(Butane-1,4-di­yl)(trimethyl­phosphane-κP)[tris­(3,5-dimethyl­pyrazol-1-yl-κN2)hydro­borato]iridium(III)

Gómez, M.; Santos, L.L.; Paneque, M.; Mereiter, K.

doi:10.1107/S1600536813008040

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Pages m234-m235

https://doi.org/10.1107/S1600536813008040

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(Butane-1,4-diyl)(trimethylphosphane-κP)[tris(3,5-dimethylpyrazol-1-yl-κN²)hydroborato]iridium(III)

Margarita Gómez,^a Laura L. Santos,^a Margarita Paneque ^a and Kurt Mereiter ^b ^*

^aInstituto de Investigaciones Químicas (IIQ) and Departamento de Química Inorgánica, Consejo Superior de Investigaciones Cientificas (CSIC) and Universidad de Sevilla, Avenida Américo Vespucio 49, 41092 Sevilla, Spain, and ^bInstitute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164SC, A-1060 Vienna, Austria
^*Correspondence e-mail: kurt.mereiter@tuwien.ac.at

(Received 17 March 2013; accepted 23 March 2013; online 5 April 2013)

In the mononuclear title iridium(III) complex, [Ir(C₄H₈)(C₁₅H₂₂BN₆)(C₃H₉P)], which is based on the [tris(3,5-dimethylpyrazol-1-yl)hydroborato]iridium moiety, Ir[Tp^Me2], the Ir^III atom is coordinated by a chelating butane-1,4-diyl fragment and a trimethylphosphane ligand in a modestly distorted octahedral coordination environment formed by three facial N, two C and one P atom. The iridium–butane-1,4-diyl ring has an envelope conformation. This ring is disordered because alternately the second or the third C atom of the butane-1,4-diyl fragment function as an envelope flap atom (the occupancy ratio is 1:1). In the crystal, molecules are organized into densely packed columns extending along [101]. Coherence between the molecules is essentially based on van der Waals interactions.

Related literature

For general aspects of hydrogen trispyrazolylborate ligands, see: Pettinari & Trofimenko (2008 ). For general information on mechanistic aspects of organometallic reactions, involving oxidative addition and reductive elimination, see: Crabtree (2005 ). For information on σ-CAM mechanisms, see: Perutz & Sabo-Etienne (2007 ). For general information on the chemistry and potential of Ir[Tp^Me2] complexes, see: Conejero et al. (2010 ). For selected aspects of the synthesis and the crystal structure of the precursor of the title compound, see: Paneque et al. (2000 ). For aspects of the chemistry of a CO- instead of PMe₃-containing analogue to the precursor of the title compound, see: Gómez et al. (2007 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[Ir(C₄H₈)(C₁₅H₂₂BN₆)(C₃H₉P)]
M_r = 621.57
Monoclinic, P 2₁ /n
a = 11.1865 (5) Å
b = 18.1771 (8) Å
c = 13.4748 (6) Å
β = 112.883 (1)°
V = 2524.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 5.37 mm⁻¹
T = 173 K
0.22 × 0.15 × 0.14 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.36, T_max = 0.47
37102 measured reflections
7359 independent reflections
6892 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.017
wR(F²) = 0.040
S = 1.08
7359 reflections
298 parameters
25 restraints
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Selected bond lengths (Å)

Ir1—C19A	2.0780 (18)
Ir1—C16A	2.0871 (19)
Ir1—N5	2.1781 (14)
Ir1—N3	2.2233 (15)
Ir1—P1	2.2381 (5)
Ir1—N1	2.2590 (15)

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813008040/gk2565sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813008040/gk2565Isup2.hkl

checkCIF report

Comment top

Iridium complexes with the stabilizing ligand hydrogen tris(3,5-dimethylpyrazolyl)borate (Tp^Me2) (Pettinari & Trofimenko, 2008) and containing carbon bearing co-ligands possess a rich chemistry (Conejero et al., 2010) and are capable of a broad range of bond activation and coupling reactions either via oxidative addition and reductive elimination (Crabtree, 2005) or via σ-CAM mechanisms (Perutz & Sabo-Etienne, 2007). When the conveniently accessible Ir(I) complex [(Tp^Me2)Ir(η⁴-CH₂═CH—CH═CH₂)] containing a π-bonded butadiene is treated with a Lewis base like PMe₃ it transforms cleanly into the Ir(III) complex [(Tp^Me2)Ir(κ²-CH₂—CH═CH—CH₂)(PMe₃)] in a process which implies the transformation of the butadiene ligand into a but-2-ene-1,4-diyl one (Paneque et al., 2000). This complex is inert to substitution of the phosphine ligand so the metallacyclic structure can experience some cyclopentene-like reactivity without rupturing the Ir—C bonds. The analogous product with a CO ligand instead of PMe₃ behaves similarly and experiences for instance a series of reactions (subsequent hydroboration-oxidation of double bond, alcohol oxidation to ketone and α-formylation of ketone) leading to the formation a new α-formyl-3-iridacyclopentanone (Gómez et al., 2007). The catalytic hydrogenation of the PMe₃ derivative under slightly harsher conditions leads to the formation of the title compound [(Tp^Me2)Ir(κ²-CH₂—CH₂—CH₂—CH₂)(PMe₃)], (I). A view of the complex is shown in Fig. 1. Iridium has a modestly distorted octahedral coordination with bond lengths given in Table 1. Bond angles about Ir are in the ranges 82.12 (8)–96.06 (7)° and 172.64 (7)–175.42 (4)° with the smallest angle (C—Ir—C = 82.12 (8)°) for the Ir butane-1,4-diyl ring. This ring has an envelope conformation but is disordered because either the 2^nd or the 3^rd carbon atom of the butane fragment is the flap atom in 1:1 ratio (cf. Fig. 1). In the first case Ir1, C16A, C18A, and C19A are flat within 0.053 Å mean deviation from planarity and C17A is the flap atom that deviates by 0.569 (6) Å from the mean plane of the four. In the second case Ir1, C16B, C17B, and C19B are flat (0.028 Å mean deviation) and C18B is the flap atom which deviates by 0.537 (7) Å from the corresponding mean plane. Except for the envelope conformation of the IrC₄ ring the molecular structure of I is closely similar to that of [(Tp^Me2)Ir(κ²-CH₂—CH═CH—CH₂)(PMe₃)] (Paneque et al., 2000; for crystal structure data see Cambridge Crystallographic Database, refcode ABIBOC; CCD version 5.33; Allen, 2002). This includes also bond lengths and bond angles about Ir, which for the latter complex are: Ir—N = 2.25 (1), 2.22 (1), 2.16 (1) Å; Ir—C = 2.09 (1), 2.09 (1) Å, Ir—P = 2.234 (3) Å; the C═C bond in the olefinic IrC₄ ring is 1.27 (2) Å compared with C—C = 1.536 (1) Å for the aliphatic IrC₄ ring in I. Despite similar shapes of the two complexes under consideration and analogous crystallization conditions (see Experimental) their crystal structures are dissimilar: [(Tp^Me2)Ir(κ²-CH₂—CH═CH—CH₂)(PMe₃)] crystallized as a dichloromethane solvate of triclinic symmetry (Paneque et al., 2000), whereas I is monoclinic and unsolvated. In the lack of distinctly polar groups on the outer surface of the molecules of I, their crystal structure is held together essentially by van der Waals interactions. The most prominent feature of the crystal structure of I are columns of tightly packed molecules extending along [101], as exemplified in Fig. 2. Mutual contacts between the columns perpendicular to [101] are more open and appear to represent weaker coherence. In the crystal structure of [(Tp^Me2)Ir(κ²-CH₂—CH═CH—CH₂)(PMe₃)].1/4CH₂Cl₂ (Paneque et al., 2000) the column motif of I is absent.

Related literature top

For general aspects of hydrogen trispyrazolylborate ligands , see: Pettinari & Trofimenko (2008). For general information on mechanistic aspects of organometallic reactions, involving oxidative addition and reductive elimination, see: Crabtree (2005). For information on σ-CAM mechanisms, see: Perutz & Sabo-Etienne (2007). For general information on the chemistry and potential of Ir[Tp^Me2] complexes, see: Conejero et al. (2010). For selected aspects of the synthesis and the crystal structure of the precursor of the title compound, see: Paneque et al. (2000). For aspects of the chemistry of a CO- instead of PMe₃-containing analogue to the precursor of the title compound, see: Gómez et al. (2007). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

A solution of [(Tp^Me2)Ir(κ²-CH₂—CH═CH—CH₂)(PMe₃)] (0.10 g, 0.16 mmol; for synthesis see Paneque et al., 2000) in dioxane (10 ml), with a small amount of PtO₂ as catalyst, was transferred to a pressure vessel, charged with H₂ at 4 bar and heated at 353 K for 4 days. Then the solvent was removed under reduced pressure and the crude product was purified by column chromatography (silicagel, hexane/Et₂O 10/1 v/v) to give the title compound I in 44% yield. Crystallization from hexane/CH₂Cl₂ (1:2) at 253 K gave I as colourless crystals. ¹H NMR (CDCl₃, 298 K) δ 5.71, 5.68 (s, 2:1, 3 CH_pz), 2.44, 2.37, 2.36, 2.26 (s, 1:2:2:1, 6 Me_pz), 2.33 (m, 4 H, 2 CH_AH_B), 1.64, 1.27 (m, 2 H cada, 2 CH_CH_D), 1.37 (d, 9 H, ²J_HP = 9.2 Hz, PMe₃). ¹³C{¹H} NMR (CDCl₃, 298 K) δ 150.5, 148.9 (d, J_CP = 3 Hz) (2:1:2:1, C_qpz), 108.3 (d, J_CP = 4 Hz), 107.9 (1:2 CH_pz), 34.8 (C², ³J_CP = 2 Hz, ¹J_CH = 122 Hz), 16.2 (d, ¹J_CP = 37 Hz, PMe₃), 16.0, 15.1, 13.7, 13.4 (2:1:1:2, Me_pz), -3.6 (C1, ²J_CP = 8 Hz, ¹J_CH = 125 Hz). ³¹P {¹H} NMR (CDCl₃, 298 K) δ -48.0 p.p.m..

Structure description top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at the 30% probability level showing the disordered butane-1,4-diyl fragment C16—C17—C18—C19 in both conformations (A-conformation dark, B-conformation pale), see text.
	Fig. 2. Stacking of the molecules of I to form efficiently packed columns parallel to [101].

(Butane-1,4-diyl)(trimethylphosphane-κP)[tris(3,5-dimethylpyrazol-1-yl-κN²)hydroborato]iridium(III) top

Crystal data top

[Ir(C₄H₈)(C₁₅H₂₂BN₆)(C₃H₉P)]	F(000) = 1240
M_r = 621.57	D_x = 1.636 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8250 reflections
a = 11.1865 (5) Å	θ = 2.3–30.0°
b = 18.1771 (8) Å	µ = 5.37 mm⁻¹
c = 13.4748 (6) Å	T = 173 K
β = 112.883 (1)°	Oval, colourless
V = 2524.3 (2) Å³	0.22 × 0.15 × 0.14 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	7359 independent reflections
Radiation source: fine-focus sealed tube	6892 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 0.11 pixels mm^-1	θ_max = 30.0°, θ_min = 2.0°
ω and φ scans	h = −15→15
Absorption correction: multi-scan (SADABS; Bruker, 2003)	k = −25→25
T_min = 0.36, T_max = 0.47	l = −18→18
37102 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)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.040	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0188P)² + 1.5354P] where P = (F_o² + 2F_c²)/3
7359 reflections	(Δ/σ)_max = 0.002
298 parameters	Δρ_max = 0.86 e Å⁻³
25 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Ir(C₄H₈)(C₁₅H₂₂BN₆)(C₃H₉P)]	V = 2524.3 (2) Å³
M_r = 621.57	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.1865 (5) Å	µ = 5.37 mm⁻¹
b = 18.1771 (8) Å	T = 173 K
c = 13.4748 (6) Å	0.22 × 0.15 × 0.14 mm
β = 112.883 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	7359 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	6892 reflections with I > 2σ(I)
T_min = 0.36, T_max = 0.47	R_int = 0.018
37102 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	25 restraints
wR(F²) = 0.040	H-atom parameters constrained
S = 1.08	Δρ_max = 0.86 e Å⁻³
7359 reflections	Δρ_min = −0.32 e Å⁻³
298 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.

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)
Ir1	0.330539 (6)	0.149427 (3)	0.140251 (5)	0.02163 (2)
P1	0.13156 (4)	0.17885 (3)	0.02261 (4)	0.02555 (9)
N1	0.41101 (15)	0.26249 (9)	0.13371 (12)	0.0279 (3)
N2	0.52542 (16)	0.26511 (9)	0.11853 (13)	0.0313 (3)
N3	0.39782 (14)	0.11256 (9)	0.01330 (12)	0.0271 (3)
N4	0.50615 (16)	0.14845 (9)	0.01311 (13)	0.0289 (3)
N5	0.52880 (14)	0.12008 (9)	0.24383 (12)	0.0258 (3)
N6	0.62443 (15)	0.14889 (9)	0.21463 (13)	0.0299 (3)
B1	0.5921 (2)	0.19391 (13)	0.11026 (17)	0.0312 (4)
H1	0.6748	0.2061	0.1017	0.037*
C1	0.2641 (3)	0.35688 (13)	0.1631 (3)	0.0507 (6)
H1A	0.2366	0.3178	0.1997	0.076*
H1B	0.1940	0.3674	0.0934	0.076*
H1C	0.2842	0.4014	0.2076	0.076*
C2	0.3816 (2)	0.33261 (11)	0.14579 (16)	0.0342 (4)
C3	0.4767 (2)	0.37982 (12)	0.13857 (17)	0.0402 (5)
H3	0.4791	0.4319	0.1446	0.048*
C4	0.5652 (2)	0.33560 (13)	0.12097 (17)	0.0406 (5)
C5	0.6899 (3)	0.35592 (16)	0.1088 (2)	0.0595 (8)
H5A	0.6973	0.4096	0.1075	0.089*
H5B	0.6894	0.3353	0.0415	0.089*
H5C	0.7639	0.3360	0.1697	0.089*
C6	0.2510 (2)	0.01374 (14)	−0.09982 (18)	0.0441 (5)
H6A	0.2293	0.0053	−0.0370	0.066*
H6B	0.2763	−0.0329	−0.1225	0.066*
H6C	0.1753	0.0339	−0.1589	0.066*
C7	0.36048 (18)	0.06676 (11)	−0.07123 (15)	0.0305 (4)
C8	0.4424 (2)	0.07415 (12)	−0.12664 (16)	0.0360 (4)
H8	0.4361	0.0486	−0.1900	0.043*
C9	0.5333 (2)	0.12547 (13)	−0.07166 (16)	0.0345 (4)
C10	0.6438 (3)	0.15446 (15)	−0.0960 (2)	0.0503 (6)
H10A	0.6357	0.2080	−0.1049	0.075*
H10B	0.6423	0.1320	−0.1626	0.075*
H10C	0.7258	0.1425	−0.0365	0.075*
C11	0.5281 (2)	0.04034 (13)	0.39711 (17)	0.0415 (5)
H11A	0.4682	0.0728	0.4134	0.062*
H11B	0.5949	0.0225	0.4645	0.062*
H11C	0.4801	−0.0016	0.3544	0.062*
C12	0.59054 (18)	0.08183 (11)	0.33483 (14)	0.0304 (4)
C13	0.72443 (19)	0.08640 (13)	0.36404 (16)	0.0375 (4)
H13	0.7898	0.0641	0.4247	0.045*
C14	0.74271 (19)	0.12949 (14)	0.28780 (16)	0.0370 (4)
C15	0.8676 (2)	0.15468 (18)	0.2836 (2)	0.0576 (8)
H15A	0.8712	0.2085	0.2857	0.086*
H15B	0.8734	0.1373	0.2168	0.086*
H15C	0.9403	0.1348	0.3455	0.086*
C16A	0.26125 (19)	0.04707 (11)	0.16388 (15)	0.0317 (4)	0.50
H16A	0.2210	0.0214	0.0938	0.038*	0.50
H16B	0.3346	0.0167	0.2114	0.038*	0.50
C17A	0.1607 (4)	0.0554 (2)	0.2149 (3)	0.0360 (8)	0.50
H17A	0.0758	0.0709	0.1603	0.043*	0.50
H17B	0.1492	0.0083	0.2471	0.043*	0.50
C18A	0.2157 (4)	0.11462 (19)	0.3022 (4)	0.0356 (10)	0.50
H18A	0.2755	0.0908	0.3692	0.043*	0.50
H18B	0.1433	0.1362	0.3174	0.043*	0.50
C19A	0.28856 (18)	0.17707 (11)	0.27285 (15)	0.0305 (3)	0.50
H19A	0.3703	0.1875	0.3351	0.037*	0.50
H19B	0.2348	0.2222	0.2567	0.037*	0.50
C16B	0.26125 (19)	0.04707 (11)	0.16388 (15)	0.0317 (4)	0.50
H16C	0.1903	0.0312	0.0963	0.038*	0.50
H16D	0.3319	0.0103	0.1821	0.038*	0.50
C17B	0.2106 (4)	0.0498 (2)	0.2547 (3)	0.0359 (8)	0.50
H17C	0.1297	0.0205	0.2327	0.043*	0.50
H17D	0.2753	0.0262	0.3197	0.043*	0.50
C18B	0.1831 (4)	0.12778 (18)	0.2842 (5)	0.0356 (10)	0.50
H18C	0.1874	0.1292	0.3590	0.043*	0.50
H18D	0.0958	0.1443	0.2349	0.043*	0.50
C19B	0.28856 (18)	0.17707 (11)	0.27285 (15)	0.0305 (3)	0.50
H19C	0.3686	0.1729	0.3389	0.037*	0.50
H19D	0.2594	0.2289	0.2660	0.037*	0.50
C20	0.0148 (2)	0.10666 (15)	−0.0424 (3)	0.0766 (11)
H20A	−0.0670	0.1289	−0.0908	0.115*
H20B	−0.0007	0.0773	0.0125	0.115*
H20C	0.0490	0.0749	−0.0839	0.115*
C21	0.0218 (2)	0.23610 (18)	0.0609 (2)	0.0561 (7)
H21A	−0.0599	0.2429	−0.0015	0.084*
H21B	0.0621	0.2841	0.0858	0.084*
H21C	0.0045	0.2120	0.1190	0.084*
C22	0.1375 (2)	0.22637 (14)	−0.09285 (17)	0.0415 (5)
H22A	0.0492	0.2385	−0.1427	0.062*
H22B	0.1786	0.1947	−0.1293	0.062*
H22C	0.1881	0.2717	−0.0693	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir1	0.01893 (3)	0.02738 (4)	0.02017 (3)	0.00079 (2)	0.00933 (2)	0.00218 (2)
P1	0.01929 (19)	0.0272 (2)	0.0285 (2)	−0.00024 (16)	0.00746 (16)	0.00237 (17)
N1	0.0266 (7)	0.0315 (8)	0.0238 (7)	−0.0045 (6)	0.0080 (6)	0.0011 (6)
N2	0.0303 (8)	0.0394 (9)	0.0256 (7)	−0.0122 (6)	0.0122 (6)	−0.0033 (6)
N3	0.0234 (7)	0.0362 (8)	0.0225 (7)	−0.0001 (6)	0.0098 (6)	−0.0009 (6)
N4	0.0251 (7)	0.0427 (9)	0.0228 (7)	−0.0014 (6)	0.0137 (6)	−0.0009 (6)
N5	0.0214 (7)	0.0345 (8)	0.0225 (7)	0.0022 (6)	0.0096 (5)	−0.0004 (6)
N6	0.0198 (7)	0.0476 (10)	0.0235 (7)	−0.0001 (6)	0.0096 (6)	−0.0025 (6)
B1	0.0238 (9)	0.0479 (12)	0.0254 (9)	−0.0078 (8)	0.0134 (8)	−0.0018 (8)
C1	0.0451 (13)	0.0331 (11)	0.0691 (18)	0.0079 (9)	0.0169 (13)	0.0008 (10)
C2	0.0351 (10)	0.0329 (9)	0.0276 (9)	−0.0014 (8)	0.0047 (8)	0.0022 (7)
C3	0.0493 (12)	0.0316 (10)	0.0318 (10)	−0.0108 (9)	0.0073 (9)	0.0005 (8)
C4	0.0473 (12)	0.0437 (11)	0.0305 (10)	−0.0227 (10)	0.0148 (9)	−0.0029 (8)
C5	0.0594 (17)	0.0677 (18)	0.0575 (16)	−0.0358 (14)	0.0295 (14)	−0.0074 (13)
C6	0.0388 (11)	0.0524 (13)	0.0364 (11)	−0.0083 (10)	0.0094 (9)	−0.0112 (10)
C7	0.0289 (9)	0.0366 (10)	0.0236 (8)	0.0043 (7)	0.0076 (7)	−0.0016 (7)
C8	0.0378 (10)	0.0473 (11)	0.0249 (8)	0.0051 (9)	0.0144 (8)	−0.0057 (8)
C9	0.0358 (10)	0.0483 (11)	0.0259 (9)	0.0044 (9)	0.0190 (8)	0.0007 (8)
C10	0.0542 (15)	0.0689 (17)	0.0444 (13)	−0.0078 (12)	0.0371 (12)	−0.0049 (11)
C11	0.0430 (11)	0.0474 (12)	0.0287 (9)	0.0013 (9)	0.0080 (8)	0.0111 (9)
C12	0.0293 (9)	0.0364 (9)	0.0229 (8)	0.0066 (7)	0.0074 (7)	−0.0002 (7)
C13	0.0273 (9)	0.0522 (12)	0.0267 (9)	0.0113 (8)	0.0036 (7)	−0.0031 (8)
C14	0.0214 (8)	0.0593 (13)	0.0288 (9)	0.0030 (8)	0.0082 (7)	−0.0085 (9)
C15	0.0223 (10)	0.100 (2)	0.0496 (15)	−0.0031 (11)	0.0125 (10)	−0.0062 (13)
C16A	0.0358 (9)	0.0280 (8)	0.0341 (9)	0.0021 (7)	0.0167 (7)	0.0057 (7)
C17A	0.033 (2)	0.0384 (19)	0.040 (2)	−0.0027 (15)	0.0187 (18)	0.0128 (13)
C18A	0.017 (2)	0.0585 (14)	0.038 (2)	0.0027 (16)	0.018 (2)	0.0024 (14)
C19A	0.0327 (9)	0.0356 (8)	0.0287 (9)	0.0026 (7)	0.0180 (7)	0.0002 (7)
C16B	0.0358 (9)	0.0280 (8)	0.0341 (9)	0.0021 (7)	0.0167 (7)	0.0057 (7)
C17B	0.034 (2)	0.0433 (12)	0.032 (2)	−0.0098 (16)	0.0145 (17)	0.0081 (19)
C18B	0.017 (2)	0.0585 (14)	0.038 (2)	0.0027 (16)	0.018 (2)	0.0024 (14)
C19B	0.0327 (9)	0.0356 (8)	0.0287 (9)	0.0026 (7)	0.0180 (7)	0.0002 (7)
C20	0.0219 (10)	0.0399 (13)	0.136 (3)	−0.0061 (9)	−0.0040 (14)	−0.0021 (16)
C21	0.0346 (11)	0.087 (2)	0.0450 (13)	0.0244 (12)	0.0136 (10)	−0.0045 (13)
C22	0.0356 (10)	0.0567 (13)	0.0292 (9)	0.0088 (9)	0.0093 (8)	0.0135 (9)

Geometric parameters (Å, º) top

Ir1—C19A	2.0780 (18)	C9—C10	1.492 (3)
Ir1—C16A	2.0871 (19)	C10—H10A	0.9800
Ir1—N5	2.1781 (14)	C10—H10B	0.9800
Ir1—N3	2.2233 (15)	C10—H10C	0.9800
Ir1—P1	2.2381 (5)	C11—C12	1.489 (3)
Ir1—N1	2.2590 (15)	C11—H11A	0.9800
P1—C22	1.803 (2)	C11—H11B	0.9800
P1—C20	1.818 (2)	C11—H11C	0.9800
P1—C21	1.830 (2)	C12—C13	1.395 (3)
N1—C2	1.342 (3)	C13—C14	1.369 (3)
N1—N2	1.373 (2)	C13—H13	0.9500
N2—C4	1.353 (3)	C14—C15	1.492 (3)
N2—B1	1.520 (3)	C15—H15A	0.9800
N3—C7	1.340 (2)	C15—H15B	0.9800
N3—N4	1.377 (2)	C15—H15C	0.9800
N4—C9	1.357 (2)	C16A—C17A	1.537 (2)
N4—B1	1.531 (3)	C16A—H16A	0.9900
N5—C12	1.344 (2)	C16A—H16B	0.9900
N5—N6	1.379 (2)	C17A—C18A	1.536 (2)
N6—C14	1.354 (2)	C17A—H17A	0.9900
N6—B1	1.544 (3)	C17A—H17B	0.9900
B1—H1	1.0000	C18A—C19A	1.536 (2)
C1—C2	1.489 (4)	C18A—H18A	0.9900
C1—H1A	0.9800	C18A—H18B	0.9900
C1—H1B	0.9800	C19A—H19A	0.9900
C1—H1C	0.9800	C19A—H19B	0.9900
C2—C3	1.399 (3)	C17B—C18B	1.536 (2)
C3—C4	1.366 (4)	C17B—H17C	0.9900
C3—H3	0.9500	C17B—H17D	0.9900
C4—C5	1.512 (3)	C18B—H18C	0.9900
C5—H5A	0.9800	C18B—H18D	0.9900
C5—H5B	0.9800	C20—H20A	0.9800
C5—H5C	0.9800	C20—H20B	0.9800
C6—C7	1.487 (3)	C20—H20C	0.9800
C6—H6A	0.9800	C21—H21A	0.9800
C6—H6B	0.9800	C21—H21B	0.9800
C6—H6C	0.9800	C21—H21C	0.9800
C7—C8	1.395 (3)	C22—H22A	0.9800
C8—C9	1.367 (3)	C22—H22B	0.9800
C8—H8	0.9500	C22—H22C	0.9800

C19A—Ir1—C16A	82.12 (8)	N4—C9—C8	107.64 (17)
C19A—Ir1—N5	91.29 (7)	N4—C9—C10	123.5 (2)
C16A—Ir1—N5	91.71 (7)	C8—C9—C10	128.87 (19)
C19A—Ir1—N3	172.64 (7)	C9—C10—H10A	109.5
C16A—Ir1—N3	96.06 (7)	C9—C10—H10B	109.5
N5—Ir1—N3	81.62 (5)	H10A—C10—H10B	109.5
C19A—Ir1—P1	93.22 (6)	C9—C10—H10C	109.5
C16A—Ir1—P1	89.71 (6)	H10A—C10—H10C	109.5
N5—Ir1—P1	175.42 (4)	H10B—C10—H10C	109.5
N3—Ir1—P1	93.90 (4)	C12—C11—H11A	109.5
C19A—Ir1—N1	92.31 (7)	C12—C11—H11B	109.5
C16A—Ir1—N1	173.83 (6)	H11A—C11—H11B	109.5
N5—Ir1—N1	85.75 (6)	C12—C11—H11C	109.5
N3—Ir1—N1	89.14 (6)	H11A—C11—H11C	109.5
P1—Ir1—N1	93.25 (4)	H11B—C11—H11C	109.5
C22—P1—C20	101.00 (15)	N5—C12—C13	109.95 (18)
C22—P1—C21	103.01 (12)	N5—C12—C11	126.10 (17)
C20—P1—C21	96.38 (14)	C13—C12—C11	123.96 (18)
C22—P1—Ir1	111.42 (7)	C14—C13—C12	106.23 (17)
C20—P1—Ir1	119.95 (9)	C14—C13—H13	126.9
C21—P1—Ir1	121.84 (8)	C12—C13—H13	126.9
C2—N1—N2	105.75 (16)	N6—C14—C13	107.86 (18)
C2—N1—Ir1	137.67 (14)	N6—C14—C15	123.8 (2)
N2—N1—Ir1	116.49 (12)	C13—C14—C15	128.3 (2)
C4—N2—N1	110.26 (18)	C14—C15—H15A	109.5
C4—N2—B1	129.95 (18)	C14—C15—H15B	109.5
N1—N2—B1	119.62 (15)	H15A—C15—H15B	109.5
C7—N3—N4	106.05 (15)	C14—C15—H15C	109.5
C7—N3—Ir1	138.98 (13)	H15A—C15—H15C	109.5
N4—N3—Ir1	114.84 (11)	H15B—C15—H15C	109.5
C9—N4—N3	109.95 (16)	C17A—C16A—Ir1	111.13 (19)
C9—N4—B1	127.88 (17)	C17A—C16A—H16A	109.4
N3—N4—B1	121.00 (14)	Ir1—C16A—H16A	109.4
C12—N5—N6	106.05 (15)	C17A—C16A—H16B	109.4
C12—N5—Ir1	138.20 (13)	Ir1—C16A—H16B	109.4
N6—N5—Ir1	115.71 (11)	H16A—C16A—H16B	108.0
C14—N6—N5	109.89 (16)	C18A—C17A—C16A	105.5 (3)
C14—N6—B1	128.16 (17)	C18A—C17A—H17A	110.6
N5—N6—B1	121.92 (15)	C16A—C17A—H17A	110.6
N2—B1—N4	111.05 (16)	C18A—C17A—H17B	110.6
N2—B1—N6	109.40 (15)	C16A—C17A—H17B	110.6
N4—B1—N6	109.86 (17)	H17A—C17A—H17B	108.8
N2—B1—H1	108.8	C17A—C18A—C19A	114.6 (3)
N4—B1—H1	108.8	C17A—C18A—H18A	108.6
N6—B1—H1	108.8	C19A—C18A—H18A	108.6
C2—C1—H1A	109.5	C17A—C18A—H18B	108.6
C2—C1—H1B	109.5	C19A—C18A—H18B	108.6
H1A—C1—H1B	109.5	H18A—C18A—H18B	107.6
C2—C1—H1C	109.5	C18A—C19A—Ir1	111.3 (2)
H1A—C1—H1C	109.5	C18A—C19A—H19A	109.4
H1B—C1—H1C	109.5	Ir1—C19A—H19A	109.4
N1—C2—C3	110.2 (2)	C18A—C19A—H19B	109.4
N1—C2—C1	124.98 (19)	Ir1—C19A—H19B	109.4
C3—C2—C1	124.8 (2)	H19A—C19A—H19B	108.0
C4—C3—C2	105.85 (19)	C18B—C17B—H17C	108.7
C4—C3—H3	127.1	C18B—C17B—H17D	108.7
C2—C3—H3	127.1	H17C—C17B—H17D	107.6
N2—C4—C3	107.92 (19)	C17B—C18B—H18C	110.6
N2—C4—C5	122.5 (2)	C17B—C18B—H18D	110.6
C3—C4—C5	129.5 (2)	H18C—C18B—H18D	108.7
C4—C5—H5A	109.5	P1—C20—H20A	109.5
C4—C5—H5B	109.5	P1—C20—H20B	109.5
H5A—C5—H5B	109.5	H20A—C20—H20B	109.5
C4—C5—H5C	109.5	P1—C20—H20C	109.5
H5A—C5—H5C	109.5	H20A—C20—H20C	109.5
H5B—C5—H5C	109.5	H20B—C20—H20C	109.5
C7—C6—H6A	109.5	P1—C21—H21A	109.5
C7—C6—H6B	109.5	P1—C21—H21B	109.5
H6A—C6—H6B	109.5	H21A—C21—H21B	109.5
C7—C6—H6C	109.5	P1—C21—H21C	109.5
H6A—C6—H6C	109.5	H21A—C21—H21C	109.5
H6B—C6—H6C	109.5	H21B—C21—H21C	109.5
N3—C7—C8	110.04 (17)	P1—C22—H22A	109.5
N3—C7—C6	125.19 (18)	P1—C22—H22B	109.5
C8—C7—C6	124.74 (18)	H22A—C22—H22B	109.5
C9—C8—C7	106.32 (17)	P1—C22—H22C	109.5
C9—C8—H8	126.8	H22A—C22—H22C	109.5
C7—C8—H8	126.8	H22B—C22—H22C	109.5

C19A—Ir1—P1—C22	139.06 (10)	C9—N4—B1—N6	−117.7 (2)
C16A—Ir1—P1—C22	−138.85 (10)	N3—N4—B1—N6	48.6 (2)
N3—Ir1—P1—C22	−42.79 (10)	C14—N6—B1—N2	−116.6 (2)
N1—Ir1—P1—C22	46.56 (10)	N5—N6—B1—N2	65.6 (2)
C19A—Ir1—P1—C20	−103.39 (16)	C14—N6—B1—N4	121.2 (2)
C16A—Ir1—P1—C20	−21.30 (16)	N5—N6—B1—N4	−56.6 (2)
N3—Ir1—P1—C20	74.76 (16)	N2—N1—C2—C3	−0.1 (2)
N1—Ir1—P1—C20	164.11 (16)	Ir1—N1—C2—C3	176.12 (14)
C19A—Ir1—P1—C21	17.18 (14)	N2—N1—C2—C1	179.2 (2)
C16A—Ir1—P1—C21	99.27 (14)	Ir1—N1—C2—C1	−4.5 (3)
N3—Ir1—P1—C21	−164.67 (13)	N1—C2—C3—C4	0.3 (2)
N1—Ir1—P1—C21	−75.32 (13)	C1—C2—C3—C4	−179.0 (2)
C19A—Ir1—N1—C2	−40.51 (19)	N1—N2—C4—C3	0.4 (2)
N5—Ir1—N1—C2	−131.63 (19)	B1—N2—C4—C3	−174.72 (18)
N3—Ir1—N1—C2	146.71 (19)	N1—N2—C4—C5	178.7 (2)
P1—Ir1—N1—C2	52.85 (19)	B1—N2—C4—C5	3.6 (3)
C19A—Ir1—N1—N2	135.43 (13)	C2—C3—C4—N2	−0.4 (2)
N5—Ir1—N1—N2	44.31 (12)	C2—C3—C4—C5	−178.6 (2)
N3—Ir1—N1—N2	−37.35 (12)	N4—N3—C7—C8	−1.2 (2)
P1—Ir1—N1—N2	−131.21 (11)	Ir1—N3—C7—C8	174.17 (15)
C2—N1—N2—C4	−0.2 (2)	N4—N3—C7—C6	176.69 (19)
Ir1—N1—N2—C4	−177.32 (13)	Ir1—N3—C7—C6	−7.9 (3)
C2—N1—N2—B1	175.50 (16)	N3—C7—C8—C9	1.1 (2)
Ir1—N1—N2—B1	−1.7 (2)	C6—C7—C8—C9	−176.8 (2)
C16A—Ir1—N3—C7	37.8 (2)	N3—N4—C9—C8	−0.2 (2)
N5—Ir1—N3—C7	128.7 (2)	B1—N4—C9—C8	167.3 (2)
P1—Ir1—N3—C7	−52.3 (2)	N3—N4—C9—C10	179.1 (2)
N1—Ir1—N3—C7	−145.5 (2)	B1—N4—C9—C10	−13.4 (3)
C16A—Ir1—N3—N4	−147.08 (13)	C7—C8—C9—N4	−0.5 (2)
N5—Ir1—N3—N4	−56.23 (12)	C7—C8—C9—C10	−179.7 (2)
P1—Ir1—N3—N4	122.79 (12)	N6—N5—C12—C13	0.3 (2)
N1—Ir1—N3—N4	29.60 (12)	Ir1—N5—C12—C13	−177.23 (15)
C7—N3—N4—C9	0.9 (2)	N6—N5—C12—C11	−179.78 (19)
Ir1—N3—N4—C9	−175.78 (13)	Ir1—N5—C12—C11	2.7 (3)
C7—N3—N4—B1	−167.66 (17)	N5—C12—C13—C14	0.5 (2)
Ir1—N3—N4—B1	15.7 (2)	C11—C12—C13—C14	−179.4 (2)
C19A—Ir1—N5—C12	45.3 (2)	N5—N6—C14—C13	1.3 (2)
C16A—Ir1—N5—C12	−36.8 (2)	B1—N6—C14—C13	−176.71 (19)
N3—Ir1—N5—C12	−132.7 (2)	N5—N6—C14—C15	−176.8 (2)
N1—Ir1—N5—C12	137.5 (2)	B1—N6—C14—C15	5.2 (3)
C19A—Ir1—N5—N6	−132.07 (13)	C12—C13—C14—N6	−1.1 (2)
C16A—Ir1—N5—N6	145.77 (13)	C12—C13—C14—C15	176.9 (2)
N3—Ir1—N5—N6	49.90 (12)	C19A—Ir1—C16A—C17A	29.0 (2)
N1—Ir1—N5—N6	−39.86 (12)	N5—Ir1—C16A—C17A	120.0 (2)
C12—N5—N6—C14	−1.0 (2)	N3—Ir1—C16A—C17A	−158.2 (2)
Ir1—N5—N6—C14	177.18 (13)	P1—Ir1—C16A—C17A	−64.3 (2)
C12—N5—N6—B1	177.15 (17)	Ir1—C16A—C17A—C18A	−42.2 (4)
Ir1—N5—N6—B1	−4.7 (2)	C16A—C17A—C18A—C19A	36.2 (5)
C4—N2—B1—N4	−123.3 (2)	C17A—C18A—C19A—Ir1	−14.3 (4)
N1—N2—B1—N4	62.0 (2)	C16A—Ir1—C19A—C18A	−8.1 (2)
C4—N2—B1—N6	115.2 (2)	N5—Ir1—C19A—C18A	−99.6 (2)
N1—N2—B1—N6	−59.4 (2)	P1—Ir1—C19A—C18A	81.2 (2)
C9—N4—B1—N2	121.1 (2)	N1—Ir1—C19A—C18A	174.6 (2)
N3—N4—B1—N2	−72.6 (2)

Experimental details

Crystal data
Chemical formula	[Ir(C₄H₈)(C₁₅H₂₂BN₆)(C₃H₉P)]
M_r	621.57
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	11.1865 (5), 18.1771 (8), 13.4748 (6)
β (°)	112.883 (1)
V (Å³)	2524.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.37
Crystal size (mm)	0.22 × 0.15 × 0.14

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.36, 0.47
No. of measured, independent and observed [I > 2σ(I)] reflections	37102, 7359, 6892
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.040, 1.08
No. of reflections	7359
No. of parameters	298
No. of restraints	25
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.32

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Ir1—C19A	2.0780 (18)	Ir1—N3	2.2233 (15)
Ir1—C16A	2.0871 (19)	Ir1—P1	2.2381 (5)
Ir1—N5	2.1781 (14)	Ir1—N1	2.2590 (15)

Acknowledgements

Financial support (FEDER) from the Spanish Ministry of Science (projects CTQ2010–17476 and Consolider-Ingenio 2010 CSD2007–00006) and the Junta de Andalucía (grant FQM-119 and project P09-FQM-4832) is acknowledged.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Bruker (2003). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Conejero, S., Paneque, M., Poveda, M. L., Santos, L. L. & Carmona, E. (2010). Acc. Chem. Res. 43, 572–580. Web of Science CrossRef CAS PubMed Google Scholar
Crabtree, R. H. (2005). The Organometallic Chemistry of the Transition Metals, 4th ed. New Jersey: John Wiley and Sons Inc. Google Scholar
Gómez, M., Paneque, M., Poveda, M. L. & Alvarez, E. (2007). J. Am. Chem. Soc. 129, 6092–6093. Web of Science PubMed Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Paneque, M., Poveda, M. L., Salazar, V., Gutiérrez-Puebla, E. & Monge, A. (2000). Organometallics, 19, 3120–3126. Web of Science CSD CrossRef CAS Google Scholar
Perutz, R. N. & Sabo-Etienne, S. (2007). Angew. Chem. Int. Ed. 46, 2578–2592. Web of Science CrossRef CAS Google Scholar
Pettinari, C. & Trofimenko, S. (2008). In Scorpionates II: Chelating Borate Ligands. London: Imperial College Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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