mer-Hydridotris(tri­methyl­phosphane-κP)(d-valinato-κ2N,O)iridium hexa­fluorido­phosphate di­chloro­methane 0.675-solvate

Merola, J.S.; Slebodnick, C.; Berg, M.; Ritchie, M.K.

doi:10.1107/S1600536814002165

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 3| March 2014| Page m82

doi:10.1107/S1600536814002165

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mer-Hydridotris(trimethylphosphane-κP)(D-valinato-κ²N,O)iridium hexafluoridophosphate dichloromethane 0.675-solvate

Joseph S. Merola,^a ^* Carla Slebodnick,^a Michael Berg ^a and Melissa K. Ritchie ^a

^aDepartment of Chemistry, Virginia Tech, Blacksburg, VA 24061, USA
^*Correspondence e-mail: jmerola@vt.edu

(Received 21 January 2014; accepted 29 January 2014; online 5 February 2014)

The title compound, [Ir(C₅H₁₀NO₂)H(C₃H₉P)₃]PF₆·0.675CH₂Cl₂, an iridium compound with a meridional arrangement of PMe₃ groups, O,N-bidentate coordination of D-valine and with a hydride ligand trans to the N atom is compared with the L-valine complex reported previously. As expected, the complexes from the corresponding L and D isomers of valine crystallize in enantiomorphic space groups (P4₃ and P4₁, respectively). In the crystal, N—H⋯O and N—H⋯F hydrogen bonding is observed, the N—H to carbonyl oxygen hydrogen bond producing a helical motif that proceeds along the 4₁ screw of the c axis.

CCDC reference: 984214

Related literature

The structure of the related L-valine complex has been described by Roy et al. (2006 ). For studies of hydrogen-bonded lattice systems that lose crystallinity on loss of solvent and an analogous one that retains crystallinity, see: Parkin & Behrman (2009 , 2011 ). An analysis of the geometric paramaters for hydrogen bonds is given by Wood et al. (2009 ).

Experimental

Crystal data

[Ir(C₅H₁₀NO₂)H(C₃H₉P)₃]PF₆·0.675CH₂Cl₂
M_r = 739.86
Tetragonal, P 4₁
a = 14.04454 (17) Å
c = 14.2657 (3) Å
V = 2813.89 (9) Å³
Z = 4
Mo Kα radiation
μ = 5.15 mm⁻¹
T = 100 K
0.17 × 0.05 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur2 (Eos, Gemini ultra) diffractometer
Absorption correction: gaussian (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.449, T_max = 0.774
39354 measured reflections
9371 independent reflections
7266 reflections with I > 2σ(I)
R_int = 0.069

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.046
S = 0.81
9371 reflections
301 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.61 e Å⁻³
Absolute structure: Flack parameter determined using 3004 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter: −0.021 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯F1	0.92 (6)	2.39 (6)	3.157 (7)	140 (5)
N1—H1B⋯O2ⁱ	0.83 (6)	2.02 (6)	2.848 (7)	172 (6)
Symmetry code: (i) $[y, -x, z-{\script{1\over 4}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

CCDC reference: 984214

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814002165/pk2516sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814002165/pk2516Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814002165/pk2516Isup3.mol

checkCIF report

Comment top

Both the D– and L-Valine complexes of the type [HIr(AA)(PMe₃)₃][PF₆] crystallize in primitive tetragonal space groups, with the L–valine complex in P4₃ and the D-valine complex in the enantiomorphic group P4₁. The former structure was measured at room temperature on a Siemens P4 diffractometer while the latter was measured on an Oxford Diffraction instrument at 100 K. Accounting for room temperature vs. 100 K, the unit-cell parameters are essentially the same. Figure 1 shows a thermal ellipsoid plot of the asymmetric unit of the title compound. N—H to carbonyl oxygen hydrogen bonding produces a helical motif that proceeds along the 4₁ screw of the c axis. The helical motif for the H-bonding is shown in figure 2. Hydrogen bonding also occurs between the second N—H atom and a fluorine atom of the PF₆^- anion. Table 1 lists the hydrogen bonding parameters for the hydrogen bonds N1—H1A···F1 and N1—H1B···O2. With an H···O distance of 2.02 (6) Å and an N—H···O angle of 172 (6)°, the N1—H1B···O bond is a strong hydrogen bond while the N—H···F bond is not as strong based on geometric parameters, but still not a "weak" H-bond (Wood et al., 2009).

In addition to the overall quality improvement of the structure of the D compound reported here at 100 K compared with the L–valine compound at RT, the issue of lattice solvent is an interesting one. In the previous report, the crystals were isolated and handled in air at room temperature for a period of days before mounting them and collecting data at room temperature. The L–valine complex showed very large voids (573 Å³) with negligible residual electron density. The current D–valine complex clearly shows dichloromethane within the structure, but each dichloromethane site is only ~68% occupied. Here, it would appear that dichloromethane of solvation is partially lost.

Often, for molecular compounds, loss of solvent of crystallization results in the collapse of the crystal lattice. The D–valine complex with partial loss and the L-valine with complete solvent loss maintain the crystal lattice structural integrity. Figure 3 shows a view of both the D– and L–valine space filling packing diagrams that show, the CH₂Cl₂ in the title compound and the empty space in the L–valine structure reported previously. The loss of solvent with preservation of the crystal lattice is the norm for metal-organic framework (MOF) compounds, but those involve strong coordination bonds between metals and linking ligands. Maintaining the crystal lattice solely with hydrogen bonding is not new, but it is somewhat rare. For another example, see Parkin and Behrman (2011).

Related literature top

The structure of the related L–valine complex has been described by Roy et al. (2006). For studies of hydrogen-bonded lattice systems that lose crystallinity on loss of solvent and an analogous one that retains crystallinity, see: Parkin & Behrman (2009, 2011). An analysis of the geometric paramaters for hydrogen bonds is given by Wood et al. (2009). [Scheme show incorrect ligand, not D-valine]

Experimental top

For a detailed description of the synthetic procedure for all of the tris-trimethylphosphine iridium amino acid complexes, see (Roy et al., 2006). The title compound was recrystallized by the layering of diethyl ether over a dichloromethane solution. After several days of slow diffusion, suitable single crystals grew at the interface.

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: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. Thermal ellipsoid plot of the title compound showing the ellipsoids at the 50% probability level. The dichloromethane of solvation has a site occupancy of ~68%.
	Fig. 2. A view of the hydrogen-bonded extended helical lattice of the title compound. Ellipsoids are shown at the 50% probability level and hydrogen atoms as well as phosphorus methyl atoms are omitted for clarity.
	Fig. 3. A space filling model of both the D– and L– valine iridium complexes packed from -0.5 → 1.0 along a, -0.5 → 1.0 along b, and -0.5→ 1.0 along c. The L–valine structure (left) shows a void while the D–valine structure (right) shows the dichloromethane in the lattice (68% occupancy). Spheres are shown at full van der Waals radii.

mer-Hydridotris(trimethylphosphane-κP)(D-valinato-κ²N,O)iridium hexafluoridophosphate dichloromethane 0.675-solvate top

Crystal data top

[Ir(C₅H₁₀NO₂)H(C₃H₉P)₃]PF₆·0.675CH₂Cl₂	D_x = 1.746 Mg m⁻³
M_r = 739.86	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₁	Cell parameters from 12856 reflections
a = 14.04454 (17) Å	θ = 3.5–31.4°
c = 14.2657 (3) Å	µ = 5.15 mm⁻¹
V = 2813.89 (9) Å³	T = 100 K
Z = 4	Needle, colourless
F(000) = 1457	0.17 × 0.05 × 0.05 mm

Data collection top

Oxford Diffraction Xcalibur2 (Eos, Gemini ultra) diffractometer	9371 independent reflections
Radiation source: Enhance (Mo) X-ray Source	7266 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
Detector resolution: 16.0122 pixels mm^-1	θ_max = 31.5°, θ_min = 3.5°
ω scans	h = −19→20
Absorption correction: gaussian (CrysAlis PRO; Oxford Diffraction, 2010)	k = −20→20
T_min = 0.449, T_max = 0.774	l = −20→20
39354 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0129P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.046	(Δ/σ)_max = 0.001
S = 0.81	Δρ_max = 0.70 e Å⁻³
9371 reflections	Δρ_min = −0.61 e Å⁻³
301 parameters	Absolute structure: Flack parameter determined using 3004 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
2 restraints	Absolute structure parameter: −0.021 (4)

Crystal data top

[Ir(C₅H₁₀NO₂)H(C₃H₉P)₃]PF₆·0.675CH₂Cl₂	Z = 4
M_r = 739.86	Mo Kα radiation
Tetragonal, P4₁	µ = 5.15 mm⁻¹
a = 14.04454 (17) Å	T = 100 K
c = 14.2657 (3) Å	0.17 × 0.05 × 0.05 mm
V = 2813.89 (9) Å³

Data collection top

Oxford Diffraction Xcalibur2 (Eos, Gemini ultra) diffractometer	9371 independent reflections
Absorption correction: gaussian (CrysAlis PRO; Oxford Diffraction, 2010)	7266 reflections with I > 2σ(I)
T_min = 0.449, T_max = 0.774	R_int = 0.069
39354 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.046	Δρ_max = 0.70 e Å⁻³
S = 0.81	Δρ_min = −0.61 e Å⁻³
9371 reflections	Absolute structure: Flack parameter determined using 3004 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
301 parameters	Absolute structure parameter: −0.021 (4)
2 restraints

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ir1	0.35067 (2)	0.06307 (2)	0.87490 (2)	0.01215 (4)
H	0.423 (3)	0.057 (4)	0.946 (3)	0.018*
O1	0.2567 (3)	0.1552 (3)	0.9483 (3)	0.0147 (9)
O2	0.1109 (3)	0.2137 (3)	0.9557 (3)	0.0185 (9)
N1	0.2309 (4)	0.0780 (4)	0.7763 (4)	0.0167 (11)
H1A	0.243 (4)	0.127 (4)	0.735 (4)	0.020*
H1B	0.221 (4)	0.023 (5)	0.758 (4)	0.020*
C1	0.1714 (4)	0.1635 (4)	0.9161 (4)	0.0139 (12)
C2	0.1437 (4)	0.1072 (4)	0.8295 (4)	0.0131 (12)
H2	0.1141	0.0469	0.8529	0.016*
C3	0.0677 (4)	0.1561 (4)	0.7699 (4)	0.0161 (12)
H3	0.0145	0.1728	0.8134	0.019*
C4	0.0260 (5)	0.0889 (5)	0.6968 (4)	0.0288 (16)
H4A	0.0754	0.0717	0.6512	0.043*
H4B	−0.0268	0.1205	0.6643	0.043*
H4C	0.0026	0.0312	0.7277	0.043*
C5	0.1009 (4)	0.2493 (4)	0.7263 (4)	0.0249 (15)
H5A	0.1337	0.2876	0.7737	0.037*
H5B	0.0456	0.2845	0.7026	0.037*
H5C	0.1446	0.2358	0.6744	0.037*
P1	0.28924 (11)	−0.05993 (12)	0.96794 (11)	0.0148 (3)
C6	0.2254 (5)	−0.0111 (5)	1.0676 (4)	0.0281 (17)
H6A	0.2641	0.0385	1.0973	0.042*
H6B	0.2126	−0.0619	1.1130	0.042*
H6C	0.1651	0.0165	1.0463	0.042*
C7	0.2042 (5)	−0.1472 (4)	0.9273 (4)	0.0255 (15)
H7A	0.1438	−0.1156	0.9126	0.038*
H7B	0.1938	−0.1949	0.9764	0.038*
H7C	0.2289	−0.1785	0.8709	0.038*
C8	0.3778 (4)	−0.1308 (5)	1.0273 (4)	0.0287 (16)
H8A	0.4116	−0.1703	0.9815	0.043*
H8B	0.3467	−0.1718	1.0737	0.043*
H8C	0.4233	−0.0888	1.0590	0.043*
P2	0.44500 (11)	−0.02850 (12)	0.78431 (11)	0.0161 (3)
C9	0.4335 (5)	−0.1576 (4)	0.7880 (4)	0.0230 (13)
H9A	0.4649	−0.1853	0.7330	0.034*
H9B	0.3660	−0.1749	0.7877	0.034*
H9C	0.4636	−0.1819	0.8451	0.034*
C10	0.4244 (4)	−0.0090 (4)	0.6599 (4)	0.0190 (14)
H10A	0.4285	0.0592	0.6461	0.028*
H10B	0.3609	−0.0325	0.6430	0.028*
H10C	0.4726	−0.0433	0.6234	0.028*
C11	0.5723 (4)	−0.0150 (5)	0.8001 (4)	0.0252 (15)
H11A	0.6059	−0.0491	0.7502	0.038*
H11B	0.5908	−0.0412	0.8611	0.038*
H11C	0.5889	0.0527	0.7976	0.038*
P3	0.42554 (11)	0.20679 (11)	0.83341 (11)	0.0156 (3)
C12	0.4899 (4)	0.2255 (5)	0.7248 (4)	0.0246 (15)
H12A	0.5181	0.2893	0.7249	0.037*
H12B	0.4460	0.2196	0.6717	0.037*
H12C	0.5405	0.1778	0.7190	0.037*
C13	0.5114 (5)	0.2398 (5)	0.9217 (4)	0.0294 (17)
H13A	0.5631	0.1929	0.9228	0.044*
H13B	0.4803	0.2416	0.9832	0.044*
H13C	0.5375	0.3028	0.9071	0.044*
C14	0.3453 (5)	0.3082 (5)	0.8334 (6)	0.037 (2)
H14A	0.3821	0.3670	0.8259	0.056*
H14B	0.3104	0.3102	0.8928	0.056*
H14C	0.3001	0.3020	0.7814	0.056*
P4	0.29616 (12)	0.22465 (12)	0.48790 (11)	0.0201 (4)
F1	0.2682 (3)	0.1526 (3)	0.5708 (3)	0.0469 (12)
F2	0.4001 (3)	0.1782 (3)	0.4853 (3)	0.0322 (9)
F3	0.3308 (3)	0.2988 (3)	0.5639 (3)	0.0554 (14)
F4	0.3246 (3)	0.2950 (3)	0.4063 (3)	0.0439 (12)
F5	0.2601 (3)	0.1496 (3)	0.4133 (3)	0.0426 (11)
F6	0.1918 (3)	0.2709 (3)	0.4920 (3)	0.0353 (10)
C15	0.5610 (11)	0.3894 (9)	0.4795 (10)	0.066 (4)	0.675 (6)
H15A	0.5070	0.3578	0.4475	0.080*	0.675 (6)
H15B	0.5730	0.3546	0.5387	0.080*	0.675 (6)
Cl1	0.6642 (3)	0.3794 (2)	0.4068 (3)	0.0708 (15)	0.675 (6)
Cl2	0.5294 (4)	0.4995 (4)	0.5055 (7)	0.157 (3)	0.675 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir1	0.01075 (12)	0.01395 (12)	0.01177 (7)	−0.00014 (11)	−0.00084 (10)	0.00094 (10)
O1	0.015 (2)	0.015 (2)	0.014 (2)	−0.0025 (18)	−0.0022 (17)	−0.0019 (16)
O2	0.016 (2)	0.023 (2)	0.017 (2)	0.0037 (19)	0.0020 (17)	−0.0052 (18)
N1	0.020 (3)	0.013 (3)	0.017 (3)	0.001 (2)	0.004 (2)	−0.002 (2)
C1	0.016 (3)	0.012 (3)	0.014 (3)	−0.001 (2)	0.005 (2)	0.004 (2)
C2	0.010 (3)	0.012 (3)	0.017 (3)	−0.003 (2)	0.000 (2)	0.000 (2)
C3	0.010 (3)	0.024 (3)	0.015 (3)	0.003 (2)	−0.003 (2)	−0.001 (3)
C4	0.022 (4)	0.032 (4)	0.033 (4)	0.015 (3)	−0.010 (3)	−0.010 (3)
C5	0.020 (4)	0.029 (4)	0.025 (3)	0.011 (3)	0.002 (3)	0.006 (3)
P1	0.0151 (9)	0.0175 (9)	0.0118 (7)	−0.0009 (7)	−0.0008 (6)	0.0031 (6)
C6	0.037 (4)	0.024 (4)	0.023 (4)	0.001 (3)	0.011 (3)	0.006 (3)
C7	0.029 (4)	0.025 (4)	0.023 (3)	−0.010 (3)	−0.005 (3)	0.004 (3)
C8	0.020 (4)	0.038 (4)	0.029 (4)	−0.004 (3)	−0.003 (3)	0.013 (3)
P2	0.0127 (8)	0.0188 (9)	0.0166 (8)	0.0015 (7)	−0.0005 (6)	0.0011 (7)
C9	0.026 (4)	0.019 (4)	0.024 (3)	0.000 (3)	0.002 (3)	−0.006 (3)
C10	0.018 (3)	0.021 (3)	0.017 (3)	0.006 (3)	0.005 (2)	0.001 (2)
C11	0.014 (3)	0.034 (4)	0.027 (4)	0.004 (3)	−0.002 (3)	−0.002 (3)
P3	0.0137 (8)	0.0155 (8)	0.0177 (8)	−0.0013 (7)	−0.0004 (6)	0.0013 (6)
C12	0.028 (4)	0.026 (4)	0.019 (3)	−0.011 (3)	0.003 (3)	0.006 (3)
C13	0.036 (4)	0.027 (4)	0.025 (4)	−0.010 (3)	−0.010 (3)	−0.001 (3)
C14	0.023 (4)	0.018 (4)	0.072 (6)	0.000 (3)	0.005 (4)	0.004 (4)
P4	0.0213 (9)	0.0208 (9)	0.0180 (8)	0.0069 (7)	−0.0001 (7)	0.0002 (7)
F1	0.049 (3)	0.049 (3)	0.043 (3)	0.026 (2)	0.021 (2)	0.025 (2)
F2	0.026 (2)	0.039 (3)	0.031 (2)	0.0158 (19)	−0.0018 (17)	0.0012 (19)
F3	0.061 (3)	0.048 (3)	0.058 (3)	0.019 (2)	−0.034 (3)	−0.028 (2)
F4	0.040 (3)	0.046 (3)	0.046 (3)	0.002 (2)	0.004 (2)	0.021 (2)
F5	0.039 (3)	0.039 (3)	0.049 (3)	0.003 (2)	−0.008 (2)	−0.015 (2)
F6	0.032 (2)	0.042 (3)	0.031 (2)	0.017 (2)	0.0028 (18)	0.0063 (19)
C15	0.089 (12)	0.036 (8)	0.074 (11)	0.011 (7)	−0.013 (9)	0.001 (7)
Cl1	0.084 (3)	0.047 (2)	0.082 (3)	−0.0090 (19)	0.017 (2)	−0.0030 (18)
Cl2	0.140 (5)	0.061 (4)	0.270 (8)	0.039 (4)	0.095 (7)	0.018 (4)

Geometric parameters (Å, º) top

Ir1—H	1.44 (3)	P2—C9	1.821 (6)
Ir1—O1	2.124 (4)	P2—C10	1.820 (5)
Ir1—N1	2.203 (6)	P2—C11	1.811 (6)
Ir1—P1	2.3430 (16)	C9—H9A	0.9800
Ir1—P2	2.2537 (16)	C9—H9B	0.9800
Ir1—P3	2.3517 (16)	C9—H9C	0.9800
O1—C1	1.288 (7)	C10—H10A	0.9800
O2—C1	1.240 (6)	C10—H10B	0.9800
N1—H1A	0.92 (6)	C10—H10C	0.9800
N1—H1B	0.83 (6)	C11—H11A	0.9800
N1—C2	1.499 (7)	C11—H11B	0.9800
C1—C2	1.518 (7)	C11—H11C	0.9800
C2—H2	1.0000	P3—C12	1.813 (6)
C2—C3	1.528 (7)	P3—C13	1.805 (6)
C3—H3	1.0000	P3—C14	1.816 (7)
C3—C4	1.524 (8)	C12—H12A	0.9800
C3—C5	1.522 (8)	C12—H12B	0.9800
C4—H4A	0.9800	C12—H12C	0.9800
C4—H4B	0.9800	C13—H13A	0.9800
C4—H4C	0.9800	C13—H13B	0.9800
C5—H5A	0.9800	C13—H13C	0.9800
C5—H5B	0.9800	C14—H14A	0.9800
C5—H5C	0.9800	C14—H14B	0.9800
P1—C6	1.815 (6)	C14—H14C	0.9800
P1—C7	1.807 (6)	P4—F1	1.605 (4)
P1—C8	1.805 (6)	P4—F2	1.599 (4)
C6—H6A	0.9800	P4—F3	1.580 (4)
C6—H6B	0.9800	P4—F4	1.578 (4)
C6—H6C	0.9800	P4—F5	1.582 (4)
C7—H7A	0.9800	P4—F6	1.604 (4)
C7—H7B	0.9800	C15—H15A	0.9900
C7—H7C	0.9800	C15—H15B	0.9900
C8—H8A	0.9800	C15—Cl1	1.789 (15)
C8—H8B	0.9800	C15—Cl2	1.651 (13)
C8—H8C	0.9800

O1—Ir1—H	97 (2)	H8A—C8—H8C	109.5
O1—Ir1—N1	77.43 (17)	H8B—C8—H8C	109.5
O1—Ir1—P1	86.61 (11)	C9—P2—Ir1	120.0 (2)
O1—Ir1—P2	174.55 (11)	C10—P2—Ir1	112.3 (2)
O1—Ir1—P3	83.06 (11)	C10—P2—C9	99.4 (3)
N1—Ir1—H	174 (2)	C11—P2—Ir1	116.7 (2)
N1—Ir1—P1	98.66 (15)	C11—P2—C9	100.9 (3)
N1—Ir1—P2	97.88 (14)	C11—P2—C10	105.2 (3)
N1—Ir1—P3	95.69 (15)	P2—C9—H9A	109.5
P1—Ir1—H	80 (2)	P2—C9—H9B	109.5
P1—Ir1—P3	160.05 (5)	P2—C9—H9C	109.5
P2—Ir1—H	88 (2)	H9A—C9—H9B	109.5
P2—Ir1—P1	96.93 (5)	H9A—C9—H9C	109.5
P2—Ir1—P3	94.74 (6)	H9B—C9—H9C	109.5
P3—Ir1—H	85 (2)	P2—C10—H10A	109.5
C1—O1—Ir1	117.2 (3)	P2—C10—H10B	109.5
Ir1—N1—H1A	110 (4)	P2—C10—H10C	109.5
Ir1—N1—H1B	104 (4)	H10A—C10—H10B	109.5
H1A—N1—H1B	122 (6)	H10A—C10—H10C	109.5
C2—N1—Ir1	109.1 (4)	H10B—C10—H10C	109.5
C2—N1—H1A	106 (4)	P2—C11—H11A	109.5
C2—N1—H1B	106 (4)	P2—C11—H11B	109.5
O1—C1—C2	118.8 (5)	P2—C11—H11C	109.5
O2—C1—O1	121.8 (5)	H11A—C11—H11B	109.5
O2—C1—C2	119.4 (5)	H11A—C11—H11C	109.5
N1—C2—C1	110.2 (5)	H11B—C11—H11C	109.5
N1—C2—H2	106.1	C12—P3—Ir1	124.2 (2)
N1—C2—C3	114.3 (5)	C12—P3—C14	101.3 (3)
C1—C2—H2	106.1	C13—P3—Ir1	110.1 (2)
C1—C2—C3	113.5 (5)	C13—P3—C12	103.1 (3)
C3—C2—H2	106.1	C13—P3—C14	102.3 (3)
C2—C3—H3	106.3	C14—P3—Ir1	113.3 (2)
C4—C3—C2	111.8 (5)	P3—C12—H12A	109.5
C4—C3—H3	106.3	P3—C12—H12B	109.5
C5—C3—C2	113.7 (5)	P3—C12—H12C	109.5
C5—C3—H3	106.3	H12A—C12—H12B	109.5
C5—C3—C4	111.8 (5)	H12A—C12—H12C	109.5
C3—C4—H4A	109.5	H12B—C12—H12C	109.5
C3—C4—H4B	109.5	P3—C13—H13A	109.5
C3—C4—H4C	109.5	P3—C13—H13B	109.5
H4A—C4—H4B	109.5	P3—C13—H13C	109.5
H4A—C4—H4C	109.5	H13A—C13—H13B	109.5
H4B—C4—H4C	109.5	H13A—C13—H13C	109.5
C3—C5—H5A	109.5	H13B—C13—H13C	109.5
C3—C5—H5B	109.5	P3—C14—H14A	109.5
C3—C5—H5C	109.5	P3—C14—H14B	109.5
H5A—C5—H5B	109.5	P3—C14—H14C	109.5
H5A—C5—H5C	109.5	H14A—C14—H14B	109.5
H5B—C5—H5C	109.5	H14A—C14—H14C	109.5
C6—P1—Ir1	110.3 (2)	H14B—C14—H14C	109.5
C7—P1—Ir1	124.2 (2)	F2—P4—F1	89.1 (2)
C7—P1—C6	100.4 (3)	F2—P4—F6	179.2 (2)
C8—P1—Ir1	114.8 (2)	F3—P4—F1	89.1 (3)
C8—P1—C6	100.5 (3)	F3—P4—F2	90.2 (2)
C8—P1—C7	103.4 (3)	F3—P4—F5	178.9 (3)
P1—C6—H6A	109.5	F3—P4—F6	89.4 (2)
P1—C6—H6B	109.5	F4—P4—F1	179.5 (2)
P1—C6—H6C	109.5	F4—P4—F2	90.4 (2)
H6A—C6—H6B	109.5	F4—P4—F3	90.9 (3)
H6A—C6—H6C	109.5	F4—P4—F5	90.1 (2)
H6B—C6—H6C	109.5	F4—P4—F6	90.3 (2)
P1—C7—H7A	109.5	F5—P4—F1	89.8 (2)
P1—C7—H7B	109.5	F5—P4—F2	90.3 (2)
P1—C7—H7C	109.5	F5—P4—F6	90.1 (2)
H7A—C7—H7B	109.5	F6—P4—F1	90.3 (2)
H7A—C7—H7C	109.5	H15A—C15—H15B	107.5
H7B—C7—H7C	109.5	Cl1—C15—H15A	108.5
P1—C8—H8A	109.5	Cl1—C15—H15B	108.5
P1—C8—H8B	109.5	Cl2—C15—H15A	108.5
P1—C8—H8C	109.5	Cl2—C15—H15B	108.5
H8A—C8—H8B	109.5	Cl2—C15—Cl1	115.0 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···F1	0.92 (6)	2.39 (6)	3.157 (7)	140 (5)
N1—H1B···O2ⁱ	0.83 (6)	2.02 (6)	2.848 (7)	172 (6)

Symmetry code: (i) y, −x, z−1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···F1	0.92 (6)	2.39 (6)	3.157 (7)	140 (5)
N1—H1B···O2ⁱ	0.83 (6)	2.02 (6)	2.848 (7)	172 (6)

Symmetry code: (i) y, −x, z−1/4.

Acknowledgements

We thank the National Science Foundation for funds (grant CHE-01311288)) for the purchase of the Oxford Diffraction Xcalibur2 single-crystal diffractometer.

References

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Parkin, S. R. & Behrman, E. J. (2009). Acta Cryst. C65, o529–o533. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Parkin, S. R. & Behrman, E. J. (2011). Acta Cryst. C67, o324–o328. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Roy, C. P., Huff, L. A., Barker, N. A., Berg, M. A. G. & Merola, J. S. (2006). J. Organomet. Chem. 691, 2270–2276. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wood, P. A., Allen, F. H. & Pidcock, E. (2009). CrystEngComm, 11, 1563–1571. Web of Science CSD CrossRef CAS Google Scholar

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