[μ-1,4-Bis(di­phenyl­phosphan­yl)butane-κ2P:P′]­bis­{(4-benzyl-2-neopentyl-1,2,4-triazol-3-yl­idene)[(1,2,5,6-η)-cyclo­octa-1,5-diene]iridium(I)} bis­(tetra­fluoro­borate) di­chloro­methane disolvate

Idrees, K.B.; Astashkin, A.V.; Rajaseelan, E.

doi:10.1107/S2414314617010811

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 7| July 2017| x171081

https://doi.org/10.1107/S2414314617010811

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[μ-1,4-Bis(diphenylphosphanyl)butane-κ²P:P′]bis{(4-benzyl-2-neopentyl-1,2,4-triazol-3-ylidene)[(1,2,5,6-η)-cycloocta-1,5-diene]iridium(I)} bis(tetrafluoroborate) dichloromethane disolvate

Karam B. Idrees,^a Andrei V. Astashkin ^b and Edward Rajaseelan ^a ^*

^aDepartment of Chemistry, Millersville University, Millersville, PA 17551, USA, and ^bDepartment of Chemistry and Biochemistry, The University of Arizona, Tucson, AZ 85716, USA
^*Correspondence e-mail: edward.rajaseelan@millersville.edu

Edited by J. Simpson, University of Otago, New Zealand (Received 22 June 2017; accepted 23 July 2017; online 28 July 2017)

The title compound, [Ir₂(C₁₄H₁₉N₃)₂(C₈H₁₂)₂(C₂₈H₂₈P₂)](BF₄)₂·2CH₂Cl₂, has triclinic (P-1) symmetry and the dication lies about an inversion center located at the mid-point of the butane chain of the phosphine ligand. The Ir^I ion has a distorted square-planar coordination geometry. The N-heterocyclic carbene ligand has an extended S-shaped conformation. The diphosphine ligand acts as a bridge between the two metal centers. This is the first structural report of a complex where the square-planar iridium centers are bridged by a phosphine ligand, and it is of interest with respect to catalysis in transfer hydrogenation reactions. Parts of the triazole and cyclooctadiene ligands and the tetrafluoroborate anion are disordered over two sets of sites.

Keywords: crystal structure; iridium complex; bridging phosphine; triazole; cycloocta-1,5-diene.

CCDC reference: 1563999

Structure description

N-heterocyclic carbene complexes are of interest because of their catalytic properties in transfer hydrogenation reactions. The title compound is the first example of a dimer bridged by a chelating phosphine ligand. Transfer hydrogenation of ketones and imines is an encouraging example of an efficient and benign chemical transformation that exemplifies some of the key aspects of green chemistry. N-heterocyclic carbene (NHC) ligands can be tuned sterically and electronically by having different alkyl groups on the nitrogen atoms (Gusev, 2009 ). Many related NHC rhodium and iridium complexes have been synthesized and structurally characterized (Köcher & Herrmann 1997 ; Wang & Lin 1998 ; Chianese et al. 2004 ; Herrmann et al. 2006 ; Nichol et al. 2009 , 2010 , 2011 , 2012 ; Lu et al. 2011 ; Huttenstine et al. 2011 ). Their catalytic activity in transfer hydrogenation reactions have been studied and reported (Hillier et al. 2001 ; Albrecht et al. 2002 ; Gnanamgari et al. 2007 ).

The title dinuclear ionic complex (Fig. 1) comprises two Ir^I cations, two cyclooctadiene ligands, two N-heterocyclic carbene ligands, a diphosphine ligand, two tetrafluoroborate counter-anions, and two dichloromethane solvent molecules. As shown in Fig. 2, the two Ir^I cations are bridged by the diphosphine ligand and the coordination sphere of each Ir^I cation is completed through bonds to cyclooctadiene and the carbene, resulting in a distorted square-planar geometry. Charge balance is achieved by two non-coordinating tetrafluoroborate anions. The carbene atom, C1, deviates from the expected sp² hybridization in that the N1—C1—N3 bond angle is 103.4 (5)^o. Other selected bond lengths [Å] and angles [^o] in the structure are: Ir1—P1 2.3257 (13) Å, Ir1—C1 2.041 (6) Å, and C1—Ir1—P1 89.58 (17)^o.

Figure 1
The structure of the half molecule of the title complex, showing the atom labelling and 30% probability displacement ellipsoids.

Figure 2
The full structure of the title complex with BF₄⁻ counter-ions and CH₂Cl₂ solvent molecules.

Synthesis and crystallization

Unless otherwise stated, all chemicals were purchased from Sigma–Aldrich and used without further purification, in the dark, and under a nitrogen atmosphere. 1-Neopentyl-1,2,4-triazole (2.2 g, 16 mmol) and benzyl bromide (4.0 g, 23 mmol) were refluxed in toluene (15 ml) for 3 d. After cooling, ether (50 ml) was added and the white solid [1] that formed was filtered, washed with ether and air dried (71%). Transmetallation in CH₂Cl₂ (10 ml) with [1] (0.0923 g, 0.298 mmol), Ag₂O (0.0345 g, 0.149 mmol), and [Ir(cod)Cl]₂ (0.100 g, 0.149 mmol), gave a bright-yellow solid [2] (82%). In a round-bottom flask, [2] (0.168 g, 0.298 mmol), 1,4-bis(diphenylphosphino)butane (0.0635 g, 0.149 mmol), and AgBF₄ (0.0580 g, 0.298 mmol) were dissolved in CH₂Cl₂ (15 ml) and stirred for 2 h to obtain a bright-red solid [3] (99%) (Fig. 3). X-ray quality crystals of [3] were grown from CH₂Cl₂/pentane by slow diffusion.

Figure 3
Scheme showing the various steps in the synthesis of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. C and H atoms of the benzyl fragment of the triazole ligand are disordered over two sets of sites with occupancy ratios fixed at 0.5766:0.4234 for the C9 atom and the adjacent atoms of the C8 methylene group and refined to 0.523 (7):0.477 (7) for the CH groups. The atoms of the CH₂ and CH groups of the cyclooctadiene ligand were similarly disordered with refined occupancies 0.541 (16):0.459 (16) while the F atoms of the tetrafluoroborate anion were also disordered over two sets of sites with occupancies 0.731 (16) and 0.269 (16).

Table 1
Experimental details

Crystal data
Chemical formula	[Ir₂(C₁₄H₁₉N₃)₂(C₈H₁₂)₂(C₂₈H₂₈P₂)](BF₄)₂·2CH₂Cl₂
M_r	1829.31
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	10.3518 (5), 11.5088 (5), 17.2483 (8)
α, β, γ (°)	73.540 (1), 87.276 (1), 72.616 (1)
V (Å³)	1879.13 (15)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	3.79
Crystal size (mm)	0.3 × 0.15 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.565, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	37976, 7733, 7082
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.06
No. of reflections	7733
No. of parameters	520
No. of restraints	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.57, −1.27
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1563999

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010811/sj4125sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010811/sj4125Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

[µ-1,4-Bis(diphenylphosphanyl)butane-κ²P:P']bis{(4-benzyl-2-neopentyl-1,2,4-triazol-3-ylidene)[(1,2,5,6-η)-cycloocta-1,5-diene]iridium(I)} bis(tetrafluoroborate) dichloromethane disolvate top

Crystal data top

[Ir₂(C₁₄H₁₉N₃)₂(C₈H₁₂)₂(C₂₈H₂₈P₂)](BF₄)₂·2CH₂Cl₂	Z = 1
M_r = 1829.31	F(000) = 914
Triclinic, P1	D_x = 1.617 Mg m⁻³
a = 10.3518 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.5088 (5) Å	Cell parameters from 9923 reflections
c = 17.2483 (8) Å	θ = 2.4–26.4°
α = 73.540 (1)°	µ = 3.79 mm⁻¹
β = 87.276 (1)°	T = 100 K
γ = 72.616 (1)°	Block, clear pink
V = 1879.13 (15) Å³	0.3 × 0.15 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	7082 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.029
Absorption correction: multi-scan (SADABS; Bruker, 2013)	θ_max = 26.5°, θ_min = 2.0°
T_min = 0.565, T_max = 0.745	h = −12→12
37976 measured reflections	k = −14→14
7733 independent reflections	l = −21→21

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0717P)² + 4.7665P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
7733 reflections	Δρ_max = 2.57 e Å⁻³
520 parameters	Δρ_min = −1.27 e Å⁻³
228 restraints

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	Occ. (<1)
Ir1	0.18525 (2)	0.41927 (2)	0.29265 (2)	0.02912 (8)
P1	0.37397 (14)	0.47225 (13)	0.32136 (8)	0.0334 (3)
Cl1	0.9205 (3)	0.0758 (3)	0.0963 (2)	0.1082 (9)
Cl2	0.7401 (3)	−0.0632 (3)	0.07378 (15)	0.0934 (7)
F1	0.6795 (11)	−0.1208 (10)	0.3272 (6)	0.062 (2)	0.731 (16)
N3	0.3615 (5)	0.2971 (5)	0.1699 (4)	0.0471 (7)
N1	0.3665 (5)	0.1627 (5)	0.2837 (4)	0.0495 (7)
F3	0.7015 (12)	−0.3137 (9)	0.4023 (7)	0.075 (3)	0.731 (16)
C1	0.3074 (6)	0.2862 (6)	0.2429 (4)	0.0467 (7)
N2	0.4563 (5)	0.1863 (5)	0.1644 (4)	0.0504 (7)
C3	0.3355 (6)	0.4109 (6)	0.1036 (4)	0.0439 (13)
H3A	0.4192	0.4369	0.0952	0.053*
H3B	0.2651	0.4789	0.1195	0.053*
C4	0.2893 (7)	0.4028 (8)	0.0223 (4)	0.0572 (17)
C15	0.0631 (6)	0.4869 (6)	0.3879 (3)	0.0380 (12)
H15	0.1186	0.4878	0.4335	0.046*
C16	−0.0418 (6)	0.4187 (6)	0.4151 (3)	0.0413 (12)
H16A	−0.0001	0.3396	0.4582	0.050*	0.541 (16)
H16B	−0.1162	0.4727	0.4391	0.050*	0.541 (16)
H16C	−0.1327	0.4786	0.3966	0.050*	0.459 (16)
H16D	−0.0390	0.3902	0.4750	0.050*	0.459 (16)
C18	0.0132 (7)	0.3455 (8)	0.2892 (5)	0.061 (2)
H18	0.0324	0.2591	0.2816	0.073*	0.541 (16)
H18A	0.0482	0.2662	0.2719	0.073*	0.459 (16)
C19	0.0046 (6)	0.4432 (7)	0.2237 (4)	0.0515 (16)
H19	0.0321	0.4100	0.1758	0.062*	0.541 (16)
H19A	0.0145	0.4275	0.1693	0.062*	0.459 (16)
C22	0.0510 (6)	0.5908 (5)	0.3191 (3)	0.0400 (12)
H22	0.0988	0.6516	0.3253	0.048*
C23	0.3886 (3)	0.6202 (3)	0.25080 (18)	0.0337 (10)
C24	0.2894 (3)	0.6885 (3)	0.1897 (2)	0.0359 (11)
H24	0.2159	0.6576	0.1842	0.043*
C25	0.2978 (3)	0.8021 (3)	0.13685 (18)	0.0439 (13)
H25	0.2301	0.8488	0.0951	0.053*
C26	0.4054 (4)	0.8473 (3)	0.1450 (2)	0.0435 (13)
H26	0.4111	0.9249	0.1089	0.052*
C27	0.5045 (3)	0.7789 (3)	0.2061 (2)	0.0416 (12)
H27	0.5780	0.8098	0.2116	0.050*
C28	0.4961 (3)	0.6654 (3)	0.25896 (18)	0.0377 (11)
H28	0.5639	0.6187	0.3007	0.045*
C29	0.5353 (3)	0.3556 (3)	0.3152 (3)	0.0454 (14)
C30	0.6111 (4)	0.3689 (4)	0.2463 (2)	0.0517 (16)
H30	0.5851	0.4451	0.2031	0.062*
C31	0.7250 (4)	0.2708 (5)	0.2404 (3)	0.075 (3)
H31	0.7768	0.2799	0.1933	0.090*
C32	0.7630 (4)	0.1593 (4)	0.3035 (4)	0.101 (4)
H32	0.8409	0.0923	0.2996	0.121*
C33	0.6872 (5)	0.1460 (3)	0.3724 (4)	0.108 (5)
H33	0.7132	0.0698	0.4155	0.129*
C34	0.5734 (5)	0.2441 (4)	0.3782 (3)	0.070 (2)
H34	0.5215	0.2350	0.4253	0.084*
C35	0.3783 (7)	0.4879 (7)	0.4234 (3)	0.0486 (15)
H35A	0.2989	0.5594	0.4274	0.058*
H35B	0.3654	0.4100	0.4614	0.058*
C36	0.5029 (8)	0.5092 (8)	0.4540 (3)	0.0576 (19)
H36A	0.5061	0.5962	0.4261	0.069*
H36B	0.5860	0.4483	0.4419	0.069*
F2	0.6024 (10)	−0.1457 (9)	0.4512 (5)	0.097 (3)	0.731 (16)
C21	−0.0693 (7)	0.6506 (6)	0.2601 (4)	0.0536 (16)
H21A	−0.0741	0.7406	0.2351	0.064*	0.541 (16)
H21B	−0.1522	0.6494	0.2910	0.064*	0.541 (16)
H21C	−0.1458	0.7001	0.2854	0.064*	0.459 (16)
H21D	−0.0459	0.7098	0.2116	0.064*	0.459 (16)
C2	0.4564 (6)	0.1088 (6)	0.2333 (5)	0.0513 (7)
H2	0.5124	0.0232	0.2485	0.062*
F4	0.8182 (10)	−0.2001 (11)	0.4370 (7)	0.112 (3)	0.731 (16)
B1	0.6976 (7)	−0.1936 (6)	0.4059 (4)	0.0453 (13)
C6	0.2319 (9)	0.5392 (9)	−0.0307 (5)	0.075 (2)
H6A	0.1531	0.5836	−0.0054	0.112*
H6B	0.2045	0.5386	−0.0841	0.112*
H6C	0.3014	0.5829	−0.0365	0.112*
C8	0.3409 (8)	0.0996 (6)	0.3659 (5)	0.069 (2)
H8BC	0.3172	0.1617	0.3978	0.082*	0.4234
H8BD	0.4244	0.0323	0.3910	0.082*	0.4234
H8AA	0.2870	0.1635	0.3923	0.082*	0.5766
H8AB	0.4280	0.0546	0.3970	0.082*	0.5766
C7	0.4088 (9)	0.3341 (10)	−0.0205 (5)	0.072 (2)
H7A	0.4807	0.3748	−0.0255	0.108*
H7B	0.3781	0.3386	−0.0744	0.108*
H7C	0.4437	0.2450	0.0112	0.108*
C5	0.1801 (8)	0.3342 (11)	0.0362 (5)	0.081 (3)
H5A	0.2201	0.2454	0.0672	0.122*
H5B	0.1437	0.3378	−0.0161	0.122*
H5C	0.1069	0.3757	0.0664	0.122*
C9A	0.2192 (12)	0.0373 (11)	0.3687 (8)	0.0662 (12)	0.4234
C10A	0.2247 (12)	−0.0325 (12)	0.3140 (7)	0.0661 (12)	0.477 (7)
H10A	0.2875	−0.0294	0.2721	0.079*	0.477 (7)
C11A	0.1383 (13)	−0.1066 (10)	0.3208 (6)	0.0661 (12)	0.477 (7)
H11A	0.1421	−0.1543	0.2835	0.079*	0.477 (7)
C12A	0.0464 (12)	−0.1111 (10)	0.3822 (7)	0.0662 (12)	0.477 (7)
H12A	−0.0126	−0.1618	0.3869	0.079*	0.477 (7)
C13A	0.0409 (11)	−0.0413 (10)	0.4368 (6)	0.0662 (12)	0.477 (7)
H13A	−0.0219	−0.0443	0.4788	0.079*	0.477 (7)
C14A	0.1273 (12)	0.0329 (10)	0.4301 (7)	0.0661 (13)	0.477 (7)
H14A	0.1235	0.0806	0.4674	0.079*	0.477 (7)
C1S	0.7754 (10)	0.0288 (10)	0.1289 (7)	0.083 (3)
H1SA	0.7892	−0.0201	0.1868	0.099*
H1SB	0.6968	0.1053	0.1238	0.099*
C11	0.1129 (18)	−0.0748 (14)	0.3012 (11)	0.0661 (12)	0.523 (7)
H11	0.0619	−0.0790	0.2582	0.079*	0.523 (7)
C10	0.1955 (17)	0.0033 (15)	0.2921 (11)	0.0661 (12)	0.523 (7)
H10	0.2075	0.0537	0.2398	0.079*	0.523 (7)
C12	0.1145 (17)	−0.1523 (14)	0.3881 (10)	0.0660 (12)	0.523 (7)
H12	0.0587	−0.2070	0.4000	0.079*	0.523 (7)
C14	0.2577 (16)	−0.0702 (13)	0.4341 (10)	0.0663 (13)	0.523 (7)
H14	0.3070	−0.0722	0.4798	0.080*	0.523 (7)
C13	0.1813 (16)	−0.1512 (14)	0.4447 (11)	0.0663 (12)	0.523 (7)
H13	0.1796	−0.2077	0.4968	0.080*	0.523 (7)
C17	−0.1010 (11)	0.3856 (12)	0.3496 (7)	0.045 (3)	0.541 (16)
H17A	−0.1752	0.4596	0.3196	0.054*	0.541 (16)
H17B	−0.1392	0.3147	0.3738	0.054*	0.541 (16)
C20	−0.0713 (15)	0.5901 (13)	0.1928 (9)	0.055 (4)	0.541 (16)
H20A	−0.0261	0.6299	0.1452	0.066*	0.541 (16)
H20B	−0.1661	0.6036	0.1761	0.066*	0.541 (16)
C20A	−0.1114 (12)	0.5542 (14)	0.2355 (10)	0.042 (4)	0.459 (16)
H20C	−0.1662	0.5960	0.1841	0.050*	0.459 (16)
H20D	−0.1704	0.5204	0.2770	0.050*	0.459 (16)
C17A	−0.0199 (13)	0.3041 (13)	0.3827 (9)	0.042 (4)	0.459 (16)
H17C	−0.1023	0.2761	0.3889	0.051*	0.459 (16)
H17D	0.0564	0.2328	0.4131	0.051*	0.459 (16)
F1A	0.733 (3)	−0.123 (3)	0.3307 (15)	0.054 (5)	0.269 (16)
F4A	0.740 (3)	−0.1544 (18)	0.4651 (11)	0.079 (6)	0.269 (16)
F3A	0.749 (2)	−0.3176 (18)	0.4242 (15)	0.056 (5)	0.269 (16)
F2A	0.5535 (19)	−0.1685 (19)	0.4151 (16)	0.076 (6)	0.269 (16)
C9	0.2672 (11)	0.0085 (9)	0.3663 (8)	0.052 (3)	0.5766

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir1	0.03192 (12)	0.03271 (12)	0.02558 (12)	−0.01251 (8)	−0.00290 (7)	−0.00892 (8)
P1	0.0385 (7)	0.0366 (7)	0.0277 (6)	−0.0193 (5)	−0.0084 (5)	−0.0029 (5)
Cl1	0.0738 (15)	0.137 (2)	0.116 (2)	−0.0331 (16)	0.0187 (14)	−0.0393 (19)
Cl2	0.127 (2)	0.0869 (15)	0.0653 (13)	−0.0450 (15)	0.0017 (13)	−0.0063 (11)
F1	0.081 (6)	0.042 (3)	0.053 (3)	−0.012 (5)	−0.013 (4)	−0.004 (2)
N3	0.0329 (13)	0.0434 (14)	0.0710 (18)	−0.0071 (11)	−0.0022 (12)	−0.0292 (13)
N1	0.0349 (13)	0.0440 (14)	0.0730 (18)	−0.0065 (11)	−0.0044 (13)	−0.0263 (13)
F3	0.100 (7)	0.059 (4)	0.084 (7)	−0.046 (4)	0.030 (5)	−0.029 (4)
C1	0.0324 (13)	0.0432 (14)	0.0705 (18)	−0.0078 (11)	−0.0037 (13)	−0.0282 (13)
N2	0.0350 (13)	0.0453 (14)	0.0741 (18)	−0.0056 (11)	−0.0019 (13)	−0.0278 (13)
C3	0.039 (3)	0.054 (3)	0.047 (3)	−0.016 (3)	0.004 (2)	−0.025 (3)
C4	0.048 (3)	0.092 (5)	0.051 (4)	−0.030 (3)	0.007 (3)	−0.041 (4)
C15	0.050 (3)	0.047 (3)	0.030 (3)	−0.024 (3)	0.015 (2)	−0.024 (2)
C16	0.044 (3)	0.053 (3)	0.037 (3)	−0.025 (3)	0.014 (2)	−0.019 (2)
C18	0.055 (4)	0.102 (6)	0.074 (5)	−0.061 (4)	0.031 (3)	−0.063 (5)
C19	0.031 (3)	0.069 (4)	0.062 (4)	−0.005 (3)	−0.016 (3)	−0.038 (4)
C22	0.051 (3)	0.033 (3)	0.041 (3)	−0.012 (2)	0.008 (2)	−0.021 (2)
C23	0.044 (3)	0.032 (2)	0.029 (2)	−0.015 (2)	0.003 (2)	−0.010 (2)
C24	0.041 (3)	0.035 (3)	0.031 (3)	−0.011 (2)	0.004 (2)	−0.009 (2)
C25	0.058 (3)	0.037 (3)	0.031 (3)	−0.008 (3)	0.001 (2)	−0.007 (2)
C26	0.062 (4)	0.032 (3)	0.037 (3)	−0.018 (3)	0.016 (3)	−0.008 (2)
C27	0.053 (3)	0.044 (3)	0.038 (3)	−0.026 (3)	0.011 (2)	−0.017 (2)
C28	0.043 (3)	0.041 (3)	0.035 (3)	−0.019 (2)	0.005 (2)	−0.014 (2)
C29	0.038 (3)	0.039 (3)	0.061 (4)	−0.019 (2)	−0.020 (3)	−0.006 (3)
C30	0.039 (3)	0.045 (3)	0.076 (5)	−0.011 (2)	−0.016 (3)	−0.022 (3)
C31	0.039 (3)	0.072 (5)	0.126 (8)	−0.005 (3)	−0.021 (4)	−0.052 (5)
C32	0.045 (4)	0.052 (5)	0.209 (13)	0.008 (4)	−0.062 (6)	−0.052 (6)
C33	0.056 (5)	0.041 (4)	0.205 (13)	−0.017 (4)	−0.066 (7)	0.014 (6)
C34	0.052 (4)	0.042 (3)	0.103 (6)	−0.021 (3)	−0.036 (4)	0.014 (4)
C35	0.068 (4)	0.068 (4)	0.024 (3)	−0.049 (3)	−0.008 (2)	−0.002 (2)
C36	0.078 (5)	0.088 (5)	0.026 (3)	−0.065 (4)	−0.010 (3)	−0.002 (3)
F2	0.089 (6)	0.097 (6)	0.081 (5)	0.020 (4)	0.011 (4)	−0.038 (4)
C21	0.053 (4)	0.044 (3)	0.052 (4)	0.002 (3)	−0.004 (3)	−0.011 (3)
C2	0.0359 (13)	0.0451 (14)	0.0750 (18)	−0.0055 (12)	−0.0033 (13)	−0.0265 (13)
F4	0.072 (5)	0.148 (8)	0.118 (7)	−0.031 (5)	−0.033 (4)	−0.038 (6)
B1	0.049 (3)	0.032 (3)	0.050 (3)	−0.006 (2)	−0.005 (2)	−0.008 (2)
C6	0.066 (5)	0.112 (7)	0.043 (4)	−0.020 (5)	−0.003 (3)	−0.025 (4)
C8	0.079 (5)	0.035 (3)	0.080 (5)	−0.015 (3)	−0.032 (4)	0.006 (3)
C7	0.069 (5)	0.106 (7)	0.064 (5)	−0.038 (5)	0.022 (4)	−0.050 (5)
C5	0.065 (5)	0.156 (9)	0.066 (5)	−0.064 (5)	0.019 (4)	−0.068 (6)
C9A	0.070 (3)	0.049 (3)	0.077 (3)	−0.017 (2)	0.002 (2)	−0.014 (2)
C10A	0.070 (3)	0.049 (3)	0.077 (3)	−0.017 (2)	0.002 (2)	−0.014 (2)
C11A	0.070 (3)	0.049 (3)	0.077 (3)	−0.017 (2)	0.002 (2)	−0.014 (2)
C12A	0.070 (3)	0.049 (3)	0.077 (3)	−0.018 (2)	0.002 (2)	−0.014 (2)
C13A	0.070 (3)	0.049 (3)	0.077 (3)	−0.017 (2)	0.002 (2)	−0.014 (2)
C14A	0.070 (3)	0.049 (3)	0.077 (3)	−0.017 (2)	0.002 (2)	−0.014 (2)
C1S	0.075 (6)	0.079 (6)	0.087 (7)	−0.015 (5)	0.011 (5)	−0.022 (5)
C11	0.070 (3)	0.049 (3)	0.077 (3)	−0.017 (2)	0.002 (2)	−0.014 (2)
C10	0.070 (3)	0.049 (3)	0.077 (3)	−0.017 (2)	0.002 (2)	−0.014 (2)
C12	0.070 (3)	0.049 (3)	0.077 (3)	−0.018 (2)	0.002 (2)	−0.014 (2)
C14	0.070 (3)	0.049 (3)	0.077 (3)	−0.018 (2)	0.002 (2)	−0.014 (2)
C13	0.070 (3)	0.049 (3)	0.077 (3)	−0.018 (2)	0.002 (2)	−0.013 (2)
C17	0.034 (6)	0.059 (8)	0.050 (7)	−0.021 (6)	0.011 (5)	−0.021 (6)
C20	0.050 (7)	0.058 (8)	0.042 (8)	0.000 (6)	−0.008 (6)	−0.007 (6)
C20A	0.021 (5)	0.055 (8)	0.040 (8)	0.003 (5)	−0.008 (5)	−0.012 (7)
C17A	0.033 (7)	0.049 (8)	0.058 (8)	−0.025 (6)	0.012 (6)	−0.022 (6)
F1A	0.062 (12)	0.035 (7)	0.051 (6)	−0.005 (9)	0.001 (7)	−0.001 (5)
F4A	0.125 (14)	0.057 (9)	0.055 (7)	−0.040 (9)	−0.010 (7)	−0.001 (6)
F3A	0.066 (11)	0.030 (5)	0.051 (10)	0.001 (5)	0.016 (7)	0.001 (4)
F2A	0.059 (6)	0.064 (9)	0.089 (13)	−0.010 (5)	0.004 (6)	−0.008 (8)
C9	0.043 (5)	0.028 (5)	0.065 (7)	−0.005 (4)	−0.024 (5)	0.016 (5)

Geometric parameters (Å, º) top

Ir1—P1	2.3257 (13)	C34—H34	0.9500
Ir1—C1	2.041 (6)	C35—H35A	0.9900
Ir1—C15	2.200 (5)	C35—H35B	0.9900
Ir1—C18	2.200 (5)	C35—C36	1.526 (8)
Ir1—C19	2.169 (5)	C36—C36ⁱ	1.541 (11)
Ir1—C22	2.202 (5)	C36—H36A	0.9900
P1—C23	1.834 (3)	C36—H36B	0.9900
P1—C29	1.824 (3)	F2—B1	1.317 (10)
P1—C35	1.824 (6)	C21—H21A	0.9900
Cl1—C1S	1.760 (10)	C21—H21B	0.9900
Cl2—C1S	1.731 (11)	C21—H21C	0.9900
F1—B1	1.366 (11)	C21—H21D	0.9900
N3—C1	1.342 (9)	C21—C20	1.518 (15)
N3—N2	1.383 (7)	C21—C20A	1.475 (16)
N3—C3	1.437 (8)	C2—H2	0.9500
N1—C1	1.357 (8)	F4—B1	1.355 (10)
N1—C2	1.375 (8)	B1—F1A	1.42 (2)
N1—C8	1.451 (10)	B1—F4A	1.36 (2)
F3—B1	1.390 (10)	B1—F3A	1.31 (2)
N2—C2	1.268 (9)	B1—F2A	1.44 (2)
C3—H3A	0.9900	C6—H6A	0.9800
C3—H3B	0.9900	C6—H6B	0.9800
C3—C4	1.538 (8)	C6—H6C	0.9800
C4—C6	1.528 (12)	C8—H8BC	0.9900
C4—C7	1.536 (10)	C8—H8BD	0.9900
C4—C5	1.536 (10)	C8—H8AA	0.9900
C15—H15	1.0000	C8—H8AB	0.9900
C15—C16	1.505 (7)	C8—C9A	1.618 (11)
C15—C22	1.404 (8)	C8—C9	1.467 (13)
C16—H16A	0.9900	C7—H7A	0.9800
C16—H16B	0.9900	C7—H7B	0.9800
C16—H16C	0.9900	C7—H7C	0.9800
C16—H16D	0.9900	C5—H5A	0.9800
C16—C17	1.499 (13)	C5—H5B	0.9800
C16—C17A	1.527 (14)	C5—H5C	0.9800
C18—H18	1.0000	C9A—C10A	1.3900
C18—H18A	1.0000	C9A—C14A	1.3900
C18—C19	1.334 (11)	C10A—H10A	0.9500
C18—C17	1.589 (12)	C10A—C11A	1.3900
C18—C17A	1.597 (15)	C11A—H11A	0.9500
C19—H19	1.0000	C11A—C12A	1.3900
C19—H19A	1.0000	C12A—H12A	0.9500
C19—C20	1.579 (14)	C12A—C13A	1.3900
C19—C20A	1.523 (13)	C13A—H13A	0.9500
C22—H22	1.0000	C13A—C14A	1.3900
C22—C21	1.507 (9)	C14A—H14A	0.9500
C23—C24	1.3900	C1S—H1SA	0.9900
C23—C28	1.3900	C1S—H1SB	0.9900
C24—H24	0.9500	C11—H11	0.9500
C24—C25	1.3900	C11—C10	1.39 (2)
C25—H25	0.9500	C11—C12	1.51 (2)
C25—C26	1.3900	C10—H10	0.9500
C26—H26	0.9500	C10—C9	1.53 (2)
C26—C27	1.3900	C12—H12	0.9500
C27—H27	0.9500	C12—C13	1.23 (2)
C27—C28	1.3900	C14—H14	0.9500
C28—H28	0.9500	C14—C13	1.36 (2)
C29—C30	1.3900	C14—C9	1.281 (19)
C29—C34	1.3900	C13—H13	0.9500
C30—H30	0.9500	C17—H17A	0.9900
C30—C31	1.3900	C17—H17B	0.9900
C31—H31	0.9500	C20—H20A	0.9900
C31—C32	1.3900	C20—H20B	0.9900
C32—H32	0.9500	C20A—H20C	0.9900
C32—C33	1.3900	C20A—H20D	0.9900
C33—H33	0.9500	C17A—H17C	0.9900
C33—C34	1.3900	C17A—H17D	0.9900

C1—Ir1—P1	89.58 (17)	C36—C35—H35B	107.5
C1—Ir1—C15	155.3 (3)	C35—C36—C36ⁱ	109.7 (6)
C1—Ir1—C18	91.4 (2)	C35—C36—H36A	109.7
C1—Ir1—C19	94.6 (2)	C35—C36—H36B	109.7
C1—Ir1—C22	167.4 (3)	C36ⁱ—C36—H36A	109.7
C15—Ir1—P1	94.96 (16)	C36ⁱ—C36—H36B	109.7
C15—Ir1—C22	37.2 (2)	H36A—C36—H36B	108.2
C18—Ir1—P1	169.1 (2)	C22—C21—H21A	108.1
C18—Ir1—C15	79.8 (2)	C22—C21—H21B	108.1
C18—Ir1—C22	91.2 (3)	C22—C21—H21C	109.3
C19—Ir1—P1	155.1 (2)	C22—C21—H21D	109.3
C19—Ir1—C15	91.5 (2)	C22—C21—C20	116.7 (6)
C19—Ir1—C18	35.6 (3)	H21A—C21—H21B	107.3
C19—Ir1—C22	80.5 (2)	H21C—C21—H21D	108.0
C22—Ir1—P1	90.23 (16)	C20—C21—H21A	108.1
C23—P1—Ir1	113.07 (11)	C20—C21—H21B	108.1
C29—P1—Ir1	114.12 (14)	C20A—C21—C22	111.6 (7)
C29—P1—C23	103.84 (18)	C20A—C21—H21C	109.3
C35—P1—Ir1	113.3 (2)	C20A—C21—H21D	109.3
C35—P1—C23	107.4 (2)	N1—C2—H2	123.8
C35—P1—C29	104.2 (3)	N2—C2—N1	112.4 (6)
C1—N3—N2	112.9 (5)	N2—C2—H2	123.8
C1—N3—C3	126.3 (5)	F1—B1—F3	104.7 (9)
N2—N3—C3	120.6 (5)	F2—B1—F1	111.6 (8)
C1—N1—C2	107.6 (6)	F2—B1—F3	114.1 (9)
C1—N1—C8	126.2 (6)	F2—B1—F4	107.4 (8)
C2—N1—C8	126.2 (6)	F4—B1—F1	110.2 (8)
N3—C1—Ir1	131.2 (5)	F4—B1—F3	108.8 (8)
N3—C1—N1	103.4 (5)	F1A—B1—F2A	113.7 (13)
N1—C1—Ir1	124.9 (5)	F4A—B1—F1A	107.3 (15)
C2—N2—N3	103.6 (5)	F4A—B1—F2A	104.4 (16)
N3—C3—H3A	108.2	F3A—B1—F1A	116.6 (17)
N3—C3—H3B	108.2	F3A—B1—F4A	107.5 (14)
N3—C3—C4	116.5 (5)	F3A—B1—F2A	106.4 (14)
H3A—C3—H3B	107.3	C4—C6—H6A	109.5
C4—C3—H3A	108.2	C4—C6—H6B	109.5
C4—C3—H3B	108.2	C4—C6—H6C	109.5
C6—C4—C3	106.7 (6)	H6A—C6—H6B	109.5
C6—C4—C7	108.3 (7)	H6A—C6—H6C	109.5
C6—C4—C5	110.5 (7)	H6B—C6—H6C	109.5
C7—C4—C3	111.5 (6)	N1—C8—H8BC	109.3
C5—C4—C3	109.8 (6)	N1—C8—H8BD	109.3
C5—C4—C7	110.0 (7)	N1—C8—H8AA	109.5
Ir1—C15—H15	113.5	N1—C8—H8AB	109.5
C16—C15—Ir1	111.3 (3)	N1—C8—C9A	111.7 (7)
C16—C15—H15	113.5	N1—C8—C9	110.6 (8)
C22—C15—Ir1	71.5 (3)	H8BC—C8—H8BD	107.9
C22—C15—H15	113.5	H8AA—C8—H8AB	108.1
C22—C15—C16	125.8 (6)	C9A—C8—H8BC	109.3
C15—C16—H16A	108.6	C9A—C8—H8BD	109.3
C15—C16—H16B	108.6	C9—C8—H8AA	109.5
C15—C16—H16C	109.1	C9—C8—H8AB	109.5
C15—C16—H16D	109.1	C4—C7—H7A	109.5
C15—C16—C17A	112.6 (6)	C4—C7—H7B	109.5
H16A—C16—H16B	107.5	C4—C7—H7C	109.5
H16C—C16—H16D	107.8	H7A—C7—H7B	109.5
C17—C16—C15	114.8 (6)	H7A—C7—H7C	109.5
C17—C16—H16A	108.6	H7B—C7—H7C	109.5
C17—C16—H16B	108.6	C4—C5—H5A	109.5
C17A—C16—H16C	109.1	C4—C5—H5B	109.5
C17A—C16—H16D	109.1	C4—C5—H5C	109.5
Ir1—C18—H18	118.1	H5A—C5—H5B	109.5
Ir1—C18—H18A	107.2	H5A—C5—H5C	109.5
C19—C18—Ir1	71.0 (3)	H5B—C5—H5C	109.5
C19—C18—H18	118.1	C10A—C9A—C8	116.0 (8)
C19—C18—H18A	107.2	C10A—C9A—C14A	120.0
C19—C18—C17	109.8 (8)	C14A—C9A—C8	123.1 (8)
C19—C18—C17A	145.3 (8)	C9A—C10A—H10A	120.0
C17—C18—Ir1	112.9 (5)	C9A—C10A—C11A	120.0
C17—C18—H18	118.1	C11A—C10A—H10A	120.0
C17A—C18—Ir1	102.2 (5)	C10A—C11A—H11A	120.0
C17A—C18—H18A	107.2	C12A—C11A—C10A	120.0
Ir1—C19—H19	108.9	C12A—C11A—H11A	120.0
Ir1—C19—H19A	118.9	C11A—C12A—H12A	120.0
C18—C19—Ir1	73.5 (4)	C11A—C12A—C13A	120.0
C18—C19—H19	108.9	C13A—C12A—H12A	120.0
C18—C19—H19A	118.9	C12A—C13A—H13A	120.0
C18—C19—C20	139.3 (9)	C12A—C13A—C14A	120.0
C18—C19—C20A	107.0 (9)	C14A—C13A—H13A	120.0
C20—C19—Ir1	107.7 (6)	C9A—C14A—H14A	120.0
C20—C19—H19	108.9	C13A—C14A—C9A	120.0
C20A—C19—Ir1	110.9 (6)	C13A—C14A—H14A	120.0
C20A—C19—H19A	118.9	Cl1—C1S—H1SA	109.1
Ir1—C22—H22	114.0	Cl1—C1S—H1SB	109.1
C15—C22—Ir1	71.3 (3)	Cl2—C1S—Cl1	112.4 (6)
C15—C22—H22	114.0	Cl2—C1S—H1SA	109.1
C15—C22—C21	125.0 (6)	Cl2—C1S—H1SB	109.1
C21—C22—Ir1	110.5 (4)	H1SA—C1S—H1SB	107.9
C21—C22—H22	114.0	C10—C11—H11	124.3
C24—C23—P1	119.40 (18)	C10—C11—C12	111.3 (15)
C24—C23—C28	120.0	C12—C11—H11	124.3
C28—C23—P1	120.59 (18)	C11—C10—H10	119.9
C23—C24—H24	120.0	C11—C10—C9	120.3 (14)
C25—C24—C23	120.0	C9—C10—H10	119.9
C25—C24—H24	120.0	C11—C12—H12	117.0
C24—C25—H25	120.0	C13—C12—C11	125.9 (16)
C26—C25—C24	120.0	C13—C12—H12	117.0
C26—C25—H25	120.0	C13—C14—H14	118.0
C25—C26—H26	120.0	C9—C14—H14	118.0
C25—C26—C27	120.0	C9—C14—C13	124.0 (16)
C27—C26—H26	120.0	C12—C13—C14	121.1 (17)
C26—C27—H27	120.0	C12—C13—H13	119.5
C28—C27—C26	120.0	C14—C13—H13	119.5
C28—C27—H27	120.0	C16—C17—C18	109.8 (7)
C23—C28—H28	120.0	C16—C17—H17A	109.7
C27—C28—C23	120.0	C16—C17—H17B	109.7
C27—C28—H28	120.0	C18—C17—H17A	109.7
C30—C29—P1	122.0 (2)	C18—C17—H17B	109.7
C30—C29—C34	120.0	H17A—C17—H17B	108.2
C34—C29—P1	117.6 (2)	C19—C20—H20A	109.8
C29—C30—H30	120.0	C19—C20—H20B	109.8
C31—C30—C29	120.0	C21—C20—C19	109.4 (9)
C31—C30—H30	120.0	C21—C20—H20A	109.8
C30—C31—H31	120.0	C21—C20—H20B	109.8
C30—C31—C32	120.0	H20A—C20—H20B	108.2
C32—C31—H31	120.0	C19—C20A—H20C	108.5
C31—C32—H32	120.0	C19—C20A—H20D	108.5
C33—C32—C31	120.0	C21—C20A—C19	114.9 (9)
C33—C32—H32	120.0	C21—C20A—H20C	108.5
C32—C33—H33	120.0	C21—C20A—H20D	108.5
C32—C33—C34	120.0	H20C—C20A—H20D	107.5
C34—C33—H33	120.0	C16—C17A—C18	107.9 (9)
C29—C34—H34	120.0	C16—C17A—H17C	110.1
C33—C34—C29	120.0	C16—C17A—H17D	110.1
C33—C34—H34	120.0	C18—C17A—H17C	110.1
P1—C35—H35A	107.5	C18—C17A—H17D	110.1
P1—C35—H35B	107.5	H17C—C17A—H17D	108.4
H35A—C35—H35B	107.0	C8—C9—C10	125.0 (10)
C36—C35—P1	119.3 (5)	C14—C9—C8	117.9 (12)
C36—C35—H35A	107.5	C14—C9—C10	117.1 (13)

Symmetry code: (i) −x+1, −y+1, −z+1.

Funding information

KI gratefully acknowledges support by a Neimeyer–Hodgson research grant and a Millersville University student research grant.

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