −2.40 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 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.

The DMSO molecule was modeled using Part 1, 2, and Part -1 statements along with the SUMP command to ensure the occupancy of the three parts was 1.00. Two SAME commands were used within each part and included SAME S1 > C24 and a SAME statement for the part itself. The distance between the sulfur atoms and oxygen atoms was restrained to 1.68 Angstrom Å with DFIX. The distance between the sulfur atoms and respective carbon atoms was also restrained to a distance of 1.86 Angstrom Å with DFIX. EADP was used to control the thermal parameters of the same atom in each of the three parts. The tolyl substituent was modeled using Part 1 and Part 2 statements with C16 serving as the anchor atom. The thermal parameters of the two parts were refined to be the same with EADP.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ir1	0.879171 (17)	0.376314 (8)	0.700962 (17)	0.02401 (6)
Cl1	1.06502 (13)	0.38087 (7)	0.84170 (14)	0.0380 (3)
Cl2	1.00449 (13)	0.39997 (6)	0.52240 (12)	0.0323 (3)
Cl3	0.68960 (12)	0.37249 (5)	0.56234 (12)	0.0280 (2)
N1	0.8286 (4)	0.45677 (19)	0.7593 (4)	0.0303 (9)
N2	0.7752 (4)	0.35540 (17)	0.8444 (4)	0.0232 (7)
N3	0.8990 (4)	0.28871 (18)	0.6942 (4)	0.0232 (7)
C1	0.8617 (6)	0.5080 (2)	0.7080 (6)	0.0349 (11)
H1A	0.9112	0.5085	0.6336	0.042*
C2	0.8245 (6)	0.5597 (3)	0.7623 (7)	0.0416 (13)
H2A	0.8491	0.5953	0.7253	0.050*
C3	0.7516 (7)	0.5595 (2)	0.8704 (6)	0.0408 (13)
H3A	0.7277	0.5948	0.9092	0.049*
C4	0.7141 (6)	0.5069 (2)	0.9211 (6)	0.0360 (11)
H4A	0.6619	0.5059	0.9934	0.043*
C5	0.7536 (5)	0.4562 (2)	0.8652 (5)	0.0285 (9)
C6	0.7199 (5)	0.3982 (2)	0.9107 (5)	0.0263 (9)
C7	0.6394 (5)	0.3835 (2)	1.0082 (5)	0.0271 (9)
H7A	0.5989	0.4129	1.0551	0.032*
C8	0.6176 (4)	0.3251 (2)	1.0376 (5)	0.0243 (9)
C9	0.6772 (4)	0.2825 (2)	0.9656 (4)	0.0234 (8)
H9A	0.6632	0.2428	0.9830	0.028*
C10	0.7569 (4)	0.29875 (19)	0.8686 (4)	0.0212 (8)
C11	0.8311 (4)	0.2605 (2)	0.7851 (4)	0.0225 (8)
C12	0.8377 (5)	0.2011 (2)	0.7986 (5)	0.0255 (9)
H12A	0.7914	0.1822	0.8628	0.031*
C13	0.9130 (5)	0.1694 (2)	0.7172 (5)	0.0296 (10)
H13A	0.9177	0.1286	0.7245	0.036*
C14	0.9812 (5)	0.1980 (2)	0.6252 (5)	0.0304 (10)
H14A	1.0329	0.1770	0.5688	0.036*
C15	0.9726 (5)	0.2577 (2)	0.6169 (5)	0.0282 (9)
H15A	1.0202	0.2773	0.5547	0.034*
C16	0.5287 (5)	0.3092 (2)	1.1396 (5)	0.0257 (9)	0.64 (4)
C17	0.505 (9)	0.349 (2)	1.236 (7)	0.039 (2)	0.64 (4)
H17A	0.5543	0.3838	1.2441	0.047*	0.64 (4)
C18	0.408 (2)	0.3381 (7)	1.3223 (17)	0.035 (3)	0.64 (4)
H18A	0.3900	0.3661	1.3857	0.042*	0.64 (4)
C19	0.3382 (16)	0.2869 (8)	1.3164 (16)	0.028 (3)	0.64 (4)
C20	0.3675 (17)	0.2461 (7)	1.2255 (17)	0.033 (3)	0.64 (4)
H20A	0.3180	0.2117	1.2168	0.040*	0.64 (4)
C21	0.471 (5)	0.2555 (13)	1.146 (4)	0.037 (4)	0.64 (4)
H21A	0.5009	0.2246	1.0952	0.045*	0.64 (4)
C22	0.2318 (15)	0.2759 (9)	1.4078 (16)	0.035 (3)	0.64 (4)
H22A	0.2458	0.3000	1.4849	0.052*	0.64 (4)
H22B	0.2326	0.2351	1.4330	0.052*	0.64 (4)
H22C	0.1481	0.2854	1.3644	0.052*	0.64 (4)
C16'	0.5287 (5)	0.3092 (2)	1.1396 (5)	0.0257 (9)	0.36 (4)
C17'	0.495 (16)	0.346 (4)	1.239 (12)	0.039 (2)	0.36 (4)
H17B	0.5265	0.3850	1.2408	0.047*	0.36 (4)
C18'	0.416 (4)	0.3271 (13)	1.336 (3)	0.035 (3)	0.36 (4)
H18B	0.4067	0.3502	1.4102	0.042*	0.36 (4)
C19'	0.352 (3)	0.2744 (12)	1.324 (3)	0.028 (3)	0.36 (4)
C20'	0.395 (3)	0.2362 (11)	1.234 (3)	0.033 (3)	0.36 (4)
H20B	0.3748	0.1963	1.2403	0.040*	0.36 (4)
C21'	0.467 (10)	0.256 (2)	1.132 (8)	0.037 (4)	0.36 (4)
H21B	0.4736	0.2329	1.0569	0.045*	0.36 (4)
C22'	0.242 (3)	0.2578 (13)	1.406 (3)	0.035 (3)	0.36 (4)
H22D	0.2188	0.2907	1.4592	0.052*	0.36 (4)
H22E	0.2681	0.2253	1.4618	0.052*	0.36 (4)
H22F	0.1668	0.2465	1.3497	0.052*	0.36 (4)
S1	0.6173 (3)	0.51044 (14)	0.3243 (3)	0.0407 (5)	0.500 (3)
O1	0.5516 (9)	0.4956 (5)	0.1819 (7)	0.044 (2)	0.500 (3)
C23	0.7860 (7)	0.4879 (7)	0.301 (2)	0.044 (3)	0.500 (3)
H23A	0.7916	0.4457	0.3027	0.066*	0.500 (3)
H23B	0.8433	0.5041	0.3696	0.066*	0.500 (3)
H23C	0.8120	0.5020	0.2168	0.066*	0.500 (3)
C24	0.6528 (18)	0.5889 (3)	0.327 (2)	0.095 (7)	0.500 (3)
H24A	0.5718	0.6106	0.3279	0.143*	0.500 (3)
H24B	0.6983	0.5993	0.2501	0.143*	0.500 (3)
H24C	0.7071	0.5982	0.4046	0.143*	0.500 (3)
S1'	0.6490 (5)	0.5333 (2)	0.2647 (5)	0.0407 (5)	0.328 (3)
O1'	0.6009 (12)	0.6014 (3)	0.2754 (15)	0.044 (2)	0.328 (3)
C23'	0.8029 (17)	0.4987 (11)	0.319 (3)	0.044 (3)	0.328 (3)
H23D	0.8593	0.4962	0.2470	0.066*	0.328 (3)
H23E	0.7857	0.4597	0.3513	0.066*	0.328 (3)
H23F	0.8451	0.5216	0.3890	0.066*	0.328 (3)
C24'	0.591 (3)	0.5212 (13)	0.4299 (15)	0.095 (7)	0.328 (3)
H24D	0.5088	0.5412	0.4379	0.143*	0.328 (3)
H24E	0.6550	0.5364	0.4945	0.143*	0.328 (3)
H24F	0.5794	0.4798	0.4441	0.143*	0.328 (3)
S1A	0.5433 (9)	0.5269 (4)	0.3082 (9)	0.0407 (5)	0.172 (3)
O1A	0.582 (3)	0.4835 (14)	0.189 (3)	0.044 (2)	0.172 (3)
C23A	0.656 (3)	0.5132 (13)	0.451 (2)	0.044 (3)	0.172 (3)
H23G	0.6330	0.4769	0.4920	0.066*	0.172 (3)
H23H	0.6505	0.5450	0.5125	0.066*	0.172 (3)
H23I	0.7446	0.5106	0.4226	0.066*	0.172 (3)
C24A	0.646 (4)	0.5901 (14)	0.271 (5)	0.095 (7)	0.172 (3)
H24G	0.6396	0.5976	0.1781	0.143*	0.172 (3)
H24H	0.7359	0.5820	0.2991	0.143*	0.172 (3)
H24I	0.6161	0.6242	0.3173	0.143*	0.172 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.02325 (9)	0.03044 (10)	0.01906 (10)	−0.00487 (6)	0.00763 (6)	0.00212 (6)
Cl1	0.0312 (6)	0.0541 (8)	0.0289 (6)	−0.0134 (5)	0.0031 (5)	0.0064 (5)
Cl2	0.0352 (6)	0.0386 (6)	0.0244 (6)	−0.0072 (5)	0.0117 (4)	0.0051 (5)
Cl3	0.0288 (5)	0.0285 (5)	0.0268 (6)	0.0007 (4)	0.0034 (4)	−0.0027 (4)
N1	0.036 (2)	0.030 (2)	0.025 (2)	−0.0102 (17)	0.0069 (17)	0.0009 (16)
N2	0.0226 (17)	0.0261 (18)	0.0216 (19)	−0.0034 (14)	0.0065 (14)	0.0008 (14)
N3	0.0212 (17)	0.0316 (19)	0.0175 (18)	0.0001 (14)	0.0065 (13)	0.0002 (14)
C1	0.039 (3)	0.032 (2)	0.034 (3)	−0.009 (2)	0.007 (2)	0.003 (2)
C2	0.047 (3)	0.029 (3)	0.049 (4)	−0.009 (2)	0.008 (3)	0.002 (2)
C3	0.053 (4)	0.029 (3)	0.041 (3)	−0.006 (2)	0.006 (3)	−0.005 (2)
C4	0.043 (3)	0.032 (3)	0.034 (3)	−0.003 (2)	0.007 (2)	−0.004 (2)
C5	0.031 (2)	0.030 (2)	0.026 (2)	−0.0050 (18)	0.0059 (18)	−0.0016 (18)
C6	0.030 (2)	0.026 (2)	0.023 (2)	−0.0034 (17)	0.0054 (17)	−0.0040 (17)
C7	0.029 (2)	0.030 (2)	0.022 (2)	−0.0014 (18)	0.0091 (17)	−0.0042 (17)
C8	0.022 (2)	0.029 (2)	0.023 (2)	−0.0005 (16)	0.0085 (16)	−0.0008 (16)
C9	0.024 (2)	0.027 (2)	0.020 (2)	−0.0014 (16)	0.0076 (16)	0.0011 (16)
C10	0.0200 (19)	0.027 (2)	0.018 (2)	−0.0012 (15)	0.0063 (14)	0.0001 (15)
C11	0.0199 (19)	0.030 (2)	0.018 (2)	−0.0002 (16)	0.0066 (15)	0.0011 (16)
C12	0.024 (2)	0.032 (2)	0.021 (2)	0.0009 (17)	0.0082 (16)	0.0018 (17)
C13	0.029 (2)	0.035 (2)	0.026 (2)	0.0048 (19)	0.0060 (18)	−0.0010 (18)
C14	0.027 (2)	0.039 (3)	0.025 (2)	0.0064 (19)	0.0079 (18)	−0.0026 (19)
C15	0.024 (2)	0.041 (3)	0.020 (2)	0.0038 (19)	0.0083 (16)	0.0027 (18)
C16	0.024 (2)	0.034 (2)	0.020 (2)	−0.0001 (17)	0.0114 (16)	−0.0004 (17)
C17	0.047 (13)	0.039 (5)	0.034 (4)	0.000 (3)	0.024 (4)	−0.003 (4)
C18	0.045 (4)	0.033 (7)	0.028 (5)	0.017 (5)	0.021 (4)	0.010 (5)
C19	0.019 (4)	0.041 (7)	0.023 (3)	0.012 (5)	0.009 (3)	0.009 (4)
C20	0.020 (7)	0.048 (6)	0.032 (4)	−0.007 (5)	0.011 (5)	−0.005 (4)
C21	0.039 (4)	0.050 (3)	0.025 (9)	−0.016 (3)	0.017 (7)	−0.012 (4)
C22	0.029 (4)	0.043 (9)	0.033 (3)	0.008 (5)	0.019 (3)	0.003 (6)
C16'	0.024 (2)	0.034 (2)	0.020 (2)	−0.0001 (17)	0.0114 (16)	−0.0004 (17)
C17'	0.047 (13)	0.039 (5)	0.034 (4)	0.000 (3)	0.024 (4)	−0.003 (4)
C18'	0.045 (4)	0.033 (7)	0.028 (5)	0.017 (5)	0.021 (4)	0.010 (5)
C19'	0.019 (4)	0.041 (7)	0.023 (3)	0.012 (5)	0.009 (3)	0.009 (4)
C20'	0.020 (7)	0.048 (6)	0.032 (4)	−0.007 (5)	0.011 (5)	−0.005 (4)
C21'	0.039 (4)	0.050 (3)	0.025 (9)	−0.016 (3)	0.017 (7)	−0.012 (4)
C22'	0.029 (4)	0.043 (9)	0.033 (3)	0.008 (5)	0.019 (3)	0.003 (6)
S1	0.0447 (14)	0.0360 (12)	0.0428 (14)	−0.0033 (10)	0.0153 (11)	0.0005 (9)
O1	0.032 (5)	0.046 (5)	0.056 (4)	−0.001 (3)	0.007 (3)	−0.026 (4)
C23	0.033 (4)	0.034 (7)	0.062 (8)	−0.003 (5)	−0.016 (4)	−0.013 (5)
C24	0.083 (10)	0.134 (15)	0.068 (12)	0.082 (11)	−0.003 (9)	−0.003 (10)
S1'	0.0447 (14)	0.0360 (12)	0.0428 (14)	−0.0033 (10)	0.0153 (11)	0.0005 (9)
O1'	0.032 (5)	0.046 (5)	0.056 (4)	−0.001 (3)	0.007 (3)	−0.026 (4)
C23'	0.033 (4)	0.034 (7)	0.062 (8)	−0.003 (5)	−0.016 (4)	−0.013 (5)
C24'	0.083 (10)	0.134 (15)	0.068 (12)	0.082 (11)	−0.003 (9)	−0.003 (10)
S1A	0.0447 (14)	0.0360 (12)	0.0428 (14)	−0.0033 (10)	0.0153 (11)	0.0005 (9)
O1A	0.032 (5)	0.046 (5)	0.056 (4)	−0.001 (3)	0.007 (3)	−0.026 (4)
C23A	0.033 (4)	0.034 (7)	0.062 (8)	−0.003 (5)	−0.016 (4)	−0.013 (5)
C24A	0.083 (10)	0.134 (15)	0.068 (12)	0.082 (11)	−0.003 (9)	−0.003 (10)

Geometric parameters (Å, º)

Ir1—N2	1.947 (4)	C20—C21	1.406 (18)
Ir1—N1	2.037 (5)	C20—H20A	0.9500
Ir1—N3	2.041 (4)	C21—H21A	0.9500
Ir1—Cl1	2.3546 (16)	C22—H22A	0.9800
Ir1—Cl3	2.3719 (14)	C22—H22B	0.9800
Ir1—Cl2	2.3856 (13)	C22—H22C	0.9800
N1—C1	1.352 (7)	C17'—C18'	1.41 (2)
N1—C5	1.382 (6)	C17'—H17B	0.9500
N2—C10	1.352 (6)	C18'—C19'	1.393 (16)
N2—C6	1.352 (6)	C18'—H18B	0.9500
N3—C15	1.346 (6)	C19'—C20'	1.377 (16)
N3—C11	1.374 (6)	C19'—C22'	1.516 (15)
C1—C2	1.388 (8)	C20'—C21'	1.41 (2)
C1—H1A	0.9500	C20'—H20B	0.9500
C2—C3	1.387 (9)	C21'—H21B	0.9500
C2—H2A	0.9500	C22'—H22D	0.9800
C3—C4	1.392 (8)	C22'—H22E	0.9800
C3—H3A	0.9500	C22'—H22F	0.9800
C4—C5	1.383 (7)	S1—O1	1.628 (5)
C4—H4A	0.9500	S1—C24	1.853 (5)
C5—C6	1.474 (7)	S1—C23	1.856 (5)
C6—C7	1.390 (7)	C23—H23A	0.9800
C7—C8	1.407 (7)	C23—H23B	0.9800
C7—H7A	0.9500	C23—H23C	0.9800
C8—C9	1.402 (6)	C24—H24A	0.9800
C8—C16	1.488 (6)	C24—H24B	0.9800
C9—C10	1.390 (6)	C24—H24C	0.9800
C9—H9A	0.9500	S1'—O1'	1.661 (5)
C10—C11	1.484 (6)	S1'—C23'	1.848 (5)
C11—C12	1.384 (7)	S1'—C24'	1.868 (5)
C12—C13	1.392 (7)	C23'—H23D	0.9800
C12—H12A	0.9500	C23'—H23E	0.9800
C13—C14	1.387 (7)	C23'—H23F	0.9800
C13—H13A	0.9500	C24'—H24D	0.9800
C14—C15	1.389 (8)	C24'—H24E	0.9800
C14—H14A	0.9500	C24'—H24F	0.9800
C15—H15A	0.9500	S1A—O1A	1.657 (5)
C16—C21	1.385 (11)	S1A—C23A	1.860 (5)
C16—C17	1.400 (10)	S1A—C24A	1.863 (5)
C17—C18	1.404 (17)	C23A—H23G	0.9800
C17—H17A	0.9500	C23A—H23H	0.9800
C18—C19	1.392 (12)	C23A—H23I	0.9800
C18—H18A	0.9500	C24A—H24G	0.9800
C19—C20	1.380 (11)	C24A—H24H	0.9800
C19—C22	1.516 (10)	C24A—H24I	0.9800
N2—Ir1—N1	80.67 (17)	C19—C18—C17	121.3 (10)
N2—Ir1—N3	80.79 (16)	C19—C18—H18A	119.4
N1—Ir1—N3	161.39 (16)	C17—C18—H18A	119.4
N2—Ir1—Cl1	90.43 (13)	C20—C19—C18	118.6 (9)
N1—Ir1—Cl1	89.45 (14)	C20—C19—C22	120.6 (10)
N3—Ir1—Cl1	89.14 (12)	C18—C19—C22	120.8 (10)
N2—Ir1—Cl3	88.70 (12)	C19—C20—C21	120.1 (11)
N1—Ir1—Cl3	89.75 (13)	C19—C20—H20A	119.9
N3—Ir1—Cl3	91.37 (11)	C21—C20—H20A	119.9
Cl1—Ir1—Cl3	178.90 (5)	C16—C21—C20	120.8 (16)
N2—Ir1—Cl2	178.61 (12)	C16—C21—H21A	119.6
N1—Ir1—Cl2	100.43 (12)	C20—C21—H21A	119.6
N3—Ir1—Cl2	98.13 (11)	C18'—C17'—H17B	119.8
Cl1—Ir1—Cl2	90.43 (5)	C19'—C18'—C17'	121 (2)
Cl3—Ir1—Cl2	90.46 (5)	C19'—C18'—H18B	119.6
C1—N1—C5	119.2 (5)	C17'—C18'—H18B	119.6
C1—N1—Ir1	127.6 (4)	C20'—C19'—C18'	117.1 (15)
C5—N1—Ir1	113.2 (3)	C20'—C19'—C22'	119.8 (18)
C10—N2—C6	123.3 (4)	C18'—C19'—C22'	123.1 (19)
C10—N2—Ir1	118.3 (3)	C19'—C20'—C21'	120 (2)
C6—N2—Ir1	118.4 (3)	C19'—C20'—H20B	119.9
C15—N3—C11	119.0 (4)	C21'—C20'—H20B	119.9
C15—N3—Ir1	127.8 (3)	C20'—C21'—H21B	119.6
C11—N3—Ir1	113.1 (3)	C19'—C22'—H22D	109.5
N1—C1—C2	121.0 (5)	C19'—C22'—H22E	109.5
N1—C1—H1A	119.5	H22D—C22'—H22E	109.5
C2—C1—H1A	119.5	C19'—C22'—H22F	109.5
C3—C2—C1	120.2 (5)	H22D—C22'—H22F	109.5
C3—C2—H2A	119.9	H22E—C22'—H22F	109.5
C1—C2—H2A	119.9	O1—S1—C24	107.1 (7)
C2—C3—C4	119.0 (5)	O1—S1—C23	99.8 (6)
C2—C3—H3A	120.5	C24—S1—C23	95.2 (8)
C4—C3—H3A	120.5	S1—C23—H23A	109.5
C5—C4—C3	119.4 (5)	S1—C23—H23B	109.5
C5—C4—H4A	120.3	H23A—C23—H23B	109.5
C3—C4—H4A	120.3	S1—C23—H23C	109.5
N1—C5—C4	121.2 (5)	H23A—C23—H23C	109.5
N1—C5—C6	114.7 (4)	H23B—C23—H23C	109.5
C4—C5—C6	124.1 (5)	S1—C24—H24A	109.5
N2—C6—C7	118.7 (4)	S1—C24—H24B	109.5
N2—C6—C5	113.0 (4)	H24A—C24—H24B	109.5
C7—C6—C5	128.3 (4)	S1—C24—H24C	109.5
C6—C7—C8	120.2 (4)	H24A—C24—H24C	109.5
C6—C7—H7A	119.9	H24B—C24—H24C	109.5
C8—C7—H7A	119.9	O1'—S1'—C23'	130.5 (10)
C9—C8—C7	118.7 (4)	O1'—S1'—C24'	88.2 (9)
C9—C8—C16	120.8 (4)	C23'—S1'—C24'	88.3 (12)
C7—C8—C16	120.4 (4)	S1'—C23'—H23D	109.5
C10—C9—C8	119.4 (4)	S1'—C23'—H23E	109.5
C10—C9—H9A	120.3	H23D—C23'—H23E	109.5
C8—C9—H9A	120.3	S1'—C23'—H23F	109.5
N2—C10—C9	119.6 (4)	H23D—C23'—H23F	109.5
N2—C10—C11	112.8 (4)	H23E—C23'—H23F	109.5
C9—C10—C11	127.5 (4)	S1'—C24'—H24D	109.5
N3—C11—C12	121.2 (4)	S1'—C24'—H24E	109.5
N3—C11—C10	114.8 (4)	H24D—C24'—H24E	109.5
C12—C11—C10	124.0 (4)	S1'—C24'—H24F	109.5
C11—C12—C13	119.3 (4)	H24D—C24'—H24F	109.5
C11—C12—H12A	120.3	H24E—C24'—H24F	109.5
C13—C12—H12A	120.3	O1A—S1A—C23A	108.8 (14)
C14—C13—C12	119.4 (5)	O1A—S1A—C24A	99.3 (15)
C14—C13—H13A	120.3	C23A—S1A—C24A	87.4 (14)
C12—C13—H13A	120.3	S1A—C23A—H23G	109.5
C13—C14—C15	119.0 (5)	S1A—C23A—H23H	109.5
C13—C14—H14A	120.5	H23G—C23A—H23H	109.5
C15—C14—H14A	120.5	S1A—C23A—H23I	109.5
N3—C15—C14	122.1 (4)	H23G—C23A—H23I	109.5
N3—C15—H15A	119.0	H23H—C23A—H23I	109.5
C14—C15—H15A	119.0	S1A—C24A—H24G	109.5
C21—C16—C17	118.0 (9)	S1A—C24A—H24H	109.5
C21—C16—C8	122.9 (7)	H24G—C24A—H24H	109.5
C17—C16—C8	119.1 (8)	S1A—C24A—H24I	109.5
C16—C17—C18	119.6 (14)	H24G—C24A—H24I	109.5
C16—C17—H17A	120.2	H24H—C24A—H24I	109.5
C18—C17—H17A	120.2
N2—Ir1—N1—C1	−180.0 (5)	C4—C5—C6—C7	4.4 (9)
N3—Ir1—N1—C1	175.2 (5)	N2—C6—C7—C8	0.8 (8)
Cl1—Ir1—N1—C1	89.5 (5)	C5—C6—C7—C8	179.4 (5)
Cl3—Ir1—N1—C1	−91.2 (5)	C6—C7—C8—C9	−0.8 (7)
Cl2—Ir1—N1—C1	−0.8 (5)	C6—C7—C8—C16	−178.4 (5)
N2—Ir1—N1—C5	1.1 (4)	C7—C8—C9—C10	0.7 (7)
N3—Ir1—N1—C5	−3.7 (8)	C16—C8—C9—C10	178.3 (4)
Cl1—Ir1—N1—C5	−89.4 (4)	C6—N2—C10—C9	0.4 (7)
Cl3—Ir1—N1—C5	89.8 (4)	Ir1—N2—C10—C9	−176.4 (3)
Cl2—Ir1—N1—C5	−179.7 (3)	C6—N2—C10—C11	−178.4 (4)
N1—Ir1—N2—C10	177.8 (4)	Ir1—N2—C10—C11	4.9 (5)
N3—Ir1—N2—C10	−3.8 (3)	C8—C9—C10—N2	−0.5 (7)
Cl1—Ir1—N2—C10	−92.8 (3)	C8—C9—C10—C11	178.1 (4)
Cl3—Ir1—N2—C10	87.8 (3)	C15—N3—C11—C12	0.3 (7)
N1—Ir1—N2—C6	0.9 (4)	Ir1—N3—C11—C12	−177.1 (4)
N3—Ir1—N2—C6	179.3 (4)	C15—N3—C11—C10	177.8 (4)
Cl1—Ir1—N2—C6	90.3 (4)	Ir1—N3—C11—C10	0.4 (5)
Cl3—Ir1—N2—C6	−89.1 (4)	N2—C10—C11—N3	−3.3 (6)
N2—Ir1—N3—C15	−175.5 (4)	C9—C10—C11—N3	178.1 (4)
N1—Ir1—N3—C15	−170.6 (5)	N2—C10—C11—C12	174.1 (4)
Cl1—Ir1—N3—C15	−84.9 (4)	C9—C10—C11—C12	−4.5 (8)
Cl3—Ir1—N3—C15	96.1 (4)	N3—C11—C12—C13	−1.1 (7)
Cl2—Ir1—N3—C15	5.4 (4)	C10—C11—C12—C13	−178.3 (5)
N2—Ir1—N3—C11	1.7 (3)	C11—C12—C13—C14	0.8 (8)
N1—Ir1—N3—C11	6.5 (7)	C12—C13—C14—C15	0.1 (8)
Cl1—Ir1—N3—C11	92.3 (3)	C11—N3—C15—C14	0.6 (7)
Cl3—Ir1—N3—C11	−86.8 (3)	Ir1—N3—C15—C14	177.6 (4)
Cl2—Ir1—N3—C11	−177.4 (3)	C13—C14—C15—N3	−0.8 (8)
C5—N1—C1—C2	1.9 (8)	C9—C8—C16—C21	−19 (4)
Ir1—N1—C1—C2	−177.0 (5)	C7—C8—C16—C21	158 (4)
N1—C1—C2—C3	−0.4 (10)	C9—C8—C16—C17	159 (6)
C1—C2—C3—C4	−1.5 (10)	C7—C8—C16—C17	−24 (6)
C2—C3—C4—C5	2.0 (10)	C21—C16—C17—C18	−11 (12)
C1—N1—C5—C4	−1.4 (8)	C8—C16—C17—C18	171 (6)
Ir1—N1—C5—C4	177.6 (4)	C16—C17—C18—C19	3 (12)
C1—N1—C5—C6	178.2 (5)	C17—C18—C19—C20	1 (6)
Ir1—N1—C5—C6	−2.8 (6)	C17—C18—C19—C22	−179 (6)
C3—C4—C5—N1	−0.5 (9)	C18—C19—C20—C21	3 (4)
C3—C4—C5—C6	179.9 (6)	C22—C19—C20—C21	−177 (4)
C10—N2—C6—C7	−0.5 (7)	C17—C16—C21—C20	16 (9)
Ir1—N2—C6—C7	176.2 (4)	C8—C16—C21—C20	−166 (3)
C10—N2—C6—C5	−179.3 (4)	C19—C20—C21—C16	−12 (7)
Ir1—N2—C6—C5	−2.6 (6)	C17'—C18'—C19'—C20'	17 (12)
N1—C5—C6—N2	3.5 (7)	C17'—C18'—C19'—C22'	−165 (11)
C4—C5—C6—N2	−176.9 (5)	C18'—C19'—C20'—C21'	−21 (8)
N1—C5—C6—C7	−175.2 (5)	C22'—C19'—C20'—C21'	161 (7)

(II) bis[4'-(p-tolyl)-2,2':6',2''-terpyridine]iridium(III) tris(hexafluorophosphate) acetonitrile disolvate

Crystal data

[Ir(C22H17N3)2](PF6)3·2C2H3N	F(000) = 2672
Mr = 1355.99	Dx = 1.814 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.6977 (14) Å	Cell parameters from 130 reflections
b = 16.3737 (16) Å	θ = 2.3–22.5°
c = 21.420 (2) Å	µ = 2.90 mm^−1
β = 105.639 (2)°	T = 173 K
V = 4964.0 (8) Å^3	Block, red
Z = 4	0.25 × 0.25 × 0.12 mm

Data collection

Bruker SMART Platform CCD area-detector diffractometer	4995 independent reflections
Radiation source: normal-focus sealed tube	3790 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
area detector, ω scans per ϕ	θmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	h = −15→18
Tmin = 0.531, Tmax = 0.722	k = −13→20
13655 measured reflections	l = −26→26

Refinement

Refinement on F^2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.146	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0837P)^2 + 2.2984P] where P = (Fo^2 + 2Fc^2)/3
4995 reflections	(Δ/σ)max = 0.001
355 parameters	Δρmax = 1.69 e Å^−3
0 restraints	Δρmin = −1.22 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 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.

Initially, a direct methods solution was attempted, but did not yield the correct position of the heavy atom. When a Patterson was used, the correct position of the iridium atom was chosen as that on the 2. Refinement of the remaining atoms proceeded without incident. No disorder was modeled within this structure.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ir1	1.0000	0.78757 (3)	0.7500	0.03946 (16)
N1	1.0228 (4)	0.6997 (4)	0.6876 (3)	0.0438 (14)
N2	0.8738 (4)	0.7832 (4)	0.6884 (3)	0.0409 (13)
N3	0.9313 (4)	0.8744 (4)	0.7889 (3)	0.0462 (14)
C1	1.1034 (6)	0.6607 (5)	0.6899 (4)	0.053 (2)
H1A	1.1585	0.6742	0.7232	0.064*
C2	1.1089 (7)	0.6016 (6)	0.6455 (4)	0.064 (2)
H2A	1.1663	0.5730	0.6490	0.077*
C3	1.0292 (6)	0.5844 (6)	0.5957 (4)	0.066 (2)
H3A	1.0318	0.5451	0.5636	0.079*
C4	0.9466 (6)	0.6246 (5)	0.5930 (4)	0.057 (2)
H4A	0.8915	0.6127	0.5592	0.068*
C5	0.9429 (5)	0.6817 (5)	0.6387 (3)	0.0423 (16)
C6	0.8581 (5)	0.7282 (5)	0.6401 (3)	0.0451 (18)
C7	0.7673 (5)	0.7191 (5)	0.5994 (3)	0.0457 (17)
H7A	0.7560	0.6819	0.5641	0.055*
C8	0.6938 (5)	0.7638 (5)	0.6103 (4)	0.0446 (17)
C9	0.7120 (5)	0.8207 (5)	0.6622 (3)	0.0479 (17)
H9A	0.6625	0.8522	0.6707	0.057*
C10	0.8026 (5)	0.8288 (5)	0.6994 (3)	0.0426 (16)
C11	0.8368 (5)	0.8834 (5)	0.7557 (3)	0.0465 (17)
C12	0.7806 (6)	0.9400 (5)	0.7751 (4)	0.057 (2)
H12A	0.7160	0.9455	0.7519	0.069*
C13	0.8183 (7)	0.9884 (6)	0.8281 (4)	0.074 (3)
H13A	0.7797	1.0264	0.8427	0.088*
C14	0.9137 (7)	0.9810 (6)	0.8601 (4)	0.068 (2)
H14A	0.9412	1.0151	0.8961	0.082*
C15	0.9676 (6)	0.9247 (5)	0.8397 (4)	0.057 (2)
H15A	1.0328	0.9206	0.8618	0.068*
C16	0.5961 (5)	0.7531 (5)	0.5685 (3)	0.0458 (17)
C17	0.5689 (6)	0.6807 (5)	0.5354 (4)	0.0545 (19)
H17A	0.6134	0.6375	0.5405	0.065*
C18	0.4792 (6)	0.6692 (6)	0.4953 (4)	0.057 (2)
H18A	0.4629	0.6182	0.4741	0.069*
C19	0.4123 (6)	0.7316 (6)	0.4854 (4)	0.056 (2)
C20	0.4379 (7)	0.8032 (6)	0.5192 (5)	0.068 (3)
H20A	0.3927	0.8459	0.5142	0.082*
C21	0.5277 (6)	0.8151 (6)	0.5606 (4)	0.060 (2)
H21A	0.5429	0.8651	0.5835	0.072*
C22	0.3166 (7)	0.7203 (6)	0.4391 (5)	0.070 (3)
H22A	0.2925	0.6658	0.4450	0.105*
H22B	0.3213	0.7258	0.3945	0.105*
H22C	0.2733	0.7618	0.4474	0.105*
P1	0.27840 (17)	0.48968 (15)	0.54259 (11)	0.0590 (6)
P2	0.0000	0.4395 (3)	0.7500	0.1062 (15)
F1	0.1721 (4)	0.4737 (4)	0.5422 (3)	0.0932 (19)
F2	0.2507 (4)	0.4845 (5)	0.4654 (3)	0.0939 (19)
F3	0.2608 (5)	0.5840 (4)	0.5400 (3)	0.0961 (19)
F4	0.2969 (5)	0.3937 (3)	0.5464 (3)	0.098 (2)
F5	0.3067 (4)	0.4927 (4)	0.6193 (3)	0.0856 (16)
F6	0.3841 (4)	0.5036 (4)	0.5426 (3)	0.0822 (16)
F7	0.0734 (8)	0.3731 (6)	0.7828 (7)	0.214 (6)
F8	0.0436 (7)	0.4399 (6)	0.6904 (5)	0.149 (3)
F9	0.0735 (6)	0.5094 (6)	0.7822 (4)	0.136 (3)
N7	1.3310 (11)	0.6668 (12)	0.7439 (8)	0.164 (6)
C23	1.3745 (13)	0.6745 (13)	0.7062 (9)	0.134 (5)
C24	1.444 (2)	0.6804 (16)	0.6733 (17)	0.29 (2)
H24A	1.4991	0.6478	0.6959	0.437*
H24B	1.4629	0.7377	0.6719	0.437*
H24C	1.4192	0.6599	0.6290	0.437*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.0307 (2)	0.0515 (3)	0.0351 (2)	0.000	0.00715 (14)	0.000
N1	0.043 (4)	0.052 (4)	0.039 (3)	0.005 (3)	0.015 (3)	0.004 (2)
N2	0.035 (3)	0.052 (3)	0.035 (3)	0.000 (3)	0.009 (2)	0.001 (3)
N3	0.039 (3)	0.056 (4)	0.044 (3)	−0.005 (3)	0.011 (3)	−0.008 (3)
C1	0.040 (5)	0.067 (6)	0.051 (4)	0.011 (4)	0.008 (3)	−0.001 (4)
C2	0.058 (6)	0.073 (6)	0.062 (5)	0.012 (5)	0.019 (4)	−0.001 (4)
C3	0.059 (6)	0.081 (6)	0.056 (5)	0.012 (5)	0.014 (4)	−0.014 (4)
C4	0.052 (5)	0.066 (5)	0.051 (4)	0.002 (4)	0.009 (4)	−0.010 (4)
C5	0.037 (4)	0.047 (4)	0.044 (4)	−0.003 (3)	0.012 (3)	−0.005 (3)
C6	0.037 (4)	0.059 (5)	0.039 (3)	0.001 (3)	0.011 (3)	0.002 (3)
C7	0.042 (4)	0.053 (4)	0.041 (3)	−0.003 (4)	0.009 (3)	−0.004 (3)
C8	0.036 (4)	0.049 (4)	0.047 (4)	0.001 (3)	0.007 (3)	0.000 (3)
C9	0.039 (4)	0.058 (4)	0.045 (4)	0.005 (4)	0.008 (3)	0.003 (3)
C10	0.034 (4)	0.053 (4)	0.041 (3)	0.001 (3)	0.010 (3)	−0.001 (3)
C11	0.036 (4)	0.056 (5)	0.047 (4)	0.002 (3)	0.010 (3)	0.003 (3)
C12	0.048 (5)	0.064 (5)	0.055 (4)	0.011 (4)	0.006 (4)	−0.005 (4)
C13	0.069 (6)	0.080 (7)	0.066 (5)	0.020 (5)	0.010 (5)	−0.017 (5)
C14	0.067 (6)	0.072 (6)	0.059 (5)	0.004 (5)	0.005 (4)	−0.019 (4)
C15	0.057 (5)	0.057 (5)	0.053 (4)	0.002 (4)	0.010 (4)	−0.001 (4)
C16	0.039 (4)	0.055 (4)	0.042 (4)	0.002 (4)	0.010 (3)	−0.002 (3)
C17	0.043 (5)	0.058 (5)	0.064 (5)	0.002 (4)	0.018 (4)	0.003 (4)
C18	0.051 (5)	0.065 (5)	0.054 (4)	−0.006 (4)	0.011 (4)	−0.005 (4)
C19	0.041 (5)	0.074 (6)	0.049 (4)	−0.010 (4)	0.006 (3)	0.000 (4)
C20	0.049 (5)	0.078 (7)	0.070 (5)	0.008 (4)	0.003 (4)	0.002 (5)
C21	0.042 (5)	0.073 (6)	0.059 (5)	−0.001 (4)	0.005 (4)	−0.006 (4)
C22	0.043 (5)	0.092 (7)	0.065 (5)	−0.007 (5)	−0.003 (4)	0.000 (5)
P1	0.0525 (14)	0.0614 (14)	0.0622 (12)	0.0032 (11)	0.0139 (10)	−0.0025 (10)
P2	0.095 (4)	0.098 (3)	0.135 (4)	0.000	0.049 (3)	0.000
F1	0.056 (3)	0.123 (5)	0.107 (4)	−0.012 (3)	0.034 (3)	−0.038 (4)
F2	0.084 (4)	0.137 (6)	0.058 (3)	−0.006 (4)	0.014 (3)	−0.005 (3)
F3	0.102 (5)	0.066 (4)	0.114 (5)	0.016 (3)	0.017 (4)	0.006 (3)
F4	0.141 (6)	0.057 (3)	0.126 (5)	0.011 (3)	0.088 (5)	0.003 (3)
F5	0.087 (4)	0.101 (4)	0.066 (3)	0.017 (3)	0.016 (3)	−0.001 (3)
F6	0.058 (3)	0.094 (4)	0.093 (4)	0.001 (3)	0.016 (3)	0.020 (3)
F7	0.164 (9)	0.158 (9)	0.350 (17)	0.085 (7)	0.122 (10)	0.122 (10)
F8	0.154 (8)	0.164 (8)	0.162 (8)	0.012 (6)	0.097 (7)	−0.027 (6)
F9	0.110 (6)	0.159 (7)	0.142 (7)	−0.041 (6)	0.039 (5)	−0.018 (5)
N7	0.124 (12)	0.230 (17)	0.150 (13)	−0.003 (12)	0.058 (10)	−0.022 (13)
C23	0.118 (13)	0.159 (14)	0.130 (13)	0.004 (12)	0.044 (11)	−0.001 (12)
C24	0.35 (4)	0.19 (2)	0.47 (5)	−0.06 (2)	0.35 (4)	−0.05 (3)

Geometric parameters (Å, º)

Ir1—N2^i	1.966 (6)	C14—C15	1.362 (12)
Ir1—N2	1.966 (6)	C14—H14A	0.9500
Ir1—N3	2.047 (6)	C15—H15A	0.9500
Ir1—N3^i	2.047 (6)	C16—C17	1.383 (12)
Ir1—N1	2.052 (6)	C16—C21	1.406 (12)
Ir1—N1^i	2.052 (6)	C17—C18	1.378 (12)
N1—C1	1.335 (10)	C17—H17A	0.9500
N1—C5	1.378 (9)	C18—C19	1.393 (12)
N2—C6	1.345 (9)	C18—H18A	0.9500
N2—C10	1.356 (9)	C19—C20	1.376 (12)
N3—C15	1.355 (10)	C19—C22	1.499 (12)
N3—C11	1.386 (9)	C20—C21	1.391 (12)
C1—C2	1.374 (12)	C20—H20A	0.9500
C1—H1A	0.9500	C21—H21A	0.9500
C2—C3	1.384 (12)	C22—H22A	0.9800
C2—H2A	0.9500	C22—H22B	0.9800
C3—C4	1.368 (12)	C22—H22C	0.9800
C3—H3A	0.9500	P1—F3	1.565 (6)
C4—C5	1.365 (10)	P1—F6	1.571 (6)
C4—H4A	0.9500	P1—F1	1.582 (6)
C5—C6	1.468 (11)	P1—F5	1.584 (6)
C6—C7	1.391 (11)	P1—F4	1.593 (6)
C7—C8	1.377 (10)	P1—F2	1.594 (6)
C7—H7A	0.9500	P2—F7	1.559 (9)
C8—C9	1.418 (11)	P2—F7^ii	1.559 (10)
C8—C16	1.483 (10)	P2—F8^ii	1.575 (8)
C9—C10	1.361 (10)	P2—F8	1.575 (8)
C9—H9A	0.9500	P2—F9	1.597 (9)
C10—C11	1.476 (10)	P2—F9^ii	1.597 (8)
C11—C12	1.380 (11)	N7—C23	1.16 (2)
C12—C13	1.371 (12)	C23—C24	1.39 (2)
C12—H12A	0.9500	C24—H24A	0.9800
C13—C14	1.390 (13)	C24—H24B	0.9800
C13—H13A	0.9500	C24—H24C	0.9800
N2^i—Ir1—N2	175.8 (3)	C13—C14—H14A	120.1
N2^i—Ir1—N3	103.4 (2)	N3—C15—C14	122.1 (8)
N2—Ir1—N3	79.5 (2)	N3—C15—H15A	119.0
N2^i—Ir1—N3^i	79.5 (2)	C14—C15—H15A	119.0
N2—Ir1—N3^i	103.4 (2)	C17—C16—C21	117.2 (7)
N3—Ir1—N3^i	92.0 (3)	C17—C16—C8	120.7 (7)
N2^i—Ir1—N1	97.0 (2)	C21—C16—C8	122.1 (7)
N2—Ir1—N1	80.1 (2)	C18—C17—C16	122.2 (8)
N3—Ir1—N1	159.6 (2)	C18—C17—H17A	118.9
N3^i—Ir1—N1	92.1 (2)	C16—C17—H17A	118.9
N2^i—Ir1—N1^i	80.1 (2)	C17—C18—C19	120.8 (8)
N2—Ir1—N1^i	97.0 (2)	C17—C18—H18A	119.6
N3—Ir1—N1^i	92.1 (2)	C19—C18—H18A	119.6
N3^i—Ir1—N1^i	159.6 (2)	C20—C19—C18	117.6 (8)
N1—Ir1—N1^i	90.9 (3)	C20—C19—C22	121.9 (8)
C1—N1—C5	119.4 (6)	C18—C19—C22	120.5 (8)
C1—N1—Ir1	127.6 (5)	C19—C20—C21	122.2 (9)
C5—N1—Ir1	113.0 (5)	C19—C20—H20A	118.9
C6—N2—C10	121.4 (6)	C21—C20—H20A	118.9
C6—N2—Ir1	118.4 (5)	C20—C21—C16	120.0 (9)
C10—N2—Ir1	119.8 (5)	C20—C21—H21A	120.0
C15—N3—C11	118.1 (7)	C16—C21—H21A	120.0
C15—N3—Ir1	128.2 (6)	C19—C22—H22A	109.5
C11—N3—Ir1	113.6 (5)	C19—C22—H22B	109.5
N1—C1—C2	121.9 (8)	H22A—C22—H22B	109.5
N1—C1—H1A	119.0	C19—C22—H22C	109.5
C2—C1—H1A	119.0	H22A—C22—H22C	109.5
C1—C2—C3	118.8 (8)	H22B—C22—H22C	109.5
C1—C2—H2A	120.6	F3—P1—F6	90.6 (4)
C3—C2—H2A	120.6	F3—P1—F1	90.5 (4)
C4—C3—C2	119.4 (8)	F6—P1—F1	178.8 (4)
C4—C3—H3A	120.3	F3—P1—F5	90.0 (3)
C2—C3—H3A	120.3	F6—P1—F5	90.7 (3)
C5—C4—C3	120.4 (8)	F1—P1—F5	89.6 (3)
C5—C4—H4A	119.8	F3—P1—F4	179.1 (4)
C3—C4—H4A	119.8	F6—P1—F4	89.3 (4)
C4—C5—N1	120.1 (7)	F1—P1—F4	89.5 (4)
C4—C5—C6	124.6 (7)	F5—P1—F4	89.1 (3)
N1—C5—C6	115.3 (6)	F3—P1—F2	91.3 (4)
N2—C6—C7	119.4 (7)	F6—P1—F2	89.1 (3)
N2—C6—C5	113.1 (6)	F1—P1—F2	90.6 (3)
C7—C6—C5	127.5 (7)	F5—P1—F2	178.7 (4)
C8—C7—C6	120.1 (7)	F4—P1—F2	89.6 (4)
C8—C7—H7A	120.0	F7—P2—F7^ii	91.6 (11)
C6—C7—H7A	120.0	F7—P2—F8^ii	91.2 (6)
C7—C8—C9	119.4 (7)	F7^ii—P2—F8^ii	89.1 (6)
C7—C8—C16	120.7 (7)	F7—P2—F8	89.1 (6)
C9—C8—C16	120.0 (7)	F7^ii—P2—F8	91.2 (6)
C10—C9—C8	118.1 (7)	F8^ii—P2—F8	179.5 (8)
C10—C9—H9A	120.9	F7—P2—F9	90.0 (6)
C8—C9—H9A	120.9	F7^ii—P2—F9	178.4 (8)
N2—C10—C9	121.6 (7)	F8^ii—P2—F9	91.3 (5)
N2—C10—C11	111.5 (6)	F8—P2—F9	88.4 (5)
C9—C10—C11	126.9 (7)	F7—P2—F9^ii	178.4 (8)
C12—C11—N3	121.0 (7)	F7^ii—P2—F9^ii	90.0 (6)
C12—C11—C10	123.7 (7)	F8^ii—P2—F9^ii	88.4 (5)
N3—C11—C10	115.3 (6)	F8—P2—F9^ii	91.3 (5)
C13—C12—C11	119.8 (8)	F9—P2—F9^ii	88.4 (7)
C13—C12—H12A	120.1	N7—C23—C24	167 (3)
C11—C12—H12A	120.1	C23—C24—H24A	109.5
C12—C13—C14	119.1 (8)	C23—C24—H24B	109.5
C12—C13—H13A	120.4	H24A—C24—H24B	109.5
C14—C13—H13A	120.4	C23—C24—H24C	109.5
C15—C14—C13	119.9 (8)	H24A—C24—H24C	109.5
C15—C14—H14A	120.1	H24B—C24—H24C	109.5
N2^i—Ir1—N1—C1	−4.8 (7)	N1—C5—C6—N2	2.1 (9)
N2—Ir1—N1—C1	178.1 (7)	C4—C5—C6—C7	4.9 (13)
N3—Ir1—N1—C1	176.5 (7)	N1—C5—C6—C7	−175.8 (7)
N3^i—Ir1—N1—C1	74.9 (7)	N2—C6—C7—C8	−2.5 (11)
N1^i—Ir1—N1—C1	−84.9 (6)	C5—C6—C7—C8	175.2 (7)
N2^i—Ir1—N1—C5	175.3 (5)	C6—C7—C8—C9	1.7 (11)
N2—Ir1—N1—C5	−1.7 (5)	C6—C7—C8—C16	−178.4 (7)
N3—Ir1—N1—C5	−3.4 (9)	C7—C8—C9—C10	0.1 (11)
N3^i—Ir1—N1—C5	−104.9 (5)	C16—C8—C9—C10	−179.9 (7)
N1^i—Ir1—N1—C5	95.2 (5)	C6—N2—C10—C9	0.3 (11)
N3—Ir1—N2—C6	−177.6 (6)	Ir1—N2—C10—C9	−172.4 (6)
N3^i—Ir1—N2—C6	92.9 (5)	C6—N2—C10—C11	178.8 (6)
N1—Ir1—N2—C6	3.0 (5)	Ir1—N2—C10—C11	6.1 (8)
N1^i—Ir1—N2—C6	−86.7 (5)	C8—C9—C10—N2	−1.1 (11)
N3—Ir1—N2—C10	−4.6 (5)	C8—C9—C10—C11	−179.4 (7)
N3^i—Ir1—N2—C10	−94.2 (6)	C15—N3—C11—C12	−2.2 (11)
N1—Ir1—N2—C10	176.0 (6)	Ir1—N3—C11—C12	−179.3 (6)
N1^i—Ir1—N2—C10	86.3 (6)	C15—N3—C11—C10	177.8 (7)
N2^i—Ir1—N3—C15	8.2 (7)	Ir1—N3—C11—C10	0.7 (8)
N2—Ir1—N3—C15	−174.8 (7)	N2—C10—C11—C12	175.8 (7)
N3^i—Ir1—N3—C15	−71.6 (6)	C9—C10—C11—C12	−5.8 (13)
N1—Ir1—N3—C15	−173.2 (6)	N2—C10—C11—N3	−4.2 (9)
N1^i—Ir1—N3—C15	88.5 (7)	C9—C10—C11—N3	174.3 (7)
N2^i—Ir1—N3—C11	−175.1 (5)	N3—C11—C12—C13	0.0 (13)
N2—Ir1—N3—C11	1.9 (5)	C10—C11—C12—C13	−180.0 (8)
N3^i—Ir1—N3—C11	105.2 (5)	C11—C12—C13—C14	2.0 (15)
N1—Ir1—N3—C11	3.6 (10)	C12—C13—C14—C15	−1.8 (15)
N1^i—Ir1—N3—C11	−94.8 (5)	C11—N3—C15—C14	2.4 (12)
C5—N1—C1—C2	−1.4 (12)	Ir1—N3—C15—C14	179.0 (7)
Ir1—N1—C1—C2	178.8 (6)	C13—C14—C15—N3	−0.5 (14)
N1—C1—C2—C3	2.6 (13)	C7—C8—C16—C17	24.9 (11)
C1—C2—C3—C4	−2.1 (14)	C9—C8—C16—C17	−155.1 (7)
C2—C3—C4—C5	0.6 (14)	C7—C8—C16—C21	−155.2 (8)
C3—C4—C5—N1	0.5 (12)	C9—C8—C16—C21	24.8 (11)
C3—C4—C5—C6	179.9 (8)	C21—C16—C17—C18	1.2 (12)
C1—N1—C5—C4	−0.2 (11)	C8—C16—C17—C18	−178.9 (7)
Ir1—N1—C5—C4	179.7 (6)	C16—C17—C18—C19	1.2 (13)
C1—N1—C5—C6	−179.5 (7)	C17—C18—C19—C20	−2.7 (12)
Ir1—N1—C5—C6	0.3 (8)	C17—C18—C19—C22	176.8 (8)
C10—N2—C6—C7	1.5 (10)	C18—C19—C20—C21	1.8 (14)
Ir1—N2—C6—C7	174.4 (5)	C22—C19—C20—C21	−177.7 (9)
C10—N2—C6—C5	−176.5 (6)	C19—C20—C21—C16	0.6 (14)
Ir1—N2—C6—C5	−3.7 (8)	C17—C16—C21—C20	−2.1 (12)
C4—C5—C6—N2	−177.3 (7)	C8—C16—C21—C20	178.0 (8)

Symmetry codes: (i) −x+2, y, −z+3/2; (ii) −x, y, −z+3/2.