Two iridanonaborane compounds

Two iridanonaborane compounds, 4-carbonyl-5,6:8,9-bis-μH-4-hydrido-4-bis­(tri­methyl­phosphine)-4-irida-arachno-nonaborane(12), [IrH(B₈H₁₂)(C₃H₉P)₂(CO)], (Ia), and 2-carbonyl-2,5:6,9:8,9-tri-μH-4-chloro-2-bis­(tri­methyl­phosphine)-2-irida-nido-nonaborane(11), [Ir(B₈H₁₀Cl)(C₃H₉P)₂(CO)], (II), are described. Compound (II) shows evidence of effective chlorine-substituent migration during its formation.

S1. Comment

The arachno-iridanonaborane [4,4,4,4-CO(PMe₃)₂H-arachno-4-IrB₈H₁₂], (Ia), and its chloro analogue [4,4,4,4-(CO)(PMe₃)₂H-arachno-4-IrB₈H₁₁-2-Cl], (Ib), are obtained from the reaction of [IrCl(CO)(PMe₃)₂] with the [nido-B₉H₁₂]^- anion (Bould et al., 1982, 1984). In the original reports on these compounds, the arachno structural type was characterized by a single-crystal X-ray diffraction analysis of the chlorinated derivative, (Ib), but the data were of insufficient quality for H-atom location, although they were reasonably positioned from the results of NMR spectroscopy. In the report on the structure of (Ib) it was surmised that the two endo-terminal H atoms may have partial bridging character (hatched lines in the scheme). However, recent experimental observations and theoretical considerations on non-metal-containing arachno nine-vertex species (Hofmann & Schleyer, 1999; Bould et al., 2000) suggest that one of these H atoms may be bridging and one endo-terminal, with rapid equilibration between the two in solution, and it is useful to attempt to investigate their character crystallographically. \sch

Compound (Ib) has the symmetric ligand disposition shown in the scheme. The structural determination of (Ia) (Fig. 1) now confirms that it has the alternative asymmetric ligand disposition reasonably proposed from NMR spectroscopy. Otherwise, interatomic dimensions in (Ia) are very similar to those in (Ib), with the main differences arising principally from metal hydride trans effects. Thus, the Ir4—P2 distance of 2.368 (2) Å trans to the hydride in (Ia) is significantly longer than the cis-to-H Ir4—P distances in (Ib) [2.334 (2) and 2.346 (2) Å] and Ir4—P1 in (Ia) [2.3319 (15) Å]. Although the Cl substituent on B2 has a noticeable effect on the thermodynamic parameters for the arachno → nido closure process (Bould et al., 1984), its absence in (Ia) shows no significant effect on the interatomic dimensions regarding vertex B2 when compared with (Ib). Unfortunately, the H atoms did not refine satisfactorily and their disposition as endo-terminal or bridging H atoms remains unresolved in nine-vertex arachno-metallanonaborane clusters.

The arachno nine-vertex iridaboranes are also interesting starting materials for a good variety of interesting metallaborane chemistry (Bould et al., 1996, 1997). Fusion of arachno metallanonaboaranes in molten decaborane affords a number of interesting fused macropolyhedral species (Bould et al., 1999). For example, compound (Ia) gives the mixed cluster fusion products [(PMe₃)₂IrB₂₆H₂₄Ir(CO)(PMe₃)₂] and [(CO)(PMe₃)₂IrB₁₇H₂₀] in low yields. In an attempt to vary these yields and products we have used the chloro-substituted species, (Ib). In the event, however, fusion of an intimate mixture of decaborane(14) and (Ib) at 396 K yielded the second title compound, [2,2,2-(CO)(PMe₃)₂-nido-2-IrB₈H₁₀-4-Cl], (II), as the only isolatable product. A single-crystal X-ray diffraction study was carried out in order to confirm the position of the Cl substituent deduced from NMR spectroscopy (Experimental).

All atoms, including H atoms, were located and freely refined in reasonable positions for (II) (Fig. 2). Additionally, the position of the Cl substituent is confirmed. It differs from the position previously reported for [2,2,2-(CO)(PMe₃)₂-nido-2-IrB₈H₁₀-3-Cl] obtained from the thermolysis of (Ib) in the absence of B₁₀H₁₄ (Bould et al., 1984). The cluster is also similar to the other structurally characterized nido-metallanonaborane species, namely, the third-row rhenaborane [(PMe₂Ph)₃H₂-nido-ReB₈H₁₁] (Beckett et al., 1988), in which all H atoms were located except for the terminal and bridging metal hydrides, and the nido-{IrB₈} subcluster in the macropolyhedral species [(PMe₃)₂IrB₂₆H₂₄Ir(CO)(PMe₃)₂] (Bould et al., 1997).

The position of the Cl substituent in (II) indicates that, during the thermolysis of the arachno-metallaborane precursor compound (Ib) to give (II), the substituent has moved from a B vertex adjacent to the metal atom in the precursor to a position one vertex removed from the metal. In this context, it may be noted that strong heating of a xylene solution of [2,2,2-(CO)(PMe₃)₂-nido-2-IrB₈H₁₀-3-Cl] results in cluster closure, to give the iso-closo species [(PMe₃)₂HIrB₈H₇Cl] in which a comparable movement of the Cl to a B vertex remote from the metal centre has been noted (Bould et al., 1982). A mechanism was proposed in which the migration would occur via a cluster diamond-square-diamond rearrangement during the nido → iso-closo step. The low yield in the precursive arachno → nido closure reported here makes the proposal of a reaction mechanism speculative, although it does suggest that the Cl-migration step could also possibly occur prior to the nido → iso-closo closure.

S2. Experimental

The previously reported arachno compounds (Ia) and (Ib) were prepared as described by Bould et al. (1984). Single crystals of (Ia) were obtained by diffusion of pentane through a benzene layer into a CDCl₃ solution of the compound. The previously unreported nido compound, (II), was isolated from the thermolysis of the arachno compound (Ib) as follows. A finely ground mixture of [4,4,4,4-(CO)(PMe₃)₂H-4-IrB₈H₁₁-2-Cl] [(Ib), 73 mg, 145 µmol] and B₁₀H₁₄ (0.51 g, 4200 µmol) was placed in a 10 mm soda glass NMR tube which was then evacuated, refilled with nitrogen and heated in an oil bath at 396 K for 55 min, after which time the excess B₁₀H₁₄ was removed by sublimation (357 K, ca 0.01 mm H g). Thin-layer chromatography of the residue (Aldrich standard grade silica gel with gypsum binder and fluorescent indicator, 70:30 CH₂Cl₂/hexane) showed a number of diffuse faint yellow and red bands between R_F 0.1 and 0.8. Separation and identification of these bands proved difficult, but one yellow band, at R_F 0.1, after further separation by high-performance liquid chromatography [silica, Lichosorb Si60 7 µm, 260 × 16 mm column, CH₂Cl₂/hexane (80:20, 5 ml min^-1), R_T 15 min] and crystallization by diffusion of pentane through a benzene layer into a CDCl₃ solution of the compound, gave crystals of (II) suitable for diffraction analysis (2 mg, 4 µmol, 3%). NMR spectroscopic analysis: (p.p.m., CDCl₃, 300 K, Bruker 250 ARX spectrometer, δ(¹¹B) [δ(¹H) in square brackets]: B1 19.9 [4.77], B4 19.9 (site of Cl substituent), B6 - 4.8 [3.01], B3, B8, B9 - 12.2 [-1.35] -14.2 (2) [-2.8 and -1.30], B5 - 35.8 [0.14], B7 - 51.7 [-1.11]; ¹H NMR (δ, p.p.m.): H2/H5 - 14.46 [²J(³¹P-¹H) 62 Hz], H6/H9 and H8/H9 - 2.76 and -2.02, P(CH₃)₃ 1.91 and 1.78 [²J(³¹P-¹H) 10 Hz]; ³¹P NMR (δ, p.p.m.): -42.0 and -51.5.

S3. Refinement

Data were collected for compound (Ia) using a mixture of area-detector ω and ϕ exposures, with the CCD detector positioned 30 mm from the sample. Methyl H atoms were constrained to calculated positions with isotropic displacement parameters equal to 1.2U_eq of the parent C atom. Cluster-associated H atoms were located via Fourier difference syntheses and were included in structure factor calculations but were not refined. For both compounds, all boron-cage H atoms were located from the difference Fourier map and were refined freely. Non-boron-cage H atoms were included in their idealized geometry and were treated with the appropriate riding model (AFIX in? SHELXTL; Sheldrick, 1998). Please clarify - s.u.s only given for (II).

Computing details

Data collection: COLLECT (Nonius, 1998) for (Ia); SMART (Bruker, 1997) for (II). Cell refinement: DENZO-SMN (Otwinowski & Minor, 1996) for (Ia); SMART for (II). Data reduction: DENZO-SMN for (Ia); SAINT (Bruker, 1997) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEX (McArdle, 1995) for (Ia); SHELXTL (Sheldrick, 1998) for (II). For both compounds, software used to prepare material for publication: local program.

Figures

	Fig. 1. A perspective view of a single molecule of (Ia) drawn with 40% probability displacement ellipsoids and with H atoms shown as small circles of arbitrary radii.
	Fig. 2. A perspective view of a single molecule of (II) drawn with 40% probability displacement ellipsoids and with H atoms shown as small circles of arbitrary radii.

(Ia) 5,6:8,9-bis-µH-4-carbonyl-4-hydrido-4-bis(trimethylphosphine)-4-irido- arachno-nonaborane(12)

Crystal data

[IrH(B8H12)(C3H9P)2(CO)]	F(000) = 912
Mr = 471.94	Dx = 1.638 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.2035 (2) Å	Cell parameters from 11332 reflections
b = 15.9788 (5) Å	θ = 1–27.5°
c = 13.2013 (3) Å	µ = 7.13 mm^−1
β = 99.670 (2)°	T = 150 K
V = 1913.81 (8) Å^3	Prism, colourless
Z = 4	0.62 × 0.25 × 0.11 mm

Data collection

Nonius KappaCCD area-detector diffractometer	3737 independent reflections
Radiation source: Fine-focus sealed tube	3547 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.075
Detector resolution: 9.091 pixels mm^-1	θmax = 26°, θmin = 3.0°
1° ϕ scans for χ = 0°, 1° ω scans for χ = 90°	h = −11→11
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −19→19
Tmin = 0.096, Tmax = 0.508	l = −16→16
15922 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.105	w = 1/[σ^2(Fo^2) + (0.0588P)^2 + 4.8183P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
3737 reflections	Δρmax = 2.01 e Å^−3
179 parameters	Δρmin = −2.88 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0037 (5)

Special details

Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10° ϕ range.

Detector set at 30 mm from sample with different 2θ offsets. 1° ϕ exposures for χ = 0° settings, 1° ω exposures for χ = 90° settings

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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq
Ir4	0.04951 (2)	0.162921 (12)	0.114177 (13)	0.02470 (14)
H4	0.0858	0.0643	0.1171	0.03*
C1	−0.0339 (7)	0.1480 (4)	−0.0250 (5)	0.0334 (12)
O1	−0.0874 (6)	0.1340 (4)	−0.1078 (4)	0.0576 (12)
P1	0.2957 (2)	0.17093 (9)	0.09333 (13)	0.0322 (3)
C11	0.3930 (8)	0.0739 (5)	0.1210 (7)	0.064 (2)
H11A	0.3416	0.0294	0.0781	0.096*
H11B	0.3968	0.0597	0.1937	0.096*
H11C	0.4934	0.0796	0.1065	0.096*
C12	0.3291 (7)	0.1918 (5)	−0.0359 (5)	0.0453 (15)
H12A	0.4354	0.1909	−0.0366	0.068*
H12B	0.2894	0.247	−0.0581	0.068*
H12C	0.2806	0.1489	−0.0827	0.068*
C13	0.4160 (7)	0.2466 (5)	0.1677 (6)	0.056 (2)
H13A	0.4075	0.2415	0.2405	0.084*
H13B	0.3873	0.3032	0.1436	0.084*
H13C	0.5181	0.2361	0.1593	0.084*
P2	0.0012 (2)	0.30854 (10)	0.10708 (10)	0.0310 (3)
C21	0.0615 (8)	0.3635 (5)	0.0001 (5)	0.049 (2)
H21A	0.0278	0.4217	−0.0012	0.073*
H21B	0.0198	0.336	−0.0646	0.073*
H21C	0.1694	0.3622	0.0087	0.073*
C22	−0.1938 (9)	0.3353 (4)	0.0875 (6)	0.047 (2)
H22A	−0.2054	0.3958	0.0773	0.071*
H22B	−0.2358	0.3185	0.1479	0.071*
H22C	−0.2453	0.306	0.0267	0.071*
C23	0.0803 (8)	0.3728 (4)	0.2165 (5)	0.0447 (15)
H23A	0.188	0.3701	0.2255	0.067*
H23B	0.0472	0.352	0.2786	0.067*
H23C	0.0481	0.4309	0.2041	0.067*
B1	−0.0623 (7)	0.1731 (4)	0.2528 (5)	0.0283 (13)
H1	−0.0949	0.2395	0.2644	0.034*
B2	−0.1763 (7)	0.0909 (4)	0.2821 (5)	0.0346 (13)
H2	−0.2786	0.1019	0.3156	0.042*
B3	−0.0038 (7)	0.1093 (4)	0.3588 (5)	0.0341 (13)
H3	−0.0024	0.1314	0.4395	0.041*
B5	−0.1714 (7)	0.1168 (5)	0.1500 (5)	0.0340 (14)
H5	−0.2668	0.1433	0.1034	0.041*
H56	−0.1523	0.0585	0.109	0.041*
B6	−0.1866 (8)	0.0075 (5)	0.1978 (6)	0.0400 (15)
H6	−0.3011	−0.0251	0.1842	0.048*
H67	−0.0773	−0.0415	0.2143	0.048*
B7	−0.0535 (8)	0.0059 (5)	0.3178 (6)	0.043 (2)
H7	−0.0682	−0.0524	0.361	0.051*
H78	0.1037	−0.0155	0.3019	0.051*
B8	0.1403 (8)	0.0416 (5)	0.3439 (5)	0.0388 (14)
H8	0.2162	0.0071	0.418	0.047*
H89	0.1901	0.0825	0.2778	0.047*
B9	0.1298 (8)	0.1493 (5)	0.2858 (6)	0.0356 (15)
H9	0.1926	0.1827	0.3184	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir4	0.0232 (2)	0.0314 (2)	0.0200 (2)	−0.00028 (6)	0.00525 (10)	−0.00015 (6)
C1	0.030 (3)	0.043 (3)	0.025 (3)	0.005 (2)	−0.002 (2)	0.000 (2)
O1	0.065 (3)	0.070 (4)	0.034 (3)	0.008 (3)	−0.003 (2)	−0.011 (2)
P1	0.0251 (7)	0.0407 (9)	0.0327 (8)	−0.0017 (5)	0.0100 (6)	0.0029 (6)
C11	0.040 (4)	0.065 (5)	0.093 (6)	0.016 (3)	0.030 (4)	0.030 (4)
C12	0.046 (4)	0.056 (4)	0.041 (3)	−0.008 (3)	0.027 (3)	−0.004 (3)
C13	0.036 (3)	0.085 (6)	0.048 (4)	−0.016 (3)	0.011 (3)	−0.011 (4)
P2	0.0352 (7)	0.0353 (8)	0.0232 (7)	0.0032 (6)	0.0072 (5)	0.0008 (6)
C21	0.062 (4)	0.044 (4)	0.043 (4)	0.003 (3)	0.019 (3)	0.014 (3)
C22	0.051 (4)	0.045 (4)	0.048 (4)	0.014 (3)	0.014 (3)	0.007 (3)
C23	0.059 (4)	0.041 (4)	0.035 (3)	−0.005 (3)	0.010 (3)	−0.011 (3)
B1	0.033 (3)	0.032 (3)	0.023 (3)	−0.001 (2)	0.015 (3)	−0.001 (2)
B2	0.033 (3)	0.039 (4)	0.034 (3)	0.001 (3)	0.013 (3)	0.002 (3)
B3	0.036 (3)	0.042 (4)	0.027 (3)	0.002 (3)	0.011 (3)	0.003 (3)
B5	0.027 (3)	0.048 (4)	0.027 (3)	−0.002 (3)	0.007 (2)	−0.004 (3)
B6	0.034 (3)	0.045 (4)	0.044 (4)	−0.007 (3)	0.016 (3)	−0.005 (3)
B7	0.046 (4)	0.045 (4)	0.041 (4)	−0.001 (3)	0.017 (3)	0.006 (3)
B8	0.043 (4)	0.040 (4)	0.035 (3)	0.002 (3)	0.012 (3)	0.005 (3)
B9	0.034 (3)	0.039 (4)	0.034 (4)	−0.009 (3)	0.005 (3)	0.000 (3)

Geometric parameters (Å, º)

Ir4—C1	1.883 (6)	B1—B2	1.764 (9)
Ir4—B1	2.251 (6)	B1—B5	1.789 (9)
Ir4—B9	2.272 (8)	B1—B9	1.789 (10)
Ir4—B5	2.285 (6)	B2—B6	1.727 (10)
Ir4—P1	2.3319 (15)	B2—B3	1.759 (9)
Ir4—P2	2.368 (2)	B2—B7	1.779 (10)
C1—O1	1.143 (7)	B2—B5	1.800 (9)
P1—C11	1.797 (7)	B3—B8	1.748 (9)
P1—C13	1.813 (7)	B3—B7	1.774 (10)
P1—C12	1.814 (6)	B3—B9	1.802 (9)
P2—C22	1.821 (8)	B5—B6	1.870 (10)
P2—C23	1.821 (6)	B6—B7	1.832 (11)
P2—C21	1.827 (6)	B7—B8	1.850 (10)
B1—B3	1.743 (9)	B8—B9	1.879 (10)
C1—Ir4—B1	129.4 (3)	B6—B2—B7	63.0 (4)
C1—Ir4—B9	166.2 (3)	B3—B2—B7	60.2 (4)
B1—Ir4—B9	46.6 (3)	B1—B2—B7	104.6 (4)
C1—Ir4—B5	86.0 (2)	B6—B2—B5	64.0 (4)
B1—Ir4—B5	46.4 (2)	B3—B2—B5	110.7 (4)
B9—Ir4—B5	85.1 (2)	B1—B2—B5	60.2 (4)
C1—Ir4—P1	97.9 (2)	B7—B2—B5	108.3 (4)
B1—Ir4—P1	132.7 (2)	B1—B3—B8	114.1 (4)
B9—Ir4—P1	87.9 (2)	B1—B3—B2	60.5 (4)
B5—Ir4—P1	163.4 (2)	B8—B3—B2	117.4 (5)
C1—Ir4—P2	92.5 (2)	B1—B3—B7	105.7 (5)
B1—Ir4—P2	81.5 (2)	B8—B3—B7	63.4 (4)
B9—Ir4—P2	99.3 (2)	B2—B3—B7	60.5 (4)
B5—Ir4—P2	99.0 (2)	B1—B3—B9	60.6 (4)
P1—Ir4—P2	96.96 (5)	B8—B3—B9	63.9 (4)
O1—C1—Ir4	175.7 (6)	B2—B3—B9	112.4 (5)
C11—P1—C13	103.2 (4)	B7—B3—B9	109.3 (5)
C11—P1—C12	101.1 (4)	B1—B5—B2	58.9 (3)
C13—P1—C12	101.7 (3)	B1—B5—B6	106.1 (4)
C11—P1—Ir4	112.9 (2)	B2—B5—B6	56.1 (4)
C13—P1—Ir4	119.3 (2)	B1—B5—Ir4	65.8 (3)
C12—P1—Ir4	116.3 (2)	B2—B5—Ir4	116.3 (4)
C22—P2—C23	103.5 (3)	B6—B5—Ir4	119.4 (4)
C22—P2—C21	101.4 (3)	B2—B6—B7	59.9 (4)
C23—P2—C21	102.1 (4)	B2—B6—B5	59.9 (4)
C22—P2—Ir4	114.2 (2)	B7—B6—B5	103.2 (5)
C23—P2—Ir4	118.4 (2)	B3—B7—B2	59.3 (4)
C21—P2—Ir4	115.0 (2)	B3—B7—B6	110.6 (5)
B3—B1—B2	60.2 (4)	B2—B7—B6	57.1 (4)
B3—B1—B5	111.9 (5)	B3—B7—B8	57.6 (4)
B2—B1—B5	60.9 (4)	B2—B7—B8	111.3 (5)
B3—B1—B9	61.3 (4)	B6—B7—B8	129.8 (5)
B2—B1—B9	112.8 (5)	B3—B8—B7	59.0 (4)
B5—B1—B9	118.9 (4)	B3—B8—B9	59.5 (4)
B3—B1—Ir4	119.3 (4)	B7—B8—B9	103.0 (5)
B2—B1—Ir4	119.6 (4)	B1—B9—B3	58.1 (4)
B5—B1—Ir4	67.8 (3)	B1—B9—B8	106.0 (4)
B9—B1—Ir4	67.3 (3)	B3—B9—B8	56.7 (4)
B6—B2—B3	116.5 (5)	B1—B9—Ir4	66.1 (3)
B6—B2—B1	113.8 (4)	B3—B9—Ir4	115.5 (4)
B3—B2—B1	59.3 (4)	B8—B9—Ir4	118.7 (4)

(II) 2,5:6,9:8,9-tri-µH-2-carbonyl-4-chloro-2-bis(trimethylphosphine)-2-irido- nido-nonaborane(11)

Crystal data

[Ir(B8H10Cl)(C3H9P)2(CO)]	F(000) = 968
Mr = 504.36	Dx = 1.766 Mg m^−3 Dm = no Mg m^−3 Dm measured by not measured
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.2655 (1) Å	Cell parameters from 8192 reflections
b = 12.1784 (1) Å	θ = 2–27°
c = 16.8668 (1) Å	µ = 7.34 mm^−1
β = 94.702 (1)°	T = 223 K
V = 1896.83 (3) Å^3	Rectangular, yellow
Z = 4	0.23 × 0.22 × 0.10 mm

Data collection

Nonius KappaCCD? area-detector diffractometer	4150 independent reflections
Radiation source: normal-focus sealed tube	3824 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ϕ and ω scans	θmax = 27.0°, θmin = 2.1°
Absorption correction: empirical (using intensity measurements) (SADABS; Blessing, 1995)	h = −11→11
Tmin = 0.283, Tmax = 0.528	k = −15→15
55769 measured reflections	l = −21→21

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.041	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ^2(Fo^2) + (0.012P)^2 + 2.6P] where P = (Fo^2 + 2Fc^2)/3
4150 reflections	(Δ/σ)max = 0.001
221 parameters	Δρmax = 1.00 e Å^−3
0 restraints	Δρmin = −0.51 e Å^−3

Special details

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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq
Ir2	−0.491487 (11)	0.265072 (8)	−0.314885 (6)	0.02152 (4)
Cl1	−0.65539 (9)	−0.03900 (7)	−0.15775 (6)	0.0440 (2)
P1	−0.58407 (10)	0.23739 (7)	−0.44779 (5)	0.03146 (17)
P2	−0.25027 (9)	0.25232 (6)	−0.34079 (5)	0.02895 (16)
O1	−0.4718 (3)	0.51658 (19)	−0.32160 (15)	0.0464 (6)
B1	−0.5458 (4)	0.0977 (3)	−0.2880 (2)	0.0271 (7)
B3	−0.4297 (4)	0.1506 (3)	−0.2098 (2)	0.0295 (7)
B4	−0.6024 (4)	0.0947 (3)	−0.1944 (2)	0.0290 (7)
B5	−0.7063 (4)	0.1694 (3)	−0.2678 (2)	0.0280 (7)
B6	−0.4431 (4)	0.2941 (3)	−0.1792 (2)	0.0318 (7)
B7	−0.5249 (4)	0.1907 (3)	−0.1227 (2)	0.0357 (8)
B8	−0.7127 (4)	0.2036 (3)	−0.1618 (2)	0.0337 (8)
B9	−0.6026 (5)	0.3170 (4)	−0.1258 (2)	0.0403 (9)
C1	−0.4794 (3)	0.4230 (3)	−0.32131 (17)	0.0295 (6)
C2	−0.4818 (5)	0.1528 (3)	−0.5118 (2)	0.0518 (10)
H2A	−0.3827	0.1790	−0.5100	0.078*
H2B	−0.5254	0.1571	−0.5660	0.078*
H2C	−0.4826	0.0772	−0.4938	0.078*
C3	−0.6099 (4)	0.3625 (3)	−0.5052 (2)	0.0471 (9)
H3A	−0.5199	0.4035	−0.5026	0.071*
H3B	−0.6845	0.4067	−0.4837	0.071*
H3C	−0.6391	0.3443	−0.5602	0.071*
C4	−0.7615 (4)	0.1749 (4)	−0.4605 (2)	0.0578 (11)
H4A	−0.7605	0.1059	−0.4318	0.087*
H4B	−0.7871	0.1615	−0.5166	0.087*
H4C	−0.8322	0.2238	−0.4400	0.087*
C5	−0.1220 (3)	0.2922 (3)	−0.2591 (2)	0.0405 (8)
H5A	−0.1394	0.2495	−0.2123	0.061*
H5B	−0.1337	0.3697	−0.2478	0.061*
H5C	−0.0243	0.2788	−0.2734	0.061*
C6	−0.1981 (4)	0.3410 (3)	−0.4203 (2)	0.0419 (8)
H6A	−0.2605	0.3268	−0.4683	0.063*
H6B	−0.0983	0.3262	−0.4303	0.063*
H6C	−0.2077	0.4172	−0.4048	0.063*
C7	−0.1878 (4)	0.1161 (3)	−0.3663 (2)	0.0457 (9)
H7A	−0.2504	0.0869	−0.4103	0.069*
H7B	−0.1904	0.0680	−0.3206	0.069*
H7C	−0.0894	0.1208	−0.3817	0.069*
H1	−0.544 (3)	0.016 (3)	−0.3286 (18)	0.030 (8)*
H3	−0.314 (3)	0.107 (2)	−0.1950 (17)	0.021 (7)*
H5	−0.807 (4)	0.150 (3)	−0.301 (2)	0.038 (9)*
H6	−0.345 (4)	0.339 (3)	−0.157 (2)	0.044 (10)*
H7	−0.472 (4)	0.132 (3)	−0.056 (2)	0.051 (11)*
H8	−0.802 (4)	0.180 (3)	−0.130 (2)	0.045 (10)*
H9	−0.612 (3)	0.375 (3)	−0.0736 (19)	0.037 (9)*
H25	−0.658 (4)	0.270 (3)	−0.284 (2)	0.052 (11)*
H69	−0.551 (4)	0.370 (3)	−0.178 (2)	0.048 (10)*
H89	−0.717 (4)	0.298 (3)	−0.169 (2)	0.053 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir2	0.02085 (6)	0.02513 (6)	0.01844 (6)	−0.00061 (4)	0.00067 (4)	0.00186 (4)
Cl1	0.0382 (4)	0.0392 (4)	0.0558 (5)	−0.0032 (3)	0.0117 (4)	0.0163 (4)
P1	0.0385 (5)	0.0338 (4)	0.0211 (4)	−0.0058 (3)	−0.0034 (3)	0.0030 (3)
P2	0.0247 (4)	0.0358 (4)	0.0270 (4)	−0.0004 (3)	0.0059 (3)	0.0031 (3)
O1	0.0509 (15)	0.0294 (13)	0.0586 (17)	−0.0043 (10)	0.0018 (13)	0.0016 (11)
B1	0.0283 (17)	0.0263 (16)	0.0267 (16)	0.0012 (13)	0.0032 (13)	0.0040 (13)
B3	0.0264 (17)	0.0361 (18)	0.0260 (17)	−0.0020 (14)	0.0025 (13)	0.0096 (13)
B4	0.0247 (16)	0.0319 (17)	0.0305 (18)	−0.0006 (13)	0.0043 (14)	0.0082 (13)
B5	0.0221 (16)	0.0310 (17)	0.0307 (17)	−0.0015 (13)	0.0020 (13)	0.0042 (13)
B6	0.0322 (18)	0.044 (2)	0.0193 (16)	−0.0062 (15)	0.0020 (13)	−0.0020 (14)
B7	0.0323 (19)	0.049 (2)	0.0265 (17)	−0.0080 (16)	0.0050 (14)	0.0043 (15)
B8	0.0293 (18)	0.041 (2)	0.0326 (18)	−0.0006 (15)	0.0096 (15)	−0.0004 (15)
B9	0.046 (2)	0.048 (2)	0.0286 (19)	−0.0086 (18)	0.0122 (17)	−0.0078 (16)
C1	0.0275 (15)	0.0355 (17)	0.0254 (15)	−0.0014 (12)	0.0009 (12)	0.0010 (12)
C2	0.073 (3)	0.044 (2)	0.038 (2)	−0.0006 (19)	0.0047 (19)	−0.0129 (16)
C3	0.065 (3)	0.044 (2)	0.0303 (18)	0.0024 (18)	−0.0043 (17)	0.0101 (15)
C4	0.054 (2)	0.083 (3)	0.0339 (19)	−0.026 (2)	−0.0151 (17)	0.0094 (19)
C5	0.0240 (16)	0.056 (2)	0.0410 (19)	−0.0087 (14)	0.0008 (14)	0.0047 (16)
C6	0.0390 (19)	0.054 (2)	0.0337 (18)	−0.0065 (16)	0.0119 (15)	0.0083 (15)
C7	0.039 (2)	0.047 (2)	0.052 (2)	0.0126 (16)	0.0110 (17)	−0.0006 (17)

Geometric parameters (Å, º)

Ir2—C1	1.930 (3)	B6—B9	1.814 (5)
Ir2—B1	2.156 (3)	B6—H6	1.10 (4)
Ir2—B3	2.291 (3)	B6—H69	1.36 (4)
Ir2—P2	2.3174 (8)	B7—B9	1.697 (6)
Ir2—B6	2.323 (3)	B7—B8	1.816 (5)
Ir2—P1	2.3578 (8)	B7—H7	1.39 (4)
Ir2—B5	2.491 (3)	B8—B9	1.793 (6)
Ir2—H25	1.67 (4)	B8—H8	1.07 (4)
Cl1—B4	1.823 (3)	B8—H89	1.16 (4)
P1—C4	1.809 (4)	B9—H9	1.14 (3)
P1—C3	1.811 (3)	B9—H69	1.23 (4)
P1—C2	1.815 (4)	B9—H89	1.26 (4)
P2—C5	1.810 (3)	C2—H2A	0.9700
P2—C6	1.818 (3)	C2—H2B	0.9700
P2—C7	1.820 (4)	C2—H2C	0.9700
O1—C1	1.142 (4)	C3—H3A	0.9700
B1—B4	1.705 (5)	C3—H3B	0.9700
B1—B3	1.756 (5)	C3—H3C	0.9700
B1—B5	1.781 (5)	C4—H4A	0.9700
B1—H1	1.21 (3)	C4—H4B	0.9700
B3—B4	1.777 (5)	C4—H4C	0.9700
B3—B6	1.830 (5)	C5—H5A	0.9700
B3—B7	1.840 (5)	C5—H5B	0.9700
B3—H3	1.21 (3)	C5—H5C	0.9700
B4—B5	1.758 (5)	C6—H6A	0.9700
B4—B8	1.788 (5)	C6—H6B	0.9700
B4—B7	1.789 (5)	C6—H6C	0.9700
B5—B8	1.841 (5)	C7—H7A	0.9700
B5—H5	1.08 (3)	C7—H7B	0.9700
B5—H25	1.34 (4)	C7—H7C	0.9700
B6—B7	1.785 (5)
C1—Ir2—B1	165.75 (13)	B7—B6—B3	61.2 (2)
C1—Ir2—B3	129.64 (13)	B9—B6—B3	111.3 (3)
B1—Ir2—B3	46.39 (13)	B7—B6—Ir2	111.2 (2)
C1—Ir2—P2	89.72 (9)	B9—B6—Ir2	114.4 (2)
B1—Ir2—P2	102.81 (9)	B3—B6—Ir2	65.71 (15)
B3—Ir2—P2	85.48 (9)	B7—B6—H6	122.7 (19)
C1—Ir2—B6	84.04 (13)	B9—B6—H6	115.7 (19)
B1—Ir2—B6	88.10 (13)	B3—B6—H6	120.0 (19)
B3—Ir2—B6	46.72 (13)	Ir2—B6—H6	120.3 (18)
P2—Ir2—B6	94.85 (9)	B7—B6—H69	97.6 (16)
C1—Ir2—P1	96.16 (9)	B9—B6—H69	42.7 (16)
B1—Ir2—P1	89.51 (9)	B3—B6—H69	136.1 (16)
B3—Ir2—P1	134.20 (9)	Ir2—B6—H69	91.8 (15)
P2—Ir2—P1	95.31 (3)	H6—B6—H69	104 (2)
B6—Ir2—P1	169.84 (9)	B9—B7—B6	62.7 (2)
C1—Ir2—B5	122.37 (12)	B9—B7—B4	115.2 (3)
B1—Ir2—B5	44.33 (12)	B6—B7—B4	105.4 (2)
B3—Ir2—B5	67.93 (11)	B9—B7—B8	61.3 (2)
P2—Ir2—B5	146.78 (8)	B6—B7—B8	100.5 (3)
B6—Ir2—B5	81.49 (12)	B4—B7—B8	59.5 (2)
P1—Ir2—B5	89.90 (8)	B9—B7—B3	116.5 (3)
C1—Ir2—H25	92.3 (12)	B6—B7—B3	60.6 (2)
B1—Ir2—H25	74.5 (12)	B4—B7—B3	58.64 (19)
B3—Ir2—H25	87.9 (13)	B8—B7—B3	104.0 (2)
P2—Ir2—H25	172.8 (14)	B9—B7—H7	127.4 (15)
B6—Ir2—H25	78.5 (14)	B6—B7—H7	131.0 (15)
P1—Ir2—H25	91.3 (14)	B4—B7—H7	108.2 (15)
B5—Ir2—H25	30.2 (12)	B8—B7—H7	127.2 (15)
C4—P1—C3	102.20 (19)	B3—B7—H7	110.7 (15)
C4—P1—C2	101.8 (2)	B4—B8—B9	110.6 (3)
C3—P1—C2	102.21 (19)	B4—B8—B7	59.5 (2)
C4—P1—Ir2	115.44 (13)	B9—B8—B7	56.1 (2)
C3—P1—Ir2	114.21 (12)	B4—B8—B5	57.93 (19)
C2—P1—Ir2	118.68 (14)	B9—B8—B5	116.1 (3)
C5—P2—C6	101.81 (16)	B7—B8—B5	103.1 (2)
C5—P2—C7	102.90 (18)	B4—B8—H8	116 (2)
C6—P2—C7	104.93 (17)	B9—B8—H8	119 (2)
C5—P2—Ir2	114.93 (12)	B7—B8—H8	123.6 (19)
C6—P2—Ir2	114.72 (12)	B5—B8—H8	121.2 (19)
C7—P2—Ir2	115.84 (13)	B4—B8—H89	135.8 (19)
B4—B1—B3	61.8 (2)	B9—B8—H89	44.3 (19)
B4—B1—B5	60.54 (19)	B7—B8—H89	98 (2)
B3—B1—B5	98.4 (2)	B5—B8—H89	96.9 (19)
B4—B1—Ir2	108.0 (2)	H8—B8—H89	108 (3)
B3—B1—Ir2	70.85 (16)	B7—B9—B8	62.6 (2)
B5—B1—Ir2	77.87 (16)	B7—B9—B6	61.0 (2)
B4—B1—H1	121.7 (15)	B8—B9—B6	100.3 (3)
B3—B1—H1	133.6 (15)	B7—B9—H9	126.6 (17)
B5—B1—H1	124.4 (15)	B8—B9—H9	131.2 (17)
Ir2—B1—H1	130.3 (15)	B6—B9—H9	126.8 (17)
B1—B3—B4	57.70 (19)	B7—B9—H69	108.2 (18)
B1—B3—B6	120.7 (2)	B8—B9—H69	114.1 (17)
B4—B3—B6	104.0 (2)	B6—B9—H69	48.7 (17)
B1—B3—B7	113.1 (2)	H9—B9—H69	107 (2)
B4—B3—B7	59.2 (2)	B7—B9—H89	100.6 (19)
B6—B3—B7	58.2 (2)	B8—B9—H89	39.9 (18)
B1—B3—Ir2	62.77 (15)	B6—B9—H89	111.2 (18)
B4—B3—Ir2	100.08 (18)	H9—B9—H89	117 (2)
B6—B3—Ir2	67.57 (15)	H69—B9—H89	92 (2)
B7—B3—Ir2	110.5 (2)	O1—C1—Ir2	177.0 (3)
B1—B3—H3	118.2 (14)	P1—C2—H2A	109.5
B4—B3—H3	126.6 (14)	P1—C2—H2B	109.5
B6—B3—H3	116.4 (14)	H2A—C2—H2B	109.5
B7—B3—H3	115.4 (14)	P1—C2—H2C	109.5
Ir2—B3—H3	126.3 (14)	H2A—C2—H2C	109.5
B1—B4—B5	61.9 (2)	H2B—C2—H2C	109.5
B1—B4—B3	60.5 (2)	P1—C3—H3A	109.5
B5—B4—B3	98.4 (2)	P1—C3—H3B	109.5
B1—B4—B8	119.7 (2)	H3A—C3—H3B	109.5
B5—B4—B8	62.5 (2)	P1—C3—H3C	109.5
B3—B4—B8	107.8 (2)	H3A—C3—H3C	109.5
B1—B4—B7	118.4 (2)	H3B—C3—H3C	109.5
B5—B4—B7	107.7 (2)	P1—C4—H4A	109.5
B3—B4—B7	62.1 (2)	P1—C4—H4B	109.5
B8—B4—B7	61.0 (2)	H4A—C4—H4B	109.5
B1—B4—Cl1	116.4 (2)	P1—C4—H4C	109.5
B5—B4—Cl1	123.6 (2)	H4A—C4—H4C	109.5
B3—B4—Cl1	131.5 (2)	H4B—C4—H4C	109.5
B8—B4—Cl1	112.4 (2)	P2—C5—H5A	109.5
B7—B4—Cl1	117.3 (2)	P2—C5—H5B	109.5
B4—B5—B1	57.60 (19)	H5A—C5—H5B	109.5
B4—B5—B8	59.5 (2)	P2—C5—H5C	109.5
B1—B5—B8	113.0 (2)	H5A—C5—H5C	109.5
B4—B5—Ir2	93.49 (18)	H5B—C5—H5C	109.5
B1—B5—Ir2	57.80 (14)	P2—C6—H6A	109.5
B8—B5—Ir2	107.08 (19)	P2—C6—H6B	109.5
B4—B5—H5	130.8 (18)	H6A—C6—H6B	109.5
B1—B5—H5	119.3 (18)	P2—C6—H6C	109.5
B8—B5—H5	117.6 (18)	H6A—C6—H6C	109.5
Ir2—B5—H5	128.2 (18)	H6B—C6—H6C	109.5
B4—B5—H25	116.7 (17)	P2—C7—H7A	109.5
B1—B5—H25	96.5 (17)	P2—C7—H7B	109.5
B8—B5—H25	92.0 (17)	H7A—C7—H7B	109.5
Ir2—B5—H25	38.7 (17)	P2—C7—H7C	109.5
H5—B5—H25	112 (3)	H7A—C7—H7C	109.5
B7—B6—B9	56.3 (2)	H7B—C7—H7C	109.5