Crystal structure of chlorido­(dimethyl sulfoxide-κS)bis­[4-(pyridin-2-yl)benzaldehyde-κ3C2,N]iridium(III) aceto­nitrile monosolvate

Peloquin, A.J.; Smith, M.B.; Balaich, G.J.; Iacono, S.T.

doi:10.1107/S2056989017010945

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ISSN: 2056-9890

Volume 73| Part 9| September 2017| Pages 1279-1281

https://doi.org/10.1107/S2056989017010945

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Crystal structure of chlorido(dimethyl sulfoxide-κS)bis[4-(pyridin-2-yl)benzaldehyde-κ³C²,N]iridium(III) acetonitrile monosolvate

Andrew J. Peloquin,^a Madelyn B. Smith,^a Gary J. Balaich ^a and Scott T. Iacono ^a ^*

^aDepartment of Chemistry & Chemistry Research Center, United States Air Force Academy, Colorado Springs, CO 80840, USA
^*Correspondence e-mail: scott.iacono@usafa.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 20 June 2017; accepted 25 July 2017; online 1 August 2017)

The title compound, [IrCl(C₁₂H₈NO)₂{(CH₃)₂SO}]·H₃CCN or [IrCl(fppy)₂(DMSO)]·H₃CCN [where fppy is 4-(pyridin-2-yl)benzaldehyde and DMSO is dimethyl sulfoxide], is a mononuclear iridium(III) complex including two fppy ligands, a sulfur-coordinating DMSO ligand, and one terminal chloride ligand that define a distorted octahedral coordination sphere. The complex crystallizes from 1:1 DMSO–acetonitrile as an acetonitrile solvate. In the crystal, weak C—H⋯O and C—H⋯N hydrogen-bonding interactions between adjacent complexes and between the acetonitrile solvent and the complex consolidate the packing.

Keywords: crystal structure; iridium; phenylpyridine derivative.

CCDC reference: 1564599

1. Chemical context

The development of iridium complexes with three ortho metallating ligands has drawn great interest due to their potential application in light-emitting devices (Henwood & Zysman-Coman, 2017 ). Many such complexes have been synthesized, often utilizing phenylpyridine-based dichlorido-bridged di-iridium complexes as starting materials. In an attempt to synthesize such a compound with 4-(pyridin-2-yl)benzaldehyde (fppy) as a ligand, viz. di-μ-chlorido-bis{bis[4-(pyridin-2-yl)benzaldehyde-κ²C²,N′]iridium(III) (Bettington et al., 2004 ), spectroscopic results indicated a product with reduced symmetry compared to the expected C_i symmetry of the known complex. Single-crystal X-ray analysis was used to elucidate the structure of the title compound.

2. Structural commentary

The title compound (Fig. 1) crystallizes in the triclinic space group P $[\overline{1}]$ with one molecule per asymmetric unit. The Ir^III atom has a distorted octahedral coordination sphere defined by the S atom of the dimethyl sulfoxide (DMSO) ligand, a chlorine ligand and C and N atoms of two fppy ligands. The S and Cl atoms occupy equatorial positions, trans to the fppy C atoms, and the fppy N atoms occupy the axial positions. The least-squares planes of each fppy ligand indicate a nearly coplanar arrangement of the pyridine and phenyl rings with small deviations of 2.42 (9)° (fppy ligand N1/C2–C12 with C4 trans to S1) and 14.71 (9)° (fppy ligand N2/C14–C24 with C16 trans to Cl1). The Ir—S bond length [2.3810 (5) Å] is longer than the average distance [2.27 (1) Å] that was reported for this coordination mode (Calligaris, 2004 ). The S—O distance [1.4903 (13) Å] is only slightly longer than the previously reported average [1.473 (4) Å]. This S—O distance shows negligible contraction from the average reported S—O bond length [1.492 (1) Å] in non-coordinating sulfoxide molecules (Calligaris, 2004).

Figure 1
The molecular structure of chlorido(dimethyl sulfoxide-κS)bis[4-(pyridin-2-yl)benzaldehyde-κ²C²,N′]iridium(III) acetonitrile monosolvate. Displacement ellipsoids are shown at the 50% probability level. Only aldehyde H atoms are shown and the acetonitrile solvent molecule has been omitted for clarity.

3. Supramolecular features

The acetonitrile solvate molecules fill voids that are visible along the b axis view direction (Fig. 2). Alignment of the acetonitrile molecules is caused by weak intermolecular contacts between acetonitrile H atoms and adjacent fppy aldehyde carbonyl O atoms (C28—H28⋯O1) in addition to weak interactions between acetonitrile N atoms and adjacent DMSO H atoms (C25—H25B⋯N3). There are also C—H⋯O interactions between adjacent complexes, involving aromatic H atoms of one of the fppy ligands and methyl groups of the DMSO ligand with the sulfoxide O atom. Numerical details of all these interactions are collated in Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19⋯O3ⁱ	0.93	2.48	3.179 (3)	132
C25—H25B⋯N3ⁱⁱ	0.96	2.53	3.403 (3)	150
C26—H26A⋯O3ⁱⁱⁱ	0.96	2.48	3.406 (2)	161
C28—H28C⋯O1^iv	0.96	2.54	3.490 (3)	173
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+2, -z+1; (iii) -x+2, -y+2, -z+2; (iv) x+1, y, z.

Figure 2
The crystal packing of the title complex, viewed along the b axis. Displacement ellipsoids are shown at the 50% probability level. H atoms have been omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (CSD, V5.38, update February 2017; Groom et al., 2016 ) for related structures revealed that the di-μ-chlorido-bis{bis[4-(pyridin-2-yl)benzaldehyde-κ²C²,N′]iridium(III)} complex from which the title complex was derived, has been reported as a dichloromethane sesquisolvate (Bettington et al., 2004).

5. Synthesis and crystallization

The parent compound, di-μ-chlorido-bis{bis[4-(pyridin-2-yl)benzaldehyde-κ²C²,N′]iridium(III), was synthesized utilizing a previously reported procedure (Bettington et al., 2004).

For the synthesis of the title compound, di-μ-chlorido-bis{bis[4-(pyridin-2-yl)benzaldehyde-k²C²,N′]iridium(III) (0.101 g, 0.077 mmol) was dissolved in DMSO (2 ml) with gentle heating over 5 min. After cooling to room temperature, acetonitrile (2 ml) was added. After 24 h, the resulting solid was collected by vacuum filtration to afford the title compound as an orange crystalline solid (0.043 g, 41.7%). Spectroscopic data: ¹H NMR (500 MHz, DMSO-d₆): δ 9.83 (d, 1H, J = 8.0 Hz), 9.61 (s, 1H), 9.55–9.53 (m, 2H), 8.42 (d, 1H, J = 8.0 Hz), 8.34 (d, 1H, J = 8.0 Hz), 8.20 (t, 1H, J = 7.5 Hz), 8.11 (t, 1H, J = 7.5 Hz), 8.01 (d, 1H, J = 7.5 Hz), 7.96 (d, 1H, J = 8.0 Hz), 7.69 (t, 1H, J = 6.5 Hz), 7.60 (t, 1H, J = 6.5 Hz), 7.40 (d, 1H, J = 8.0 Hz), 7.36 (d, 1H, J = 8.0 Hz), 6.71 (s, 1H), 6.10 (s, 1H) and ¹³C NMR (500 MHz, DMSO-d₆): δ 193.6, 193.5, 166.1, 165.7, 153.1, 152.1, 151.7, 150.5, 149.9, 145.5, 140.4, 139.4, 136.6, 135.9, 131.2, 129.4, 126.4, 125.9, 125.7, 125.5, 125.2, 124.8, 122.4, 121.8, 72.3, 66.0, 60.8, 40.5, 40.3, 40.1, 40.0, 39.8, 39.6, 39.5, 15.7.

6. Refinement

Crystal data as well as data collection and structure refinement details are summarized in Table 2. The aldehyde hydrogen atoms were found in a difference-Fourier map and were refined freely. The remaining hydrogen atoms were included in calculated positions and refined with a riding model: C—H = 0.95-0.98 Å with U_iso(H) = 1.5 U_eq(C-methyl) and 1.2 U_eq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	[IrCl(C₁₂H₈NO)₂(C₂H₆OS)]·C₂H₃N
M_r	711.22
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	8.7837 (12), 12.0910 (16), 14.0097 (19)
α, β, γ (°)	97.5367 (15), 105.1501 (14), 109.3176 (14)
V (Å³)	1316.1 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	5.29
Crystal size (mm)	0.32 × 0.24 × 0.17

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.26, 0.47
No. of measured, independent and observed [I > 2σ(I)] reflections	28976, 6983, 6828
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.015, 0.037, 1.68
No. of reflections	6983
No. of parameters	345
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.47, −0.65
Computer programs: APEX3 and SAINT (Bruker, 2017 ), SHELXS (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC reference: 1564599

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989017010945/wm5400sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017010945/wm5400Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015).

Chlorido(dimethyl sulfoxide-κS)bis[4-(pyridin-2-yl)benzaldehyde-κ²C³,N]iridium(III) acetonitrile monosolvate top

Crystal data top

[IrCl(C₁₂H₈NO)₂(C₂H₆OS)]·C₂H₃N	Z = 2
M_r = 711.22	F(000) = 696
Triclinic, P1	D_x = 1.795 Mg m⁻³
a = 8.7837 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.0910 (16) Å	Cell parameters from 9979 reflections
c = 14.0097 (19) Å	θ = 2.6–30.0°
α = 97.5367 (15)°	µ = 5.29 mm⁻¹
β = 105.1501 (14)°	T = 100 K
γ = 109.3176 (14)°	Rectangular prism, orange
V = 1316.1 (3) Å³	0.32 × 0.24 × 0.17 mm

Data collection top

Bruker SMART APEX CCD diffractometer	6983 independent reflections
Radiation source: fine focus sealed tube	6828 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 8.3333 pixels mm^-1	θ_max = 29.1°, θ_min = 1.8°
ω Scans scans	h = −11→11
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −16→16
T_min = 0.26, T_max = 0.47	l = −19→19
28976 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)] = 0.015	Hydrogen site location: mixed
wR(F²) = 0.037	H atoms treated by a mixture of independent and constrained refinement
S = 1.68	w = 1/[σ²(F_o²)] where P = (F_o² + 2F_c²)/3
6983 reflections	(Δ/σ)_max = 0.003
345 parameters	Δρ_max = 1.47 e Å⁻³
0 restraints	Δρ_min = −0.65 e Å⁻³

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1	−0.0050 (3)	0.6613 (2)	0.33167 (17)	0.0243 (5)
H1	−0.088 (3)	0.596 (2)	0.278 (2)	0.042 (8)*
C2	0.1092 (2)	0.62505 (18)	0.40746 (15)	0.0157 (4)
H2	0.077 (3)	0.594 (2)	0.9857 (18)	0.028 (6)*
C3	0.2305 (2)	0.71022 (17)	0.49507 (14)	0.0134 (4)
H3	0.239758	0.790067	0.505177	0.016*
C4	0.3376 (2)	0.67614 (16)	0.56730 (14)	0.0100 (3)
C5	0.3222 (2)	0.55552 (16)	0.54791 (14)	0.0116 (4)
C6	0.2015 (2)	0.46989 (17)	0.46076 (14)	0.0151 (4)
H6	0.193066	0.390228	0.449892	0.018*
C7	0.0941 (2)	0.50534 (17)	0.39041 (15)	0.0164 (4)
H7	0.012541	0.449242	0.332285	0.02*
C8	0.6532 (2)	0.60005 (17)	0.78483 (14)	0.0134 (4)
H8	0.724573	0.664417	0.840195	0.016*
C9	0.6625 (2)	0.48877 (17)	0.78530 (15)	0.0167 (4)
H9	0.737233	0.47808	0.840651	0.02*
C10	0.5597 (3)	0.39315 (17)	0.70259 (15)	0.0175 (4)
H10	0.566006	0.317648	0.70063	0.021*
C11	0.4471 (2)	0.41157 (16)	0.62266 (15)	0.0153 (4)
H11	0.37664	0.348031	0.566469	0.018*
C12	0.4389 (2)	0.52483 (16)	0.62615 (14)	0.0112 (3)
C13	0.1550 (3)	0.57976 (18)	0.94959 (15)	0.0176 (4)
C14	0.1860 (2)	0.66267 (16)	0.88152 (14)	0.0128 (4)
C15	0.3053 (2)	0.66650 (16)	0.83096 (14)	0.0122 (4)
H15	0.363082	0.614479	0.838132	0.015*
C16	0.3375 (2)	0.74788 (16)	0.77005 (13)	0.0098 (3)
C17	0.2417 (2)	0.82202 (16)	0.75755 (14)	0.0108 (3)
C18	0.1194 (2)	0.81540 (17)	0.80579 (14)	0.0133 (4)
H18	0.055266	0.863072	0.795451	0.016*
C19	0.0948 (2)	0.73674 (16)	0.86940 (14)	0.0143 (4)
H19	0.016858	0.733882	0.903893	0.017*
C20	0.5027 (2)	1.00524 (16)	0.62983 (14)	0.0120 (4)
H20	0.605771	1.014028	0.61919	0.014*
C21	0.4188 (2)	1.07846 (16)	0.59468 (14)	0.0141 (4)
H21	0.464917	1.135452	0.560855	0.017*
C22	0.2647 (2)	1.06543 (17)	0.61075 (14)	0.0157 (4)
H22	0.204513	1.111646	0.585708	0.019*
C23	0.2021 (2)	0.98295 (17)	0.66440 (14)	0.0145 (4)
H23	0.100937	0.97487	0.67742	0.017*
C24	0.2915 (2)	0.91196 (16)	0.69888 (14)	0.0111 (3)
C25	0.6344 (2)	0.96111 (17)	0.94371 (14)	0.0157 (4)
H25A	0.559874	0.894382	0.96093	0.024*
H25B	0.570208	1.004318	0.911162	0.024*
H25C	0.722715	1.014181	1.004546	0.024*
C26	0.8560 (2)	1.04751 (17)	0.84339 (15)	0.0164 (4)
H26A	0.94507	1.092567	0.906542	0.025*
H26B	0.786226	1.092503	0.823195	0.025*
H26C	0.905534	1.033313	0.791846	0.025*
C27	0.5454 (3)	0.76301 (18)	0.12214 (16)	0.0216 (4)
C28	0.6709 (3)	0.7132 (2)	0.1106 (2)	0.0364 (6)
H28A	0.723039	0.747741	0.063586	0.055*
H28B	0.615895	0.62727	0.085237	0.055*
H28C	0.756838	0.731849	0.175519	0.055*
Cl1	0.74293 (5)	0.83320 (4)	0.62149 (3)	0.01155 (8)
Ir1	0.51788 (2)	0.78209 (2)	0.70247 (2)	0.00795 (2)
N1	0.54447 (18)	0.61957 (13)	0.70713 (11)	0.0097 (3)
N2	0.43895 (18)	0.92185 (13)	0.67888 (11)	0.0097 (3)
N3	0.4464 (3)	0.80168 (17)	0.13125 (15)	0.0286 (4)
O1	−0.0021 (2)	0.76266 (15)	0.33564 (13)	0.0390 (4)
O2	0.21023 (19)	0.50165 (13)	0.95953 (12)	0.0254 (3)
O3	0.84599 (17)	0.85806 (12)	0.92054 (10)	0.0171 (3)
S1	0.72772 (6)	0.90632 (4)	0.85936 (3)	0.01024 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0214 (11)	0.0248 (12)	0.0157 (11)	0.0071 (9)	−0.0064 (9)	−0.0016 (9)
C2	0.0133 (9)	0.0191 (10)	0.0105 (9)	0.0047 (8)	0.0002 (7)	0.0014 (8)
C3	0.0139 (9)	0.0122 (9)	0.0120 (9)	0.0044 (7)	0.0025 (7)	0.0009 (7)
C4	0.0090 (8)	0.0121 (8)	0.0086 (8)	0.0029 (7)	0.0042 (7)	0.0018 (7)
C5	0.0110 (8)	0.0134 (9)	0.0089 (9)	0.0030 (7)	0.0032 (7)	0.0018 (7)
C6	0.0161 (9)	0.0110 (9)	0.0128 (9)	0.0017 (7)	0.0024 (8)	−0.0008 (7)
C7	0.0147 (9)	0.0165 (10)	0.0096 (9)	0.0012 (8)	−0.0010 (7)	−0.0022 (7)
C8	0.0123 (9)	0.0137 (9)	0.0116 (9)	0.0046 (7)	0.0007 (7)	0.0018 (7)
C9	0.0192 (10)	0.0158 (10)	0.0149 (10)	0.0082 (8)	0.0020 (8)	0.0056 (8)
C10	0.0227 (10)	0.0124 (9)	0.0184 (10)	0.0075 (8)	0.0069 (8)	0.0050 (8)
C11	0.0191 (10)	0.0101 (9)	0.0127 (9)	0.0024 (7)	0.0040 (8)	0.0002 (7)
C12	0.0111 (8)	0.0125 (9)	0.0085 (9)	0.0029 (7)	0.0033 (7)	0.0011 (7)
C13	0.0199 (10)	0.0180 (10)	0.0151 (10)	0.0048 (8)	0.0089 (8)	0.0043 (8)
C14	0.0124 (9)	0.0130 (9)	0.0084 (9)	0.0012 (7)	0.0015 (7)	0.0007 (7)
C15	0.0112 (8)	0.0124 (9)	0.0098 (9)	0.0033 (7)	0.0007 (7)	0.0008 (7)
C16	0.0094 (8)	0.0086 (8)	0.0070 (8)	0.0032 (7)	−0.0019 (7)	−0.0025 (7)
C17	0.0088 (8)	0.0112 (8)	0.0080 (8)	0.0019 (7)	−0.0005 (7)	−0.0008 (7)
C18	0.0092 (8)	0.0154 (9)	0.0131 (9)	0.0052 (7)	0.0010 (7)	0.0000 (7)
C19	0.0106 (9)	0.0160 (9)	0.0133 (9)	0.0020 (7)	0.0044 (7)	0.0003 (7)
C20	0.0127 (9)	0.0114 (9)	0.0089 (9)	0.0024 (7)	0.0021 (7)	0.0011 (7)
C21	0.0194 (9)	0.0103 (9)	0.0099 (9)	0.0044 (7)	0.0023 (7)	0.0023 (7)
C22	0.0184 (10)	0.0141 (9)	0.0132 (9)	0.0093 (8)	−0.0008 (8)	0.0024 (8)
C23	0.0122 (9)	0.0161 (9)	0.0135 (9)	0.0063 (7)	0.0016 (7)	0.0009 (8)
C24	0.0111 (8)	0.0103 (8)	0.0083 (9)	0.0031 (7)	0.0005 (7)	−0.0014 (7)
C25	0.0198 (10)	0.0157 (9)	0.0099 (9)	0.0069 (8)	0.0044 (8)	−0.0015 (7)
C26	0.0152 (9)	0.0126 (9)	0.0154 (10)	0.0006 (7)	0.0029 (8)	0.0007 (8)
C27	0.0265 (11)	0.0167 (10)	0.0151 (10)	0.0054 (9)	−0.0007 (9)	0.0057 (8)
C28	0.0377 (14)	0.0438 (15)	0.0351 (15)	0.0235 (12)	0.0108 (12)	0.0149 (12)
Cl1	0.01124 (19)	0.0134 (2)	0.0103 (2)	0.00477 (16)	0.00389 (16)	0.00282 (16)
Ir1	0.00779 (4)	0.00810 (4)	0.00644 (4)	0.00263 (3)	0.00083 (3)	0.00086 (3)
N1	0.0098 (7)	0.0095 (7)	0.0091 (7)	0.0035 (6)	0.0024 (6)	0.0017 (6)
N2	0.0107 (7)	0.0096 (7)	0.0065 (7)	0.0032 (6)	0.0008 (6)	0.0004 (6)
N3	0.0378 (11)	0.0250 (10)	0.0226 (10)	0.0156 (9)	0.0042 (9)	0.0067 (8)
O1	0.0454 (11)	0.0286 (9)	0.0291 (10)	0.0197 (8)	−0.0143 (8)	0.0008 (8)
O2	0.0343 (9)	0.0235 (8)	0.0257 (9)	0.0135 (7)	0.0150 (7)	0.0131 (7)
O3	0.0172 (7)	0.0168 (7)	0.0129 (7)	0.0100 (6)	−0.0048 (6)	−0.0009 (6)
S1	0.0108 (2)	0.0099 (2)	0.0079 (2)	0.00406 (16)	0.00035 (16)	0.00033 (16)

Geometric parameters (Å, º) top

C1—O1	1.211 (3)	C16—C17	1.416 (2)
C1—C2	1.477 (3)	C16—Ir1	2.0077 (18)
C2—C7	1.391 (3)	C17—C18	1.398 (2)
C2—C3	1.400 (3)	C17—C24	1.469 (2)
C3—C4	1.396 (3)	C18—C19	1.390 (3)
C4—C5	1.402 (3)	C20—N2	1.346 (2)
C4—Ir1	2.0466 (18)	C20—C21	1.388 (3)
C5—C6	1.397 (3)	C21—C22	1.391 (3)
C5—C12	1.470 (3)	C22—C23	1.383 (3)
C6—C7	1.392 (3)	C23—C24	1.394 (3)
C8—N1	1.351 (2)	C24—N2	1.366 (2)
C8—C9	1.376 (3)	C25—S1	1.7799 (19)
C9—C10	1.381 (3)	C26—S1	1.7870 (19)
C10—C11	1.384 (3)	C27—N3	1.141 (3)
C11—C12	1.390 (3)	C27—C28	1.453 (3)
C12—N1	1.366 (2)	Cl1—Ir1	2.4748 (5)
C13—O2	1.204 (2)	Ir1—N2	2.0609 (15)
C13—C14	1.481 (3)	Ir1—N1	2.0614 (15)
C14—C19	1.384 (3)	Ir1—S1	2.3810 (5)
C14—C15	1.402 (2)	O3—S1	1.4903 (13)
C15—C16	1.392 (2)

O1—C1—C2	125.8 (2)	C20—C21—C22	119.06 (17)
C7—C2—C3	120.72 (18)	C23—C22—C21	119.21 (17)
C7—C2—C1	119.00 (18)	C22—C23—C24	119.65 (17)
C3—C2—C1	120.28 (18)	N2—C24—C23	120.64 (16)
C4—C3—C2	120.47 (18)	N2—C24—C17	113.70 (15)
C3—C4—C5	117.90 (17)	C23—C24—C17	125.66 (16)
C3—C4—Ir1	127.61 (14)	N3—C27—C28	179.7 (2)
C5—C4—Ir1	114.48 (13)	C16—Ir1—C4	89.71 (7)
C6—C5—C4	122.04 (17)	C16—Ir1—N2	80.48 (6)
C6—C5—C12	122.36 (17)	C4—Ir1—N2	89.53 (7)
C4—C5—C12	115.59 (16)	C16—Ir1—N1	93.83 (6)
C7—C6—C5	119.15 (18)	C4—Ir1—N1	79.63 (7)
C2—C7—C6	119.70 (18)	N2—Ir1—N1	167.83 (6)
N1—C8—C9	122.61 (18)	C16—Ir1—S1	90.41 (5)
C8—C9—C10	119.19 (19)	C4—Ir1—S1	179.68 (5)
C9—C10—C11	118.86 (18)	N2—Ir1—S1	90.19 (4)
C10—C11—C12	120.15 (18)	N1—Ir1—S1	100.65 (4)
N1—C12—C11	120.48 (17)	C16—Ir1—Cl1	177.65 (5)
N1—C12—C5	113.96 (16)	C4—Ir1—Cl1	91.58 (5)
C11—C12—C5	125.56 (17)	N2—Ir1—Cl1	97.56 (4)
O2—C13—C14	126.05 (18)	N1—Ir1—Cl1	88.33 (4)
C19—C14—C15	120.78 (17)	S1—Ir1—Cl1	88.295 (18)
C19—C14—C13	118.36 (17)	C8—N1—C12	118.67 (16)
C15—C14—C13	120.86 (17)	C8—N1—Ir1	124.98 (12)
C16—C15—C14	120.26 (17)	C12—N1—Ir1	116.32 (12)
C15—C16—C17	118.19 (16)	C20—N2—C24	119.49 (15)
C15—C16—Ir1	127.48 (13)	C20—N2—Ir1	124.76 (12)
C17—C16—Ir1	114.21 (13)	C24—N2—Ir1	114.59 (11)
C18—C17—C16	121.29 (17)	O3—S1—C25	106.03 (9)
C18—C17—C24	123.30 (17)	O3—S1—C26	107.19 (9)
C16—C17—C24	115.18 (15)	C25—S1—C26	98.72 (9)
C19—C18—C17	119.24 (17)	O3—S1—Ir1	119.58 (6)
C14—C19—C18	120.16 (17)	C25—S1—Ir1	111.64 (7)
N2—C20—C21	121.84 (17)	C26—S1—Ir1	111.52 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···O3ⁱ	0.93	2.48	3.179 (3)	132
C25—H25B···N3ⁱⁱ	0.96	2.53	3.403 (3)	150
C26—H26A···O3ⁱⁱⁱ	0.96	2.48	3.406 (2)	161
C28—H28C···O1^iv	0.96	2.54	3.490 (3)	173

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+2, −z+1; (iii) −x+2, −y+2, −z+2; (iv) x+1, y, z.

Funding information

This work was supported by the Defense Threat Reduction Agency (DTRA) - Joint Science and Technology Transfer Office for Chemical and Biological Defense (MIPR No. HDTRA13964) and the Air Force Office of Scientific Research (AFOSR).

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