mer-Bis[2-(1,3-benzothiazol-2-yl)phenyl-κ2C1,N][3-phenyl-5-(2-pyridyl)-1,2,4-triazol-1-ido-κ2N1,N5]iridium(III) deuterochloro­form 3.5-solvate

Jones, P.G.; Freund, A.; Weinkauf, A.; Kowalsky, W.; Johannes, H.-H.

doi:10.1107/S1600536810031624

mer-Bis[2-(1,3-benzothiazol-2-yl)phenyl-κ²C¹,N][3-phenyl-5-(2-pyridyl)-1,2,4-triazol-1-ido-κ²N¹,N⁵]iridium(III) deuterochloroform 3.5-solvate

P. G. Jones, A. Freund, A. Weinkauf, W. Kowalsky and H.-H. Johannes

In the title compound, [Ir(C₁₃H₉N₄)(C₁₃H₈NS)₂]·3.5CDCl₃, the coordination at iridium is octahedral, but with narrow ligand bite angles. The bond lengths at iridium show the expected trans influence, with the Ir—N bonds trans to C being appreciably longer than those trans to N. The chelate rings are mutually perpendicular, the interplanar angles between them all lying within 6° of 90°. All ligands are approximately planar; the maximum interplanar angles within ligands are ca 10°. The three ordered deuterochloroform molecules are all involved in C

D—A contacts that can be interpreted as hydrogen bonds of various types. The fourth deuterochloroform is disordered over an inversion centre.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810031624/bt5321sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810031624/bt5321Isup2.hkl Contains datablock I

CCDC reference: 792263

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.004 Å
Disorder in solvent or counterion
R factor = 0.027
wR factor = 0.047
Data-to-parameter ratio = 23.4

checkCIF/PLATON results

No syntax errors found



Alert level B
CHEMS01_ALERT_1_B  The sum formula contains elements in the wrong order.
            D  precedes Cl
            Sequence must be C, H, then alphabetical.

Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          5
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          5
PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.75 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.77 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.67 eA-3
PLAT973_ALERT_2_C Large Calcd. Positive Residual Density on     Ir       1.04 eA-3
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ          ?
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of         C98
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of         C99
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of         C96
PLAT480_ALERT_4_C Long H...A H-Bond Reported D98    ..  S3'     ..       3.04 Ang.
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........    CG(C27-
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C H Cl3
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              C H Cl3
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              C H Cl3
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        232

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C42.5 H25 Cl10.5 D3.5 Ir1 N6 S
            Atom count from the _atom_site data:  C42.5 H28.5 Cl10.5 Ir1 N6 S2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: Large difference may be due to a
            symmetry error - see SYMMG tests
           From the CIF: _cell_formula_units_Z    2
           From the CIF: _chemical_formula_sum  C42.5 H25 D3.5 Cl10.5 Ir N6 S2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         85.00     85.00    0.00
           H         50.00     57.00   -7.00
           D          7.00      0.00    7.00
           Cl        21.00     21.00    0.00
           Ir         2.00      2.00    0.00
           N         12.00     12.00    0.00
           S          4.00      4.00    0.00
PLAT431_ALERT_2_G Short Inter HL..A Contact  Cl5    ..  Cl11    ..       3.22 Ang.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          6
PLAT153_ALERT_1_G The su's on the Cell Axes   are Equal (x 100000)         40 Ang.
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        300 Deg.
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................      13.00 Perc.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          3

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  19 ALERT level C = Check and explain
   9 ALERT level G = General alerts; check

   9 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
  11 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Organometallic phosphorescent materials based on iridium(III) play an important role in the field of organic light-emitting diodes (OLEDs). They exhibit high quantum efficiencies, relatively short phosphorescent lifetimes, and facile colour tuning by modification of the ligand structures. Moreover, this class of materials can lead to OLEDs with 100% internal quantum efficiencies by harvesting both singlet and triplet excitons. In this contribution, we have synthesized and characterized a new iridium(III) complex with two 2-phenylbenzothiazoles as chromophoric ligands and 3-phenyl-5-(2-pyridine)-1,2,4-triazole as ancillary ligand, and report here the crystal structure of this compound.

The structure of the title complex is shown in Fig. 1. It crystallizes with four molecules of deuterochloroform, one of which is disordered cleanly over an inversion centre. The coordination at iridium is octahedral, with the major deviations in angles arising from the restricted bite of the chelating ligands: N1—Ir—C11 79.54 (9), N1'—Ir—C11' 79.98 (9), N16—Ir—N22 76.03 (8)°. The bond lengths at iridium show the expected trans influence, with Ir—N16 and Ir—N22, 2.126 (2) and 2.160 (2) Å respectively, trans to C being appreciably longer than the mutually trans Ir—N1 2.060 (2) and Ir—N1' 2.064 (2) Å. The interplanar angles between the chelate rings all lie within 6° of 90°. Within the ligands, the interplanar angles between phenyl and benzothiazole are 9.9 (1) and 10.8 (1)°, whereas in the triazole ligand the pyridyl and phenyl rings subtend angles of 0.4 (2) and 9.2 (2)° respectively to the triazole ring.

The three ordered deuterochloroform molecules are all involved in C···D—A contacts that can be interpreted as hydrogen bonds of various types (Table 1); D99···N19 2.18, D98···S3' 3.04 (but with a narrow angle of 121°), D97···Cg(C27–C32) 2.50 Å.

Related literature top

For the preparation of iridium complexes, see: Lamansky et al. (2001); Tamayo et al. (2003). For the photoluminescent properties and color tuning of cyclometalated iridium complexes, see: Grushin et al. (2001); Kwon et al. (2005); You & Park (2005). For general background to organic light-emitting diodes (OLEDs), see: Holder et al. (2005); Kappaun et al. (2008). For a related recent publication from our groups, see Jones et al. (2010).

Experimental top

A mixture of bis(2-phenylbenzo[d]thiazole)-iridium(III)-µ-chloro bridged dimer (300 mg, 231 µmol), 3-phenyl-5-(2-pyridyl)-1,2,4-triazole (129 mg, 579 µmol) and potassium tert-butoxide (65 mg, 579 µmol) in dry dichloromethane (10 ml) and dry ethanol (3 ml) was stirred overnight at room temperature under nitrogen atmosphere. The solvent was then removed under reduced pressure and the residue was purified via flash-chromatography on silica gel (eluent: dichloromethane/acetone = 10: 1, R_f = 0.57) to yield an orange solid (299 mg, 77%). m.p. 306 °C.

- ¹H NMR (CDCl₃, 600 MHz): δ = 8.22 (d, J = 7.9 Hz, 1H), 8.13–8.11 (m, 2H), 7.83 (ddd, J = 5.5, 1.5, 0.9 Hz, 1H), 7.80 (ddd, J = 7.8, 7.8, 1.6 Hz, 1H), 7.78–7.77 (m, 1H), 7.75–7.73 (m, 3H), 7.34–7.31 (m, 2H), 7.27–7.23 (m, 2H), 7.21 (ddd, J = 8.2, 7.3, 1.0 Hz, 1H), 7.13–7.10 (m, 2H), 7.02 (ddd, J = 7.5, 7.5, 1.1 Hz, 1H), 6.99 (ddd, J = 7.5, 7.5, 1.1 Hz, 1H), 6.97 (d, J = 8.4 Hz, 1H), 6.93 (ddd, J = 8.5, 7.3, 1.2 Hz, 1H), 6.83 (ddd, J = 7.5, 7.5, 1.3 Hz, 1H), 6.80 (ddd, J = 7.5, 7.5, 1.4 Hz, 1H), 6.54 (d, J = 7.4 Hz, 1H), 6.48 (dd, J = 7.7, 0.4 Hz, 1H), 6.23 (d, J = 8.4 Hz, 1H) p.p.m..

- ¹³C NMR (CDCl₃, 150 MHz): δ = 180.96, 180.35, 165.06, 163.63, 154.92, 152.95, 149.80, 149.75, 149.71, 149.60, 141.22, 140.77, 138.27, 134.18, 133.52, 132.93, 131.43, 131.37, 130.93, 130.83, 128.32, 128.21, 127.66, 127.02, 126.20, 126.04, 125.94, 125.46, 124.89, 123.84, 122.94, 122.15, 122.10, 121.73, 121.16, 120.36, 118.04 p.p.m..

- EI—MS: m/z (%) = 834 (100) [M⁺], 756 (9), 613 (35), 286 (12), 211 (41).

- IR: ν-tilde = 3055 (w), 1606 (w), 1581 (w), 1436 (m), 1408 (m), 1322 (w), 1297 (w), 1266 (m), 1157 (w), 1024 (m), 993 (m), 791 (w), 752 (s), 723 (versus), 696 (m), 582 (w) cm^-1.

- UV/Vis (CH₂Cl₂): λ (ε [cm^-1M^-1]) = 228 (47000), 272 (45500), 310 (36600), 323 (35600), 350 (15400), 383 (9400), 454 (4200) nm.

- Elemental analysis: calculated for C₃₉H₂₅IrN₆S₂: C 56.16, H 3.02, N 10.08, S 7.69%; found: C 56.29, H 3.02, N 10.39 S 7.47%.

Single crystals were obtained by evaporation from CDCl₃ in an NMR tube.

Structure description top

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Structure of the title compound in the crystal. Ellipsoids represent 50% probability levels. Solvent molecules and hydrogen atoms are omitted for clarity.

mer-Bis[2-(1,3-benzothiazol-2-yl)phenyl-κ²C¹,N]{3- phenyl-5-(2-pyridyl)-1,2,4-triazol-1-ido- κ²N¹,N⁵}iridium(III) deuterochloroform 3.5-solvate top

Crystal data top

[Ir(C₁₃H₉N₄)(C₁₃H₈NS)₂]·3.5CDCl₃	Z = 2
M_r = 1254.78	F(000) = 1226
Triclinic, P1	D_x = 1.785 Mg m⁻³
a = 11.7521 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.5592 (4) Å	Cell parameters from 31145 reflections
c = 15.8373 (4) Å	θ = 2.2–30.8°
α = 74.045 (3)°	µ = 3.59 mm⁻¹
β = 79.247 (3)°	T = 100 K
γ = 76.002 (3)°	Prism, orange
V = 2334.80 (12) Å³	0.20 × 0.10 × 0.08 mm

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	13407 independent reflections
Radiation source: fine-focus sealed tube	10433 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
Detector resolution: 16.1419 pixels mm^-1	θ_max = 30.0°, θ_min = 2.2°
ω–scan	h = −16→16
Absorption correction: multi-scan CrysAlis PRO, Oxford Diffraction (2010).	k = −19→18
T_min = 0.902, T_max = 1.000	l = −22→22
94997 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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.047	H-atom parameters constrained
S = 0.88	w = 1/[σ²(F_o²) + (0.0175P)²] where P = (F_o² + 2F_c²)/3
13407 reflections	(Δ/σ)_max = 0.002
572 parameters	Δρ_max = 1.88 e Å⁻³
6 restraints	Δρ_min = −1.70 e Å⁻³

Crystal data top

[Ir(C₁₃H₉N₄)(C₁₃H₈NS)₂]·3.5CDCl₃	γ = 76.002 (3)°
M_r = 1254.78	V = 2334.80 (12) Å³
Triclinic, P1	Z = 2
a = 11.7521 (4) Å	Mo Kα radiation
b = 13.5592 (4) Å	µ = 3.59 mm⁻¹
c = 15.8373 (4) Å	T = 100 K
α = 74.045 (3)°	0.20 × 0.10 × 0.08 mm
β = 79.247 (3)°

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	13407 independent reflections
Absorption correction: multi-scan CrysAlis PRO, Oxford Diffraction (2010).	10433 reflections with I > 2σ(I)
T_min = 0.902, T_max = 1.000	R_int = 0.058
94997 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	6 restraints
wR(F²) = 0.047	H-atom parameters constrained
S = 0.88	Δρ_max = 1.88 e Å⁻³
13407 reflections	Δρ_min = −1.70 e Å⁻³
572 parameters

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

7.9800 (0.0061) x - 1.7224 (0.0133) y + 10.9969 (0.0085) z = 7.6717 (0.0069)

* -0.0488 (0.0009) Ir * 0.0413 (0.0012) N1 * -0.0066 (0.0014) C2 * -0.0540 (0.0015) C10 * 0.0680 (0.0013) C11

Rms deviation of fitted atoms = 0.0483

8.3461 (0.0059) x + 9.9411 (0.0076) y - 1.7893 (0.0166) z = 2.3716 (0.0114)

Angle to previous plane (with approximate e.s.d.) = 87.72 (0.06)

* -0.0493 (0.0009) Ir * 0.0551 (0.0013) N1' * -0.0297 (0.0015) C2' * -0.0327 (0.0016) C10' * 0.0566 (0.0013) C11'

Rms deviation of fitted atoms = 0.0461

- 2.3439 (0.0116) x + 9.9572 (0.0069) y + 10.8389 (0.0095) z = 7.7705 (0.0077)

Angle to previous plane (with approximate e.s.d.) = 84.16 (0.06)

* -0.0054 (0.0009) Ir * 0.0091 (0.0014) N16 * -0.0083 (0.0016) C20 * 0.0006 (0.0016) C21 * 0.0041 (0.0013) N22

Rms deviation of fitted atoms = 0.0063

7.9800 (0.0061) x - 1.7224 (0.0133) y + 10.9969 (0.0085) z = 7.6717 (0.0069)

Angle to previous plane (with approximate e.s.d.) = 89.73 (0.07)

* -0.0488 (0.0009) Ir * 0.0413 (0.0012) N1 * -0.0066 (0.0014) C2 * -0.0540 (0.0015) C10 * 0.0680 (0.0013) C11

Rms deviation of fitted atoms = 0.0483

8.2788 (0.0045) x - 0.5241 (0.0062) y + 11.4855 (0.0070) z = 8.1544 (0.0022)

Angle to previous plane (with approximate e.s.d.) = 5.08 (0.10)

* 0.0042 (0.0016) N1 * 0.0078 (0.0016) C2 * -0.0070 (0.0011) S3 * -0.0048 (0.0020) C4 * -0.0050 (0.0020) C5 * -0.0049 (0.0018) C6 * 0.0005 (0.0018) C7 * 0.0043 (0.0018) C8 * 0.0049 (0.0017) C9

Rms deviation of fitted atoms = 0.0052

8.4858 (0.0077) x - 2.4161 (0.0127) y + 9.6572 (0.0118) z = 7.0197 (0.0090)

Angle to previous plane (with approximate e.s.d.) = 9.93 (0.11)

* 0.0136 (0.0016) C10 * -0.0217 (0.0016) C11 * 0.0118 (0.0016) C12 * 0.0070 (0.0017) C13 * -0.0158 (0.0017) C14 * 0.0052 (0.0017) C15

Rms deviation of fitted atoms = 0.0137

7.1925 (0.0056) x + 9.8261 (0.0068) y - 3.8421 (0.0083) z = 0.9988 (0.0081)

Angle to previous plane (with approximate e.s.d.) = 85.34 (0.06)

* -0.0364 (0.0018) N1' * 0.0610 (0.0017) C2' * 0.0364 (0.0013) S3' * -0.0552 (0.0023) C4' * -0.0535 (0.0022) C5' * 0.0058 (0.0021) C6' * 0.0512 (0.0022) C7' * 0.0250 (0.0022) C8' * -0.0342 (0.0021) C9'

Rms deviation of fitted atoms = 0.0431

8.1235 (0.0081) x + 10.5535 (0.0086) y - 0.9454 (0.0159) z = 2.9872 (0.0090)

Angle to previous plane (with approximate e.s.d.) = 10.83 (0.12)

* 0.0050 (0.0017) C10' * 0.0034 (0.0017) C11' * -0.0084 (0.0018) C12' * 0.0049 (0.0018) C13' * 0.0036 (0.0018) C14' * -0.0084 (0.0017) C15'

Rms deviation of fitted atoms = 0.0060

- 2.5414 (0.0127) x + 9.7359 (0.0101) y + 10.9194 (0.0127) z = 7.8052 (0.0089)

Angle to previous plane (with approximate e.s.d.) = 81.42 (0.07)

* 0.0037 (0.0018) C21 * -0.0086 (0.0016) N22 * 0.0048 (0.0018) C23 * 0.0039 (0.0020) C24 * -0.0087 (0.0020) C25 * 0.0048 (0.0019) C26

Rms deviation of fitted atoms = 0.0061

- 2.5107 (0.0151) x + 9.8045 (0.0109) y + 10.8623 (0.0148) z = 7.7407 (0.0143)

Angle to previous plane (with approximate e.s.d.) = 0.43 (0.17)

* -0.0022 (0.0014) N16 * 0.0011 (0.0014) N17 * 0.0003 (0.0015) C18 * -0.0016 (0.0014) N19 * 0.0024 (0.0015) C20

Rms deviation of fitted atoms = 0.0017

- 2.4518 (0.0127) x + 10.9099 (0.0091) y + 9.0926 (0.0145) z = 6.2049 (0.0171)

Angle to previous plane (with approximate e.s.d.) = 9.27 (0.16)

* 0.0117 (0.0018) C27 * -0.0068 (0.0019) C28 * -0.0042 (0.0019) C29 * 0.0103 (0.0019) C30 * -0.0052 (0.0019) C31 * -0.0058 (0.0019) C32

Rms deviation of fitted atoms = 0.0078

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)
Ir	0.185225 (9)	0.183852 (9)	0.587566 (7)	0.01036 (3)
N1	0.29011 (17)	0.09344 (16)	0.50550 (13)	0.0113 (5)
C2	0.3713 (2)	0.1390 (2)	0.44934 (16)	0.0113 (5)
S3	0.46148 (5)	0.06657 (5)	0.37977 (4)	0.01364 (13)
C4	0.3867 (2)	−0.0356 (2)	0.42917 (16)	0.0115 (5)
C5	0.2971 (2)	−0.00772 (19)	0.49503 (16)	0.0115 (5)
C6	0.2262 (2)	−0.0791 (2)	0.54288 (16)	0.0150 (6)
H6	0.1647	−0.0615	0.5877	0.018*
C7	0.2476 (2)	−0.1758 (2)	0.52351 (17)	0.0158 (6)
H7	0.2001	−0.2250	0.5556	0.019*
C8	0.3378 (2)	−0.2028 (2)	0.45764 (16)	0.0153 (6)
H8	0.3504	−0.2698	0.4457	0.018*
C9	0.4085 (2)	−0.1336 (2)	0.40982 (16)	0.0135 (5)
H9	0.4701	−0.1519	0.3652	0.016*
C10	0.3802 (2)	0.24172 (19)	0.45468 (16)	0.0118 (5)
C11	0.3038 (2)	0.2743 (2)	0.52632 (16)	0.0120 (5)
C12	0.3162 (2)	0.3678 (2)	0.54230 (17)	0.0145 (6)
H12	0.2699	0.3914	0.5916	0.017*
C13	0.3950 (2)	0.4261 (2)	0.48715 (18)	0.0179 (6)
H13	0.4009	0.4895	0.4991	0.022*
C14	0.4655 (2)	0.3945 (2)	0.41489 (18)	0.0181 (6)
H14	0.5173	0.4366	0.3768	0.022*
C15	0.4593 (2)	0.3009 (2)	0.39911 (17)	0.0163 (6)
H15	0.5084	0.2770	0.3509	0.020*
N16	0.26737 (17)	0.08428 (16)	0.69814 (13)	0.0120 (5)
N17	0.36908 (17)	0.07191 (16)	0.73312 (13)	0.0133 (5)
C18	0.3628 (2)	−0.0086 (2)	0.80427 (16)	0.0143 (5)
N19	0.26461 (18)	−0.04920 (17)	0.81804 (13)	0.0151 (5)
C20	0.2083 (2)	0.0125 (2)	0.74975 (16)	0.0125 (5)
C21	0.0947 (2)	0.0096 (2)	0.72860 (16)	0.0138 (5)
N22	0.06182 (18)	0.08334 (16)	0.65410 (13)	0.0129 (5)
C23	−0.0419 (2)	0.0868 (2)	0.62811 (17)	0.0157 (6)
H23	−0.0659	0.1387	0.5772	0.019*
C24	−0.1149 (2)	0.0181 (2)	0.67229 (19)	0.0225 (6)
H24	−0.1876	0.0227	0.6520	0.027*
C25	−0.0811 (2)	−0.0577 (2)	0.74654 (19)	0.0221 (6)
H25	−0.1295	−0.1066	0.7773	0.026*
C26	0.0244 (2)	−0.0613 (2)	0.77559 (17)	0.0188 (6)
H26	0.0483	−0.1119	0.8272	0.023*
C27	0.4565 (2)	−0.0474 (2)	0.86363 (17)	0.0155 (6)
C28	0.4390 (2)	−0.1198 (2)	0.94374 (17)	0.0192 (6)
H28	0.3699	−0.1488	0.9584	0.023*
C29	0.5226 (2)	−0.1498 (2)	1.00257 (18)	0.0241 (7)
H29	0.5103	−0.1990	1.0574	0.029*
C30	0.6229 (2)	−0.1082 (2)	0.98128 (18)	0.0230 (7)
H30	0.6790	−0.1277	1.0221	0.028*
C31	0.6426 (2)	−0.0383 (2)	0.90106 (18)	0.0216 (6)
H31	0.7130	−0.0111	0.8863	0.026*
C32	0.5599 (2)	−0.0074 (2)	0.84167 (17)	0.0179 (6)
H32	0.5737	0.0406	0.7864	0.021*
N1'	0.08049 (17)	0.29382 (16)	0.65163 (13)	0.0123 (5)
C2'	−0.0090 (2)	0.35294 (19)	0.60986 (16)	0.0125 (5)
S3'	−0.10350 (6)	0.44093 (5)	0.66450 (4)	0.01738 (14)
C4'	−0.0142 (2)	0.3993 (2)	0.74905 (17)	0.0155 (6)
C5'	0.0825 (2)	0.3214 (2)	0.73020 (16)	0.0132 (5)
C6'	0.1713 (2)	0.2840 (2)	0.78538 (17)	0.0182 (6)
H6'	0.2378	0.2315	0.7734	0.022*
C7'	0.1597 (2)	0.3254 (2)	0.85796 (18)	0.0232 (7)
H7'	0.2198	0.3013	0.8958	0.028*
C8'	0.0621 (3)	0.4016 (2)	0.87686 (18)	0.0243 (7)
H8'	0.0564	0.4279	0.9275	0.029*
C9'	−0.0265 (2)	0.4394 (2)	0.82311 (17)	0.0219 (6)
H9'	−0.0935	0.4909	0.8361	0.026*
C10'	−0.0148 (2)	0.34173 (19)	0.52221 (16)	0.0124 (5)
C11'	0.0796 (2)	0.26639 (19)	0.49410 (16)	0.0111 (5)
C12'	0.0820 (2)	0.2557 (2)	0.40818 (17)	0.0163 (6)
H12'	0.1427	0.2053	0.3860	0.020*
C13'	−0.0031 (2)	0.3177 (2)	0.35466 (17)	0.0179 (6)
H13'	0.0018	0.3097	0.2963	0.021*
C14'	−0.0948 (2)	0.3908 (2)	0.38492 (17)	0.0167 (6)
H14'	−0.1522	0.4324	0.3477	0.020*
C15'	−0.1017 (2)	0.4026 (2)	0.46962 (17)	0.0160 (6)
H15'	−0.1646	0.4514	0.4918	0.019*
C97	0.7155 (2)	−0.3134 (2)	0.88203 (17)	0.0221 (6)
D97	0.6606	−0.2466	0.8897	0.026*
Cl1	0.67186 (6)	−0.41646 (6)	0.96693 (5)	0.02871 (17)
Cl2	0.70766 (6)	−0.32965 (6)	0.77698 (4)	0.02763 (17)
Cl3	0.86049 (6)	−0.30466 (6)	0.89109 (5)	0.02593 (16)
C98	−0.3809 (3)	0.3533 (3)	0.7609 (2)	0.0494 (11)
D98	−0.3574	0.4101	0.7099	0.059*
Cl4	−0.52591 (11)	0.34664 (11)	0.75553 (8)	0.1027 (6)
Cl5	−0.28516 (11)	0.23563 (9)	0.75073 (7)	0.0721 (3)
Cl6	−0.36850 (8)	0.38391 (8)	0.85894 (7)	0.0564 (3)
C99	0.2676 (2)	−0.2928 (2)	0.85817 (19)	0.0258 (7)
D99	0.2719	−0.2173	0.8456	0.031*
Cl7	0.23359 (9)	−0.31505 (9)	0.76311 (6)	0.0599 (3)
Cl8	0.40549 (7)	−0.36806 (7)	0.88483 (6)	0.0412 (2)
Cl9	0.15616 (7)	−0.31749 (7)	0.94744 (6)	0.0427 (2)
C96	0.9372 (5)	0.0481 (5)	1.0020 (4)	0.0311 (15)*	0.50
H96	0.8893	0.0731	1.0541	0.037*	0.50
Cl10	1.0842 (4)	0.0597 (5)	0.9970 (5)	0.0593 (16)	0.50
Cl11	0.88004 (16)	0.12749 (14)	0.90568 (11)	0.0413 (4)	0.50
Cl12	0.9281 (5)	−0.0812 (5)	1.0147 (5)	0.0587 (15)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir	0.00954 (5)	0.00903 (5)	0.01150 (5)	−0.00029 (4)	−0.00206 (3)	−0.00174 (3)
N1	0.0096 (11)	0.0124 (12)	0.0118 (11)	−0.0018 (9)	−0.0041 (8)	−0.0014 (9)
C2	0.0079 (12)	0.0131 (14)	0.0127 (12)	0.0000 (10)	−0.0030 (10)	−0.0035 (10)
S3	0.0124 (3)	0.0138 (3)	0.0148 (3)	−0.0027 (3)	0.0001 (2)	−0.0048 (3)
C4	0.0093 (13)	0.0142 (14)	0.0118 (13)	−0.0036 (11)	−0.0032 (10)	−0.0022 (11)
C5	0.0106 (12)	0.0110 (13)	0.0140 (13)	−0.0014 (10)	−0.0058 (10)	−0.0026 (10)
C6	0.0126 (13)	0.0160 (15)	0.0157 (13)	−0.0022 (11)	−0.0009 (10)	−0.0039 (11)
C7	0.0161 (14)	0.0141 (14)	0.0183 (14)	−0.0055 (11)	−0.0026 (11)	−0.0031 (11)
C8	0.0175 (14)	0.0126 (14)	0.0171 (14)	−0.0005 (11)	−0.0064 (11)	−0.0052 (11)
C9	0.0102 (13)	0.0142 (14)	0.0162 (13)	−0.0002 (11)	−0.0041 (10)	−0.0043 (11)
C10	0.0113 (12)	0.0094 (13)	0.0141 (13)	−0.0006 (10)	−0.0062 (10)	−0.0003 (10)
C11	0.0102 (13)	0.0113 (14)	0.0145 (13)	0.0015 (10)	−0.0062 (10)	−0.0034 (11)
C12	0.0111 (13)	0.0120 (14)	0.0198 (14)	0.0023 (11)	−0.0056 (11)	−0.0046 (11)
C13	0.0152 (14)	0.0124 (14)	0.0278 (16)	−0.0010 (11)	−0.0079 (12)	−0.0056 (12)
C14	0.0139 (14)	0.0172 (15)	0.0229 (15)	−0.0078 (12)	−0.0013 (11)	−0.0008 (12)
C15	0.0121 (13)	0.0195 (15)	0.0151 (13)	−0.0030 (11)	−0.0013 (10)	−0.0010 (11)
N16	0.0091 (10)	0.0112 (12)	0.0142 (11)	0.0020 (9)	−0.0030 (8)	−0.0033 (9)
N17	0.0112 (11)	0.0144 (12)	0.0144 (11)	0.0015 (9)	−0.0033 (9)	−0.0062 (9)
C18	0.0166 (13)	0.0122 (14)	0.0125 (13)	0.0016 (11)	−0.0018 (10)	−0.0043 (11)
N19	0.0159 (11)	0.0134 (12)	0.0132 (11)	0.0006 (9)	−0.0023 (9)	−0.0016 (9)
C20	0.0129 (13)	0.0098 (13)	0.0122 (13)	0.0011 (10)	−0.0004 (10)	−0.0020 (10)
C21	0.0124 (13)	0.0122 (14)	0.0149 (13)	0.0008 (11)	0.0005 (10)	−0.0047 (11)
N22	0.0123 (11)	0.0110 (12)	0.0148 (11)	−0.0015 (9)	0.0006 (9)	−0.0044 (9)
C23	0.0133 (13)	0.0137 (14)	0.0188 (14)	0.0011 (11)	−0.0052 (11)	−0.0031 (11)
C24	0.0134 (14)	0.0198 (16)	0.0331 (17)	−0.0036 (12)	−0.0044 (12)	−0.0033 (13)
C25	0.0159 (14)	0.0174 (16)	0.0298 (17)	−0.0075 (12)	0.0031 (12)	−0.0011 (13)
C26	0.0180 (14)	0.0153 (15)	0.0178 (14)	−0.0011 (12)	0.0002 (11)	0.0014 (11)
C27	0.0200 (14)	0.0130 (14)	0.0141 (13)	0.0022 (11)	−0.0057 (11)	−0.0068 (11)
C28	0.0217 (15)	0.0174 (15)	0.0163 (14)	0.0026 (12)	−0.0047 (11)	−0.0045 (12)
C29	0.0315 (17)	0.0180 (16)	0.0161 (14)	0.0074 (13)	−0.0057 (12)	−0.0021 (12)
C30	0.0261 (16)	0.0193 (16)	0.0231 (15)	0.0105 (13)	−0.0155 (13)	−0.0092 (13)
C31	0.0182 (14)	0.0223 (17)	0.0263 (16)	0.0028 (12)	−0.0081 (12)	−0.0115 (13)
C32	0.0222 (15)	0.0150 (15)	0.0167 (14)	−0.0003 (12)	−0.0067 (11)	−0.0043 (11)
N1'	0.0127 (11)	0.0096 (11)	0.0132 (11)	−0.0025 (9)	−0.0010 (9)	−0.0005 (9)
C2'	0.0109 (12)	0.0105 (14)	0.0154 (13)	−0.0043 (10)	−0.0005 (10)	−0.0007 (10)
S3'	0.0144 (3)	0.0143 (4)	0.0223 (4)	0.0022 (3)	−0.0028 (3)	−0.0069 (3)
C4'	0.0177 (14)	0.0125 (15)	0.0155 (14)	−0.0033 (11)	−0.0014 (11)	−0.0022 (11)
C5'	0.0140 (13)	0.0104 (14)	0.0144 (13)	−0.0033 (11)	0.0012 (10)	−0.0029 (11)
C6'	0.0216 (15)	0.0134 (15)	0.0169 (14)	0.0019 (11)	−0.0044 (11)	−0.0028 (11)
C7'	0.0289 (16)	0.0206 (16)	0.0191 (15)	0.0032 (13)	−0.0100 (12)	−0.0056 (12)
C8'	0.0368 (18)	0.0206 (16)	0.0166 (14)	−0.0039 (14)	−0.0036 (13)	−0.0080 (12)
C9'	0.0265 (16)	0.0157 (15)	0.0213 (15)	0.0021 (12)	−0.0004 (12)	−0.0082 (12)
C10'	0.0119 (13)	0.0093 (13)	0.0170 (13)	−0.0064 (10)	−0.0013 (10)	−0.0014 (10)
C11'	0.0093 (12)	0.0095 (13)	0.0150 (13)	−0.0045 (10)	−0.0021 (10)	−0.0012 (10)
C12'	0.0143 (13)	0.0155 (15)	0.0181 (14)	−0.0043 (11)	−0.0002 (11)	−0.0023 (11)
C13'	0.0183 (14)	0.0216 (16)	0.0132 (13)	−0.0077 (12)	−0.0035 (11)	0.0007 (11)
C14'	0.0151 (14)	0.0139 (14)	0.0212 (14)	−0.0049 (11)	−0.0096 (11)	0.0019 (11)
C15'	0.0126 (13)	0.0114 (14)	0.0222 (14)	−0.0012 (11)	−0.0035 (11)	−0.0013 (11)
C97	0.0251 (16)	0.0190 (16)	0.0178 (14)	−0.0001 (13)	−0.0009 (12)	−0.0026 (12)
Cl1	0.0313 (4)	0.0276 (4)	0.0228 (4)	−0.0093 (3)	−0.0032 (3)	0.0041 (3)
Cl2	0.0270 (4)	0.0354 (5)	0.0185 (4)	−0.0021 (3)	−0.0046 (3)	−0.0058 (3)
Cl3	0.0289 (4)	0.0236 (4)	0.0264 (4)	−0.0078 (3)	−0.0048 (3)	−0.0048 (3)
C98	0.050 (2)	0.062 (3)	0.038 (2)	−0.035 (2)	−0.0144 (18)	0.0116 (19)
Cl4	0.0817 (9)	0.1328 (12)	0.0878 (9)	−0.0809 (9)	−0.0533 (7)	0.0629 (8)
Cl5	0.1107 (9)	0.0559 (7)	0.0643 (7)	−0.0447 (7)	0.0182 (6)	−0.0335 (6)
Cl6	0.0527 (6)	0.0587 (7)	0.0685 (7)	−0.0135 (5)	0.0029 (5)	−0.0381 (6)
C99	0.0222 (16)	0.0226 (17)	0.0308 (17)	−0.0056 (13)	−0.0076 (13)	0.0003 (13)
Cl7	0.0526 (6)	0.0868 (8)	0.0485 (6)	0.0014 (6)	−0.0201 (5)	−0.0343 (6)
Cl8	0.0207 (4)	0.0381 (5)	0.0544 (5)	−0.0053 (4)	−0.0109 (4)	0.0093 (4)
Cl9	0.0332 (5)	0.0363 (5)	0.0422 (5)	0.0023 (4)	0.0037 (4)	0.0035 (4)
Cl10	0.0186 (13)	0.119 (5)	0.053 (2)	−0.0228 (19)	0.0042 (13)	−0.040 (3)
Cl11	0.0549 (11)	0.0361 (10)	0.0335 (9)	−0.0055 (8)	−0.0084 (8)	−0.0106 (8)
Cl12	0.080 (3)	0.0339 (14)	0.058 (2)	−0.0109 (16)	0.0000 (19)	−0.0114 (14)

Geometric parameters (Å, º) top

Ir—C11	2.014 (3)	C28—C29	1.392 (3)
Ir—C11'	2.022 (2)	C28—H28	0.9500
Ir—N1'	2.060 (2)	C29—C30	1.375 (4)
Ir—N1	2.064 (2)	C29—H29	0.9500
Ir—N16	2.1264 (19)	C30—C31	1.378 (4)
Ir—N22	2.160 (2)	C30—H30	0.9500
N1—C2	1.323 (3)	C31—C32	1.390 (3)
N1—C5	1.407 (3)	C31—H31	0.9500
C2—C10	1.447 (3)	C32—H32	0.9500
C2—S3	1.720 (3)	N1'—C2'	1.322 (3)
S3—C4	1.744 (3)	N1'—C5'	1.400 (3)
C4—C9	1.398 (3)	C2'—C10'	1.453 (3)
C4—C5	1.398 (3)	C2'—S3'	1.724 (3)
C5—C6	1.399 (3)	S3'—C4'	1.742 (3)
C6—C7	1.382 (3)	C4'—C9'	1.393 (4)
C6—H6	0.9500	C4'—C5'	1.401 (3)
C7—C8	1.398 (3)	C5'—C6'	1.397 (3)
C7—H7	0.9500	C6'—C7'	1.384 (4)
C8—C9	1.377 (3)	C6'—H6'	0.9500
C8—H8	0.9500	C7'—C8'	1.394 (4)
C9—H9	0.9500	C7'—H7'	0.9500
C10—C15	1.397 (3)	C8'—C9'	1.380 (4)
C10—C11	1.412 (3)	C8'—H8'	0.9500
C11—C12	1.405 (3)	C9'—H9'	0.9500
C12—C13	1.385 (4)	C10'—C15'	1.395 (3)
C12—H12	0.9500	C10'—C11'	1.411 (3)
C13—C14	1.387 (4)	C11'—C12'	1.402 (3)
C13—H13	0.9500	C12'—C13'	1.394 (3)
C14—C15	1.379 (4)	C12'—H12'	0.9500
C14—H14	0.9500	C13'—C14'	1.388 (4)
C15—H15	0.9500	C13'—H13'	0.9500
N16—C20	1.333 (3)	C14'—C15'	1.379 (4)
N16—N17	1.365 (3)	C14'—H14'	0.9500
N17—C18	1.341 (3)	C15'—H15'	0.9500
C18—N19	1.352 (3)	C97—Cl1	1.755 (3)
C18—C27	1.486 (3)	C97—Cl2	1.759 (3)
N19—C20	1.345 (3)	C97—Cl3	1.771 (3)
C20—C21	1.447 (3)	C97—D97	1.0000
C21—N22	1.370 (3)	C98—Cl5	1.745 (4)
C21—C26	1.387 (3)	C98—Cl4	1.747 (3)
N22—C23	1.345 (3)	C98—Cl6	1.752 (4)
C23—C24	1.377 (4)	C98—D98	1.0000
C23—H23	0.9500	C99—Cl7	1.746 (3)
C24—C25	1.382 (4)	C99—Cl8	1.750 (3)
C24—H24	0.9500	C99—Cl9	1.757 (3)
C25—C26	1.387 (3)	C99—D99	1.0000
C25—H25	0.9500	C96—Cl12	1.737 (8)
C26—H26	0.9500	C96—Cl11	1.752 (6)
C27—C28	1.390 (3)	C96—Cl10	1.758 (7)
C27—C32	1.396 (4)	C96—H96	1.0000

C11—Ir—C11'	88.18 (9)	C21—C26—H26	120.3
C11—Ir—N1'	94.17 (9)	C28—C27—C32	119.5 (2)
C11'—Ir—N1'	79.98 (9)	C28—C27—C18	120.0 (2)
C11—Ir—N1	79.54 (9)	C32—C27—C18	120.4 (2)
C11'—Ir—N1	92.98 (9)	C27—C28—C29	120.1 (3)
N1'—Ir—N1	170.77 (8)	C27—C28—H28	120.0
C11—Ir—N16	102.78 (8)	C29—C28—H28	120.0
C11'—Ir—N16	168.90 (8)	C30—C29—C28	120.0 (3)
N1'—Ir—N16	97.25 (8)	C30—C29—H29	120.0
N1—Ir—N16	90.77 (8)	C28—C29—H29	120.0
C11—Ir—N22	178.49 (9)	C29—C30—C31	120.4 (2)
C11'—Ir—N22	93.05 (8)	C29—C30—H30	119.8
N1'—Ir—N22	86.91 (8)	C31—C30—H30	119.8
N1—Ir—N22	99.51 (8)	C30—C31—C32	120.3 (3)
N16—Ir—N22	76.03 (8)	C30—C31—H31	119.9
C2—N1—C5	110.8 (2)	C32—C31—H31	119.9
C2—N1—Ir	114.19 (17)	C31—C32—C27	119.7 (3)
C5—N1—Ir	134.97 (17)	C31—C32—H32	120.1
N1—C2—C10	117.8 (2)	C27—C32—H32	120.1
N1—C2—S3	115.97 (19)	C2'—N1'—C5'	111.6 (2)
C10—C2—S3	126.14 (19)	C2'—N1'—Ir	113.96 (16)
C2—S3—C4	89.36 (12)	C5'—N1'—Ir	134.48 (16)
C9—C4—C5	121.9 (2)	N1'—C2'—C10'	117.8 (2)
C9—C4—S3	127.7 (2)	N1'—C2'—S3'	115.30 (18)
C5—C4—S3	110.37 (19)	C10'—C2'—S3'	126.80 (19)
C4—C5—C6	119.5 (2)	C2'—S3'—C4'	89.47 (12)
C4—C5—N1	113.5 (2)	C9'—C4'—C5'	121.9 (2)
C6—C5—N1	127.1 (2)	C9'—C4'—S3'	127.6 (2)
C7—C6—C5	118.6 (2)	C5'—C4'—S3'	110.33 (19)
C7—C6—H6	120.7	C6'—C5'—N1'	127.0 (2)
C5—C6—H6	120.7	C6'—C5'—C4'	119.7 (2)
C6—C7—C8	121.3 (2)	N1'—C5'—C4'	113.2 (2)
C6—C7—H7	119.3	C7'—C6'—C5'	118.2 (2)
C8—C7—H7	119.3	C7'—C6'—H6'	120.9
C9—C8—C7	121.0 (2)	C5'—C6'—H6'	120.9
C9—C8—H8	119.5	C6'—C7'—C8'	121.6 (2)
C7—C8—H8	119.5	C6'—C7'—H7'	119.2
C8—C9—C4	117.7 (2)	C8'—C7'—H7'	119.2
C8—C9—H9	121.1	C9'—C8'—C7'	121.0 (3)
C4—C9—H9	121.1	C9'—C8'—H8'	119.5
C15—C10—C11	122.7 (2)	C7'—C8'—H8'	119.5
C15—C10—C2	124.8 (2)	C8'—C9'—C4'	117.6 (3)
C11—C10—C2	112.4 (2)	C8'—C9'—H9'	121.2
C12—C11—C10	116.1 (2)	C4'—C9'—H9'	121.2
C12—C11—Ir	128.7 (2)	C15'—C10'—C11'	123.4 (2)
C10—C11—Ir	115.08 (18)	C15'—C10'—C2'	123.5 (2)
C13—C12—C11	120.9 (2)	C11'—C10'—C2'	113.0 (2)
C13—C12—H12	119.6	C12'—C11'—C10'	115.6 (2)
C11—C12—H12	119.6	C12'—C11'—Ir	129.8 (2)
C12—C13—C14	121.8 (3)	C10'—C11'—Ir	114.42 (17)
C12—C13—H13	119.1	C13'—C12'—C11'	121.2 (3)
C14—C13—H13	119.1	C13'—C12'—H12'	119.4
C15—C14—C13	119.0 (2)	C11'—C12'—H12'	119.4
C15—C14—H14	120.5	C14'—C13'—C12'	121.3 (2)
C13—C14—H14	120.5	C14'—C13'—H13'	119.3
C14—C15—C10	119.4 (2)	C12'—C13'—H13'	119.3
C14—C15—H15	120.3	C15'—C14'—C13'	119.3 (2)
C10—C15—H15	120.3	C15'—C14'—H14'	120.3
C20—N16—N17	107.33 (19)	C13'—C14'—H14'	120.3
C20—N16—Ir	115.60 (15)	C14'—C15'—C10'	119.0 (2)
N17—N16—Ir	137.07 (16)	C14'—C15'—H15'	120.5
C18—N17—N16	103.6 (2)	C10'—C15'—H15'	120.5
N17—C18—N19	114.9 (2)	Cl1—C97—Cl2	111.48 (16)
N17—C18—C27	121.6 (2)	Cl1—C97—Cl3	109.43 (14)
N19—C18—C27	123.5 (2)	Cl2—C97—Cl3	110.84 (15)
C20—N19—C18	100.8 (2)	Cl1—C97—D97	108.3
N16—C20—N19	113.2 (2)	Cl2—C97—D97	108.3
N16—C20—C21	118.9 (2)	Cl3—C97—D97	108.3
N19—C20—C21	127.9 (2)	Cl5—C98—Cl4	110.2 (2)
N22—C21—C26	121.2 (2)	Cl5—C98—Cl6	110.47 (18)
N22—C21—C20	113.6 (2)	Cl4—C98—Cl6	111.8 (2)
C26—C21—C20	125.2 (2)	Cl5—C98—D98	108.1
C23—N22—C21	118.4 (2)	Cl4—C98—D98	108.1
C23—N22—Ir	125.73 (17)	Cl6—C98—D98	108.1
C21—N22—Ir	115.91 (16)	Cl7—C99—Cl8	110.99 (17)
N22—C23—C24	122.7 (2)	Cl7—C99—Cl9	110.85 (15)
N22—C23—H23	118.6	Cl8—C99—Cl9	111.02 (15)
C24—C23—H23	118.6	Cl7—C99—D99	107.9
C23—C24—C25	119.2 (2)	Cl8—C99—D99	107.9
C23—C24—H24	120.4	Cl9—C99—D99	107.9
C25—C24—H24	120.4	Cl12—C96—Cl11	110.5 (4)
C24—C25—C26	119.1 (3)	Cl12—C96—Cl10	111.1 (4)
C24—C25—H25	120.4	Cl11—C96—Cl10	109.3 (4)
C26—C25—H25	120.4	Cl12—C96—H96	108.6
C25—C26—C21	119.4 (2)	Cl11—C96—H96	108.6
C25—C26—H26	120.3	Cl10—C96—H96	108.6

C11—Ir—N1—C2	−6.33 (16)	C11'—Ir—N22—C23	2.0 (2)
C11'—Ir—N1—C2	81.27 (17)	N1'—Ir—N22—C23	81.8 (2)
N16—Ir—N1—C2	−109.18 (16)	N1—Ir—N22—C23	−91.5 (2)
N22—Ir—N1—C2	174.86 (16)	N16—Ir—N22—C23	−179.9 (2)
C11—Ir—N1—C5	173.0 (2)	C11'—Ir—N22—C21	−178.67 (18)
C11'—Ir—N1—C5	−99.5 (2)	N1'—Ir—N22—C21	−98.88 (18)
N16—Ir—N1—C5	70.1 (2)	N1—Ir—N22—C21	87.79 (18)
N22—Ir—N1—C5	−5.9 (2)	N16—Ir—N22—C21	−0.63 (17)
C5—N1—C2—C10	−176.80 (19)	C21—N22—C23—C24	−1.3 (4)
Ir—N1—C2—C10	2.7 (3)	Ir—N22—C23—C24	178.0 (2)
C5—N1—C2—S3	0.3 (2)	N22—C23—C24—C25	0.1 (4)
Ir—N1—C2—S3	179.74 (10)	C23—C24—C25—C26	1.2 (4)
N1—C2—S3—C4	−0.48 (18)	C24—C25—C26—C21	−1.3 (4)
C10—C2—S3—C4	176.3 (2)	N22—C21—C26—C25	0.1 (4)
C2—S3—C4—C9	−179.1 (2)	C20—C21—C26—C25	−177.9 (3)
C2—S3—C4—C5	0.53 (18)	N17—C18—C27—C28	170.1 (2)
C9—C4—C5—C6	−0.4 (3)	N19—C18—C27—C28	−8.5 (4)
S3—C4—C5—C6	179.93 (17)	N17—C18—C27—C32	−6.5 (4)
C9—C4—C5—N1	179.1 (2)	N19—C18—C27—C32	174.9 (2)
S3—C4—C5—N1	−0.5 (2)	C32—C27—C28—C29	1.8 (4)
C2—N1—C5—C4	0.2 (3)	C18—C27—C28—C29	−174.8 (2)
Ir—N1—C5—C4	−179.15 (16)	C27—C28—C29—C30	−0.3 (4)
C2—N1—C5—C6	179.7 (2)	C28—C29—C30—C31	−1.3 (4)
Ir—N1—C5—C6	0.4 (4)	C29—C30—C31—C32	1.4 (4)
C4—C5—C6—C7	0.2 (3)	C30—C31—C32—C27	0.1 (4)
N1—C5—C6—C7	−179.3 (2)	C28—C27—C32—C31	−1.7 (4)
C5—C6—C7—C8	−0.1 (4)	C18—C27—C32—C31	174.9 (2)
C6—C7—C8—C9	0.1 (4)	C11—Ir—N1'—C2'	95.28 (18)
C7—C8—C9—C4	−0.3 (3)	C11'—Ir—N1'—C2'	7.87 (17)
C5—C4—C9—C8	0.5 (3)	N16—Ir—N1'—C2'	−161.26 (17)
S3—C4—C9—C8	−179.98 (18)	N22—Ir—N1'—C2'	−85.78 (17)
N1—C2—C10—C15	−178.6 (2)	C11—Ir—N1'—C5'	−84.3 (2)
S3—C2—C10—C15	4.7 (3)	C11'—Ir—N1'—C5'	−171.7 (2)
N1—C2—C10—C11	4.8 (3)	N16—Ir—N1'—C5'	19.2 (2)
S3—C2—C10—C11	−171.96 (17)	N22—Ir—N1'—C5'	94.6 (2)
C15—C10—C11—C12	−3.5 (3)	C5'—N1'—C2'—C10'	173.0 (2)
C2—C10—C11—C12	173.2 (2)	Ir—N1'—C2'—C10'	−6.6 (3)
C15—C10—C11—Ir	173.17 (18)	C5'—N1'—C2'—S3'	−3.8 (3)
C2—C10—C11—Ir	−10.1 (3)	Ir—N1'—C2'—S3'	176.50 (11)
C11'—Ir—C11—C12	91.8 (2)	N1'—C2'—S3'—C4'	2.0 (2)
N1'—Ir—C11—C12	12.0 (2)	C10'—C2'—S3'—C4'	−174.5 (2)
N1—Ir—C11—C12	−174.8 (2)	C2'—S3'—C4'—C9'	175.7 (3)
N16—Ir—C11—C12	−86.4 (2)	C2'—S3'—C4'—C5'	0.3 (2)
C11'—Ir—C11—C10	−84.38 (18)	C2'—N1'—C5'—C6'	−172.2 (2)
N1'—Ir—C11—C10	−164.20 (17)	Ir—N1'—C5'—C6'	7.4 (4)
N1—Ir—C11—C10	8.99 (17)	C2'—N1'—C5'—C4'	4.0 (3)
N16—Ir—C11—C10	97.39 (18)	Ir—N1'—C5'—C4'	−176.37 (18)
C10—C11—C12—C13	3.3 (3)	C9'—C4'—C5'—C6'	−1.7 (4)
Ir—C11—C12—C13	−172.88 (18)	S3'—C4'—C5'—C6'	174.0 (2)
C11—C12—C13—C14	−0.7 (4)	C9'—C4'—C5'—N1'	−178.2 (2)
C12—C13—C14—C15	−1.9 (4)	S3'—C4'—C5'—N1'	−2.5 (3)
C13—C14—C15—C10	1.7 (4)	N1'—C5'—C6'—C7'	176.5 (3)
C11—C10—C15—C14	1.1 (4)	C4'—C5'—C6'—C7'	0.5 (4)
C2—C10—C15—C14	−175.2 (2)	C5'—C6'—C7'—C8'	0.7 (4)
C11—Ir—N16—C20	−177.88 (18)	C6'—C7'—C8'—C9'	−0.6 (4)
N1'—Ir—N16—C20	86.15 (18)	C7'—C8'—C9'—C4'	−0.5 (4)
N1—Ir—N16—C20	−98.43 (18)	C5'—C4'—C9'—C8'	1.7 (4)
N22—Ir—N16—C20	1.18 (18)	S3'—C4'—C9'—C8'	−173.2 (2)
C11—Ir—N16—N17	1.8 (2)	N1'—C2'—C10'—C15'	−177.1 (2)
N1'—Ir—N16—N17	−94.2 (2)	S3'—C2'—C10'—C15'	−0.6 (4)
N1—Ir—N16—N17	81.2 (2)	N1'—C2'—C10'—C11'	0.1 (3)
N22—Ir—N16—N17	−179.2 (2)	S3'—C2'—C10'—C11'	176.57 (18)
C20—N16—N17—C18	0.3 (3)	C15'—C10'—C11'—C12'	0.2 (4)
Ir—N16—N17—C18	−179.34 (19)	C2'—C10'—C11'—C12'	−177.0 (2)
N16—N17—C18—N19	−0.1 (3)	C15'—C10'—C11'—Ir	−176.18 (19)
N16—N17—C18—C27	−178.8 (2)	C2'—C10'—C11'—Ir	6.6 (3)
N17—C18—N19—C20	−0.2 (3)	C11—Ir—C11'—C12'	81.9 (2)
C27—C18—N19—C20	178.5 (2)	N1'—Ir—C11'—C12'	176.5 (2)
N17—N16—C20—N19	−0.5 (3)	N1—Ir—C11'—C12'	2.5 (2)
Ir—N16—C20—N19	179.27 (16)	N22—Ir—C11'—C12'	−97.2 (2)
N17—N16—C20—C21	178.6 (2)	C11—Ir—C11'—C10'	−102.35 (19)
Ir—N16—C20—C21	−1.6 (3)	N1'—Ir—C11'—C10'	−7.78 (17)
C18—N19—C20—N16	0.4 (3)	N1—Ir—C11'—C10'	178.23 (18)
C18—N19—C20—C21	−178.6 (3)	N22—Ir—C11'—C10'	78.53 (18)
N16—C20—C21—N22	1.0 (3)	C10'—C11'—C12'—C13'	1.1 (4)
N19—C20—C21—N22	−180.0 (2)	Ir—C11'—C12'—C13'	176.80 (19)
N16—C20—C21—C26	179.2 (2)	C11'—C12'—C13'—C14'	−1.3 (4)
N19—C20—C21—C26	−1.8 (4)	C12'—C13'—C14'—C15'	0.1 (4)
C26—C21—N22—C23	1.2 (4)	C13'—C14'—C15'—C10'	1.1 (4)
C20—C21—N22—C23	179.4 (2)	C11'—C10'—C15'—C14'	−1.3 (4)
C26—C21—N22—Ir	−178.2 (2)	C2'—C10'—C15'—C14'	175.6 (2)
C20—C21—N22—Ir	0.0 (3)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C27–C32 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C99—D99···N19	1.00	2.18	3.180 (4)	175
C98—D98···S3′	1.00	3.04	3.660 (3)	121
C97—D97···Cg	1.00	2.50	3.50	173

Experimental details

Crystal data
Chemical formula	[Ir(C₁₃H₉N₄)(C₁₃H₈NS)₂]·3.5CDCl₃
M_r	1254.78
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	11.7521 (4), 13.5592 (4), 15.8373 (4)
α, β, γ (°)	74.045 (3), 79.247 (3), 76.002 (3)
V (Å³)	2334.80 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.59
Crystal size (mm)	0.20 × 0.10 × 0.08

Data collection
Diffractometer	Oxford Diffraction Xcalibur, Eos
Absorption correction	Multi-scan CrysAlis PRO, Oxford Diffraction (2010).
T_min, T_max	0.902, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	94997, 13407, 10433
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.047, 0.88
No. of reflections	13407
No. of parameters	572
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.88, −1.70

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Siemens, 1994).