Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107022378/ga3042sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107022378/ga3042Isup2.hkl |
CCDC reference: 655493
The synthesis was performed under an argon atmosphere using standard Schlenk and glovebox techniques. tBuPCP-H was synthesized according to the method of Moulton & Shaw (1976). tBuPCP-H (2.000 g, 5.068 mmol) was dissolved in toluene (100 ml) to which [Ir(COD)Cl]2 (1.660 g, 2.472 mmol) was added, and the resulting solution was refluxed under argon for 2 d. The solution was cooled to room temperature and the solvent was removed by vacuum, followed by addition of hexane (50 ml) to the resulting solid. The red solution was pipetted away from the yellow insoluble material and filtered through glass wool before being placed in the freezer for one week. The resulting solid material (0.4299 g) contained large red crystals of complex (I), as well as a significant amount of microcrystalline (tBuPCP)IrHCl. Further details and 31P{1H} NMR data are given in the archived CIF.
The hydrido H atom was refined with a restrained Ir—H distance of 1.60 (1) Å and Uiso(H) = 1.5Ueq(Ir1), then with a fixed position for the last cycle of refinement. All other non-methyl H atoms were constrained to their respective idealized sp2 or sp3 geometries of 0.95 and 0.99 Å, respectively [Please check added text], and given Uiso(H) values of 1.2 times Ueq of the atom to which they are bonded. The methyl H atoms were given Uiso(H) values of 1.5 times Ueq of the C atom to which they are bonded (C—H = 0.98 Å [Please check added text]) and allowed to rotate as a rigid group to the angle that maximized the sum of the electron density at the three calculated H-atom positions.
There has been great interest in recent years in the development of pincer complexes (Albrecht & van Koten, 2001; Singleton, 2003; Van der Boom & Milstein, 2003), i.e. complexes of tridentate meridionally bound ligands (Moulton & Shaw, 1976). Derivatives of the pincer complex (tBuPCP)IrH2 [tBuPCP is κ3-2,6-(tBu2PCH2)2C6H3] (Gupta et al., 1996) have proven highly effective as catalysts for the dehydrogenation of alkanes (Gupta et al., 1996, 1997; Xu et al., 1997; Liu et al., 1999; Zhu et al., 2004; Goldman et al., 2006). The synthetic precursor to (tBuPCP)IrH2 (Gupta et al., 1996) is (tBuPCP)IrHCl (Moulton & Shaw, 1976). We have previously reported the hexanuclear iridium η4-2,5-cyclooctadiene complex [(COD)Ir]2{η6-[κ4-C6H2(CH2PtBu2)2] Ir2H2Cl3}2 (COD is 1,5-cyclooctadiene), which has been observed as a by-product of the synthesis of the (tBuPCP)IrHCl complex (Zhang, Emge et al., 2004). Here, we report another such by-product, an orange–red material that has been identified as (tBuPCP)IrH(µ2Cl)2Ir(COD), which was isolated as the hexane hemisolvate, (I).
Complex (I) (Fig. 1) is best viewed as the di(chloride-bridged) mixed-valence addition product of (PCP)IrHCl (Moulton & Shaw, 1976) and `(COD)IrCl'. The latter can be viewed as a monomeric unit of the dimer [Ir(COD)Cl]2, which has been crystallographically characterized previously (Cotton et al., 1986). The hydride was found in this complex using electron difference maps. The Ir—H distance, which is known from neutron diffraction measurements to be 1.60 Å (Eckert et al., 1995; Bau et al., 1993, 1984; Garlaschelli et al., 1985) and found on difference Fourier maps here at 1.60 Å, refines to a much shorter distance (~1.37 Å), but still along the difference Fourier map Ir—H vector, because of the close proximity to the metal atom (Z = 77). In such cases, it is preferable to restrain the distance to 1.60 Å, as was done here, using the SHELXL97 command `DFIX 1.60. 01' (Sheldrick, 1997).
The pincer-bound atom Ir1 is best considered as being formally in the +3 oxidation state. The Ir1—C1 distance (Table 1) is similar to the Ir—C distance found in other PCP complexes of either IrI or IrIII (Table 2). The Ir—P bond lengths (average 2.327 Å; Table 1) are consistent with the Ir—P bond lengths in reported PCP complexes of IrIII (Table 2), but somewhat outside the range reported for PCP complexes of IrI (2.27–2.30 Å; Table 2). As in other (PCP)Ir complexes, the P—Ir—P angle is decidedly not linear (Gupta et al., 1997; Zhang et al., 2005, 2006; Ghosh et al., 2007). Both P atoms are bent away from the Cl ligand cis to the PCP aryl C—Ir bond, as seen by the corresponding P1—Ir1—Cl2 and P2—Ir1—Cl2 angles given in Table 1. The COD-bound atom Ir2 is formally in the +1 oxidation state and can be viewed as approximately square planar if one considers the centers of the coordinating C—C double bonds as single coordination points.
The Ir(COD)Cl2 portion of (I) has a geometry consistent with either Ir(COD)Cl2 part of [Ir(COD)Cl]2. However, presumably due to the steric bulk of the tBuPCP ligand, the considerable folding about the Cl···Cl vector observed in [Ir(COD)Cl]2 is not present in compound (I). The dihedral angle between the Cl2—Ir1 and Cl2— Ir2 portions of the central Ir2Cl2 group is only 13.04 (4)°, compared with the 86° dihedral angle in [Ir(COD)Cl]2 (Cotton et al., 1986). This gives rise to a significantly greater Ir···Ir distance: in [Ir(COD)Cl]2 this distance is 2.910 (1) Å, while in complex (I) the value is 3.6754 (2) Å.
The Ir—Cl bond lengths for the trivalent atom Ir1 are noticeably longer (average 2.55 Å) than those for the monovalent atom Ir2 (average 2.40 Å) or those found in the [Ir(COD)Cl]2 dimer (average 2.40 Å) (Cotton et al., 1986). As seen in Table 1, the specific values of the Ir2—Cl distances are fairly similar. The two Ir1—Cl distances, however, are substantially different, with the bond to the Cl atom trans to the strong trans-influence hydride ligand being substantially longer than that trans to the PCP aryl C atom. Not surprisingly, the Ir1—Cl distances in (I) are longer than the Ir—Cl distances in (PCP)Ir complexes with terminal chloride ligands (Table 2).
The geometries of both weaker and significant C—H···Cl interactions are described in Table 3, where it is shown that the intramolecular Cl···H distances are as short as 2.66 Å from atom Cl2 to the PCP methyl atom H16A and as short as 2.79 Å from atom Cl1 to the COD methylenyl atom H26. There are two weak intermolecular (COD) C—H···Cl2 interactions (last two entries in Table 3). The hexane solvate molecule lies across the inversion center at y = 1/2 in a channel that propagates along the crystallographic b axis. As a result, each solvate molecule is surrounded by the methyl and methylenyl groups of six Ir2 dimer complexes. The packing of the Ir dimer complexes and the hexane solvate molecules yields only long C—H···H—C contacts (>2.54 Å) and the nearest Cl atom to any H atom on the hexane solvent is quite remote (>5 Å).
For related literature, see: Albrecht & van Koten (2001); Bau et al. (1984, 1993); Cotton et al. (1986); Eckert et al. (1995); Garlaschelli et al. (1985); Ghosh et al. (2007); Goldman et al. (2006); Gupta et al. (1996, 1997); Liu et al. (1999); Moulton & Shaw (1976); Sheldrick (1997); Singleton (2003); Van der Boom & Milstein (2003); Xu et al. (1997); Zhang et al. (2005, 2006); Zhang, Emge & Goldman (2004); Zhu et al. (2004).
Data collection: SMART (Bruker, 2005); cell refinement: SMART; data reduction: SAINT-Plus (Bruker,2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL.
[Ir2(C8H12)(C24H44P2)Cl2]·0.5C6H14 | F(000) = 1964 |
Mr = 1001.09 | Dx = 1.764 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8331 reflections |
a = 14.8424 (7) Å | θ = 2.6–30.6° |
b = 11.6735 (5) Å | µ = 7.30 mm−1 |
c = 22.0589 (10) Å | T = 100 K |
β = 99.416 (1)° | Lath, orange |
V = 3770.5 (3) Å3 | 0.19 × 0.12 × 0.08 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 11498 independent reflections |
Radiation source: fine-focus sealed tube | 10259 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
φ and ω scans | θmax = 30.6°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | h = −21→21 |
Tmin = 0.361, Tmax = 0.558 | k = −16→16 |
42778 measured reflections | l = −31→31 |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.03P)2 + 7.5P] where P = (Fo2 + 2Fc2)/3 |
11498 reflections | (Δ/σ)max = 0.003 |
383 parameters | Δρmax = 2.04 e Å−3 |
0 restraints | Δρmin = −1.03 e Å−3 |
[Ir2(C8H12)(C24H44P2)Cl2]·0.5C6H14 | V = 3770.5 (3) Å3 |
Mr = 1001.09 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.8424 (7) Å | µ = 7.30 mm−1 |
b = 11.6735 (5) Å | T = 100 K |
c = 22.0589 (10) Å | 0.19 × 0.12 × 0.08 mm |
β = 99.416 (1)° |
Bruker SMART CCD area-detector diffractometer | 11498 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | 10259 reflections with I > 2σ(I) |
Tmin = 0.361, Tmax = 0.558 | Rint = 0.033 |
42778 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.00 | Δρmax = 2.04 e Å−3 |
11498 reflections | Δρmin = −1.03 e Å−3 |
383 parameters |
Experimental. All solvents were purchased as anhydrous from Aldrich and degassed before use. NMR spectra were recorded on a Varian 400-MHz NMR spectrometer; 1H NMR signals are referenced to the residual proton peaks of the deuterated solvent and 31P{1H} NMR signals are referenced to PMe3 dissolved in p-xylene-d10, in a capillary. 31P{1H} (400 MHz, toluene-d8, δ, p.p.m.): 54.89 (d, J = 13 Hz); 1H (400 MHz, toluene-d8, δ, p.p.m.): 3.95 (d, J = 17 Hz, 4H, COD), 3.29 (dt, JH—H = 17 Hz, JP—H = 3 Hz, 2H, CH2), 2.86 (dt, JH—H = 15 Hz, JP—H = 4 Hz, 2H, CH2), 1.73 (t, J = 6 Hz, 18H, tBu), 1.22 (t, J = 6 Hz, 18H, tBu), -25.73 (t, J = 16 Hz, 1H, Ir—H). |
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. |
x | y | z | Uiso*/Ueq | ||
Ir1 | 0.680138 (8) | 0.126447 (9) | 0.159875 (5) | 0.00922 (3) | |
H1 | 0.6890 | 0.0307 | 0.1101 | 0.020* | |
Ir2 | 0.838754 (8) | 0.322798 (10) | 0.254009 (6) | 0.01107 (3) | |
P1 | 0.66778 (5) | 0.23654 (7) | 0.07101 (4) | 0.01129 (14) | |
P2 | 0.65536 (5) | −0.02464 (7) | 0.22407 (4) | 0.01062 (14) | |
Cl1 | 0.84815 (5) | 0.15376 (6) | 0.19479 (4) | 0.01398 (14) | |
Cl2 | 0.67694 (5) | 0.28732 (6) | 0.24043 (3) | 0.01297 (13) | |
C1 | 0.5440 (2) | 0.1114 (3) | 0.13518 (15) | 0.0125 (6) | |
C2 | 0.4993 (2) | 0.1449 (3) | 0.07595 (15) | 0.0132 (6) | |
C3 | 0.4046 (2) | 0.1378 (3) | 0.06018 (15) | 0.0163 (6) | |
H3 | 0.3756 | 0.1640 | 0.0210 | 0.020* | |
C4 | 0.3521 (2) | 0.0926 (3) | 0.10132 (16) | 0.0168 (6) | |
H4 | 0.2875 | 0.0896 | 0.0909 | 0.020* | |
C5 | 0.3954 (2) | 0.0518 (3) | 0.15791 (15) | 0.0150 (6) | |
H5 | 0.3602 | 0.0178 | 0.1854 | 0.018* | |
C6 | 0.4896 (2) | 0.0604 (3) | 0.17462 (15) | 0.0133 (6) | |
C7 | 0.5583 (2) | 0.1817 (3) | 0.02973 (15) | 0.0147 (6) | |
H7A | 0.5268 | 0.2422 | 0.0028 | 0.018* | |
H7B | 0.5693 | 0.1157 | 0.0037 | 0.018* | |
C8 | 0.5373 (2) | 0.0084 (3) | 0.23435 (15) | 0.0140 (6) | |
H8A | 0.5055 | −0.0623 | 0.2439 | 0.017* | |
H8B | 0.5373 | 0.0632 | 0.2686 | 0.017* | |
C9 | 0.7517 (2) | 0.2027 (3) | 0.01761 (15) | 0.0152 (6) | |
C10 | 0.7097 (3) | 0.2189 (3) | −0.05021 (16) | 0.0220 (7) | |
H10A | 0.7575 | 0.2114 | −0.0758 | 0.033* | |
H10B | 0.6820 | 0.2952 | −0.0560 | 0.033* | |
H10C | 0.6627 | 0.1605 | −0.0621 | 0.033* | |
C11 | 0.8374 (2) | 0.2786 (3) | 0.03346 (18) | 0.0223 (7) | |
H11A | 0.8852 | 0.2506 | 0.0114 | 0.033* | |
H11B | 0.8595 | 0.2755 | 0.0778 | 0.033* | |
H11C | 0.8220 | 0.3579 | 0.0213 | 0.033* | |
C12 | 0.7828 (2) | 0.0779 (3) | 0.02649 (16) | 0.0194 (7) | |
H12A | 0.7294 | 0.0273 | 0.0187 | 0.029* | |
H12B | 0.8142 | 0.0669 | 0.0687 | 0.029* | |
H12C | 0.8245 | 0.0596 | −0.0023 | 0.029* | |
C13 | 0.6481 (2) | 0.3965 (3) | 0.07266 (15) | 0.0155 (6) | |
C14 | 0.6308 (3) | 0.4552 (3) | 0.00934 (16) | 0.0206 (7) | |
H14A | 0.6124 | 0.5349 | 0.0141 | 0.031* | |
H14B | 0.5820 | 0.4146 | −0.0176 | 0.031* | |
H14C | 0.6868 | 0.4533 | −0.0088 | 0.031* | |
C15 | 0.7286 (2) | 0.4570 (3) | 0.11265 (16) | 0.0185 (7) | |
H15A | 0.7104 | 0.5347 | 0.1223 | 0.028* | |
H15B | 0.7804 | 0.4610 | 0.0903 | 0.028* | |
H15C | 0.7465 | 0.4139 | 0.1509 | 0.028* | |
C16 | 0.5621 (2) | 0.4128 (3) | 0.10254 (16) | 0.0192 (7) | |
H16A | 0.5708 | 0.3747 | 0.1427 | 0.029* | |
H16B | 0.5092 | 0.3793 | 0.0760 | 0.029* | |
H16C | 0.5515 | 0.4948 | 0.1080 | 0.029* | |
C17 | 0.6489 (2) | −0.1668 (3) | 0.18208 (15) | 0.0150 (6) | |
C18 | 0.6285 (3) | −0.2683 (3) | 0.22221 (16) | 0.0203 (7) | |
H18A | 0.6215 | −0.3383 | 0.1974 | 0.030* | |
H18B | 0.5719 | −0.2533 | 0.2384 | 0.030* | |
H18C | 0.6791 | −0.2778 | 0.2565 | 0.030* | |
C19 | 0.7398 (2) | −0.1883 (3) | 0.15836 (16) | 0.0185 (7) | |
H19A | 0.7367 | −0.2617 | 0.1366 | 0.028* | |
H19B | 0.7901 | −0.1903 | 0.1932 | 0.028* | |
H19C | 0.7504 | −0.1265 | 0.1303 | 0.028* | |
C20 | 0.5725 (3) | −0.1644 (3) | 0.12607 (16) | 0.0194 (7) | |
H20A | 0.5829 | −0.1008 | 0.0991 | 0.029* | |
H20B | 0.5135 | −0.1541 | 0.1398 | 0.029* | |
H20C | 0.5722 | −0.2368 | 0.1035 | 0.029* | |
C21 | 0.7184 (2) | −0.0469 (3) | 0.30485 (14) | 0.0147 (6) | |
C22 | 0.6597 (3) | −0.1087 (3) | 0.34640 (16) | 0.0191 (7) | |
H22A | 0.6953 | −0.1182 | 0.3876 | 0.029* | |
H22B | 0.6416 | −0.1841 | 0.3290 | 0.029* | |
H22C | 0.6051 | −0.0631 | 0.3489 | 0.029* | |
C23 | 0.8089 (2) | −0.1112 (3) | 0.30518 (17) | 0.0205 (7) | |
H23A | 0.8430 | −0.0753 | 0.2758 | 0.031* | |
H23B | 0.7961 | −0.1913 | 0.2935 | 0.031* | |
H23C | 0.8452 | −0.1080 | 0.3464 | 0.031* | |
C24 | 0.7421 (2) | 0.0709 (3) | 0.33318 (15) | 0.0190 (7) | |
H24A | 0.7695 | 0.0619 | 0.3764 | 0.029* | |
H24B | 0.6865 | 0.1171 | 0.3303 | 0.029* | |
H24C | 0.7856 | 0.1092 | 0.3110 | 0.029* | |
C25 | 0.9804 (2) | 0.3312 (3) | 0.28602 (16) | 0.0163 (6) | |
H25 | 1.0085 | 0.2634 | 0.2809 | 0.020* | |
C26 | 0.9592 (2) | 0.3831 (3) | 0.22771 (16) | 0.0156 (6) | |
H26 | 0.9702 | 0.3361 | 0.1952 | 0.020* | |
C27 | 0.9541 (2) | 0.5107 (3) | 0.21596 (16) | 0.0161 (6) | |
H27A | 0.9253 | 0.5246 | 0.1729 | 0.019* | |
H27B | 1.0168 | 0.5424 | 0.2215 | 0.019* | |
C28 | 0.8996 (2) | 0.5730 (3) | 0.25895 (17) | 0.0182 (6) | |
H28A | 0.9413 | 0.5965 | 0.2966 | 0.022* | |
H28B | 0.8721 | 0.6431 | 0.2385 | 0.022* | |
C29 | 0.8246 (2) | 0.4972 (3) | 0.27637 (16) | 0.0151 (6) | |
H29 | 0.7639 | 0.5201 | 0.2588 | 0.020* | |
C30 | 0.8350 (2) | 0.4293 (3) | 0.33026 (16) | 0.0160 (6) | |
H30 | 0.7849 | 0.4100 | 0.3435 | 0.020* | |
C31 | 0.9225 (2) | 0.4216 (3) | 0.37679 (16) | 0.0204 (7) | |
H31A | 0.9166 | 0.3591 | 0.4062 | 0.024* | |
H31B | 0.9315 | 0.4942 | 0.4002 | 0.024* | |
C32 | 1.0064 (2) | 0.3990 (3) | 0.34575 (16) | 0.0186 (7) | |
H32A | 1.0341 | 0.4729 | 0.3367 | 0.022* | |
H32B | 1.0525 | 0.3554 | 0.3742 | 0.022* | |
C33 | 0.9658 (4) | 0.5435 (6) | −0.0152 (2) | 0.071 (2) | |
H33A | 0.9108 | 0.5023 | −0.0356 | 0.085* | |
H33B | 0.9925 | 0.5838 | −0.0475 | 0.085* | |
C34 | 0.9364 (5) | 0.6329 (7) | 0.0284 (3) | 0.080 (3) | |
H34A | 0.9917 | 0.6718 | 0.0501 | 0.096* | |
H34B | 0.9072 | 0.5929 | 0.0597 | 0.096* | |
C35 | 0.8698 (6) | 0.7245 (9) | −0.0031 (3) | 0.105 (3) | |
H35A | 0.8974 | 0.7637 | −0.0348 | 0.157* | |
H35B | 0.8568 | 0.7802 | 0.0276 | 0.157* | |
H35C | 0.8127 | 0.6876 | −0.0221 | 0.157* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ir1 | 0.00906 (5) | 0.00824 (5) | 0.01056 (5) | −0.00065 (4) | 0.00222 (4) | 0.00001 (4) |
Ir2 | 0.00963 (6) | 0.00950 (5) | 0.01433 (6) | −0.00023 (4) | 0.00268 (4) | −0.00050 (4) |
P1 | 0.0123 (4) | 0.0105 (3) | 0.0112 (3) | −0.0007 (3) | 0.0025 (3) | 0.0007 (3) |
P2 | 0.0120 (3) | 0.0092 (3) | 0.0109 (3) | −0.0002 (3) | 0.0027 (3) | 0.0005 (3) |
Cl1 | 0.0100 (3) | 0.0126 (3) | 0.0192 (4) | 0.0004 (2) | 0.0020 (3) | −0.0027 (3) |
Cl2 | 0.0116 (3) | 0.0121 (3) | 0.0157 (3) | −0.0001 (3) | 0.0034 (3) | −0.0012 (3) |
C1 | 0.0124 (14) | 0.0095 (12) | 0.0151 (14) | −0.0011 (10) | 0.0003 (11) | −0.0023 (11) |
C2 | 0.0146 (15) | 0.0118 (13) | 0.0135 (14) | −0.0018 (11) | 0.0030 (11) | −0.0001 (11) |
C3 | 0.0155 (15) | 0.0176 (15) | 0.0147 (15) | −0.0023 (12) | −0.0005 (12) | −0.0013 (12) |
C4 | 0.0091 (14) | 0.0189 (15) | 0.0224 (16) | −0.0024 (11) | 0.0025 (12) | −0.0049 (13) |
C5 | 0.0125 (14) | 0.0148 (14) | 0.0188 (15) | −0.0025 (11) | 0.0059 (12) | −0.0034 (12) |
C6 | 0.0136 (14) | 0.0122 (13) | 0.0148 (14) | −0.0006 (11) | 0.0039 (11) | −0.0018 (11) |
C7 | 0.0135 (14) | 0.0188 (15) | 0.0114 (14) | −0.0025 (12) | 0.0005 (11) | 0.0043 (12) |
C8 | 0.0158 (15) | 0.0140 (14) | 0.0134 (14) | −0.0011 (11) | 0.0060 (12) | 0.0010 (11) |
C9 | 0.0183 (15) | 0.0154 (14) | 0.0136 (14) | −0.0017 (12) | 0.0077 (12) | 0.0004 (11) |
C10 | 0.0304 (19) | 0.0240 (17) | 0.0135 (15) | −0.0004 (15) | 0.0094 (14) | 0.0008 (13) |
C11 | 0.0188 (16) | 0.0225 (17) | 0.0281 (19) | −0.0054 (14) | 0.0109 (14) | 0.0001 (14) |
C12 | 0.0246 (17) | 0.0173 (15) | 0.0177 (16) | −0.0003 (13) | 0.0081 (13) | −0.0027 (13) |
C13 | 0.0179 (16) | 0.0126 (14) | 0.0159 (15) | 0.0013 (11) | 0.0027 (12) | 0.0007 (11) |
C14 | 0.0264 (18) | 0.0158 (15) | 0.0195 (16) | 0.0026 (13) | 0.0027 (14) | 0.0063 (13) |
C15 | 0.0236 (17) | 0.0114 (14) | 0.0210 (16) | −0.0011 (12) | 0.0058 (13) | −0.0005 (12) |
C16 | 0.0212 (17) | 0.0167 (15) | 0.0200 (16) | 0.0031 (13) | 0.0048 (13) | −0.0003 (13) |
C17 | 0.0211 (16) | 0.0099 (13) | 0.0144 (15) | −0.0009 (12) | 0.0043 (12) | −0.0007 (11) |
C18 | 0.0273 (18) | 0.0124 (14) | 0.0219 (17) | −0.0036 (13) | 0.0059 (14) | −0.0007 (13) |
C19 | 0.0227 (17) | 0.0133 (14) | 0.0205 (16) | 0.0037 (12) | 0.0067 (13) | −0.0005 (12) |
C20 | 0.0245 (18) | 0.0138 (14) | 0.0193 (16) | −0.0012 (13) | 0.0014 (13) | −0.0037 (12) |
C21 | 0.0183 (15) | 0.0152 (14) | 0.0108 (14) | 0.0012 (12) | 0.0037 (12) | 0.0018 (11) |
C22 | 0.0236 (17) | 0.0215 (16) | 0.0127 (15) | −0.0020 (13) | 0.0041 (13) | 0.0039 (12) |
C23 | 0.0202 (17) | 0.0229 (17) | 0.0179 (16) | 0.0034 (13) | 0.0019 (13) | 0.0010 (13) |
C24 | 0.0258 (18) | 0.0168 (15) | 0.0130 (15) | −0.0016 (13) | −0.0013 (13) | −0.0006 (12) |
C25 | 0.0116 (14) | 0.0138 (14) | 0.0235 (17) | −0.0003 (11) | 0.0033 (12) | −0.0020 (12) |
C26 | 0.0124 (14) | 0.0158 (14) | 0.0198 (16) | −0.0038 (11) | 0.0056 (12) | −0.0048 (12) |
C27 | 0.0135 (15) | 0.0163 (15) | 0.0187 (15) | −0.0040 (12) | 0.0029 (12) | 0.0026 (12) |
C28 | 0.0197 (16) | 0.0108 (13) | 0.0249 (17) | −0.0025 (12) | 0.0055 (13) | 0.0016 (13) |
C29 | 0.0143 (15) | 0.0115 (13) | 0.0199 (16) | 0.0008 (11) | 0.0037 (12) | −0.0011 (12) |
C30 | 0.0139 (14) | 0.0146 (14) | 0.0202 (16) | −0.0002 (12) | 0.0047 (12) | −0.0015 (12) |
C31 | 0.0176 (16) | 0.0254 (17) | 0.0178 (16) | −0.0033 (14) | 0.0016 (13) | −0.0035 (14) |
C32 | 0.0135 (15) | 0.0197 (16) | 0.0212 (17) | −0.0010 (12) | −0.0014 (12) | 0.0011 (13) |
C33 | 0.079 (4) | 0.103 (5) | 0.025 (2) | −0.073 (4) | −0.010 (2) | 0.016 (3) |
C34 | 0.085 (5) | 0.124 (6) | 0.027 (3) | −0.078 (5) | −0.005 (3) | 0.008 (3) |
C35 | 0.107 (7) | 0.138 (8) | 0.055 (4) | −0.040 (6) | −0.030 (4) | −0.007 (5) |
Ir1—C1 | 2.012 (3) | C16—H16C | 0.9800 |
Ir1—P1 | 2.326 (1) | C17—C20 | 1.535 (5) |
Ir1—P2 | 2.328 (1) | C17—C18 | 1.538 (5) |
Ir1—Cl1 | 2.507 (1) | C17—C19 | 1.546 (5) |
Ir1—Cl2 | 2.591 (1) | C18—H18A | 0.9800 |
Ir1—H1 | 1.59 | C18—H18B | 0.9800 |
Ir2—C26 | 2.090 (3) | C18—H18C | 0.9800 |
Ir2—C30 | 2.100 (3) | C19—H19A | 0.9800 |
Ir2—C25 | 2.108 (3) | C19—H19B | 0.9800 |
Ir2—C29 | 2.113 (3) | C19—H19C | 0.9800 |
Ir2—Cl1 | 2.383 (1) | C20—H20A | 0.9800 |
Ir2—Cl2 | 2.407 (1) | C20—H20B | 0.9800 |
P1—C7 | 1.843 (3) | C20—H20C | 0.9800 |
P1—C9 | 1.891 (3) | C21—C24 | 1.528 (5) |
P1—C13 | 1.891 (3) | C21—C23 | 1.537 (5) |
P2—C8 | 1.845 (3) | C21—C22 | 1.543 (5) |
P2—C21 | 1.891 (3) | C22—H22A | 0.9800 |
P2—C17 | 1.896 (3) | C22—H22B | 0.9800 |
C1—C6 | 1.412 (4) | C22—H22C | 0.9800 |
C1—C2 | 1.420 (4) | C23—H23A | 0.9800 |
C2—C3 | 1.394 (5) | C23—H23B | 0.9800 |
C2—C7 | 1.511 (4) | C23—H23C | 0.9800 |
C3—C4 | 1.393 (5) | C24—H24A | 0.9800 |
C3—H3 | 0.9500 | C24—H24B | 0.9800 |
C4—C5 | 1.391 (5) | C24—H24C | 0.9800 |
C4—H4 | 0.9500 | C25—C26 | 1.410 (5) |
C5—C6 | 1.390 (4) | C25—C32 | 1.531 (5) |
C5—H5 | 0.9500 | C25—H25 | 0.910 |
C6—C8 | 1.516 (4) | C26—C27 | 1.512 (5) |
C7—H7A | 0.9900 | C26—H26 | 0.938 |
C7—H7B | 0.9900 | C27—C28 | 1.528 (5) |
C8—H8A | 0.9900 | C27—H27A | 0.9900 |
C8—H8B | 0.9900 | C27—H27B | 0.9900 |
C9—C12 | 1.531 (5) | C28—C29 | 1.520 (4) |
C9—C10 | 1.536 (5) | C28—H28A | 0.9900 |
C9—C11 | 1.542 (5) | C28—H28B | 0.9900 |
C10—H10A | 0.9800 | C29—C30 | 1.416 (5) |
C10—H10B | 0.9800 | C29—H29 | 0.959 |
C10—H10C | 0.9800 | C30—C31 | 1.520 (5) |
C11—H11A | 0.9800 | C30—H30 | 0.871 |
C11—H11B | 0.9800 | C31—C32 | 1.540 (5) |
C11—H11C | 0.9800 | C31—H31A | 0.9900 |
C12—H12A | 0.9800 | C31—H31B | 0.9900 |
C12—H12B | 0.9800 | C32—H32A | 0.9900 |
C12—H12C | 0.9800 | C32—H32B | 0.9900 |
C13—C15 | 1.537 (5) | C33—C33i | 1.514 (14) |
C13—C14 | 1.539 (5) | C33—C34 | 1.529 (11) |
C13—C16 | 1.542 (5) | C33—H33A | 0.9900 |
C14—H14A | 0.9800 | C33—H33B | 0.9900 |
C14—H14B | 0.9800 | C34—C35 | 1.543 (12) |
C14—H14C | 0.9800 | C34—H34A | 0.9900 |
C15—H15A | 0.9800 | C34—H34B | 0.9900 |
C15—H15B | 0.9800 | C35—H35A | 0.9800 |
C15—H15C | 0.9800 | C35—H35B | 0.9800 |
C16—H16A | 0.9800 | C35—H35C | 0.9800 |
C16—H16B | 0.9800 | ||
C1—Ir1—P1 | 83.27 (9) | H16A—C16—H16B | 109.5 |
C1—Ir1—P2 | 81.21 (9) | C13—C16—H16C | 109.5 |
P1—Ir1—P2 | 158.83 (3) | H16A—C16—H16C | 109.5 |
C1—Ir1—Cl1 | 176.79 (9) | H16B—C16—H16C | 109.5 |
P1—Ir1—Cl1 | 97.23 (3) | C20—C17—C18 | 106.8 (3) |
P2—Ir1—Cl1 | 99.07 (3) | C20—C17—C19 | 107.6 (3) |
C1—Ir1—Cl2 | 96.80 (9) | C18—C17—C19 | 109.6 (3) |
P1—Ir1—Cl2 | 99.77 (3) | C20—C17—P2 | 110.4 (2) |
P2—Ir1—Cl2 | 96.29 (3) | C18—C17—P2 | 113.1 (2) |
Cl1—Ir1—Cl2 | 79.98 (2) | C19—C17—P2 | 109.3 (2) |
C1—Ir1—H1 | 87 | C17—C18—H18A | 109.5 |
P1—Ir1—H1 | 79 | C17—C18—H18B | 109.5 |
P2—Ir1—H1 | 86 | H18A—C18—H18B | 109.5 |
Cl1—Ir1—H1 | 96 | C17—C18—H18C | 109.5 |
Cl2—Ir1—H1 | 176 | H18A—C18—H18C | 109.5 |
C26—Ir2—C30 | 99.14 (13) | H18B—C18—H18C | 109.5 |
C26—Ir2—C25 | 39.25 (13) | C17—C19—H19A | 109.5 |
C30—Ir2—C25 | 81.93 (13) | C17—C19—H19B | 109.5 |
C26—Ir2—C29 | 82.09 (12) | H19A—C19—H19B | 109.5 |
C30—Ir2—C29 | 39.27 (13) | C17—C19—H19C | 109.5 |
C25—Ir2—C29 | 90.49 (12) | H19A—C19—H19C | 109.5 |
C26—Ir2—Cl1 | 89.84 (9) | H19B—C19—H19C | 109.5 |
C30—Ir2—Cl1 | 160.23 (9) | C17—C20—H20A | 109.5 |
C25—Ir2—Cl1 | 94.45 (9) | C17—C20—H20B | 109.5 |
C29—Ir2—Cl1 | 160.48 (9) | H20A—C20—H20B | 109.5 |
C26—Ir2—Cl2 | 154.80 (10) | C17—C20—H20C | 109.5 |
C30—Ir2—Cl2 | 92.58 (9) | H20A—C20—H20C | 109.5 |
C25—Ir2—Cl2 | 165.92 (10) | H20B—C20—H20C | 109.5 |
C29—Ir2—Cl2 | 93.42 (9) | C24—C21—C23 | 107.2 (3) |
Cl1—Ir2—Cl2 | 86.33 (3) | C24—C21—C22 | 107.0 (3) |
C7—P1—C9 | 103.74 (15) | C23—C21—C22 | 110.3 (3) |
C7—P1—C13 | 103.07 (15) | C24—C21—P2 | 107.9 (2) |
C9—P1—C13 | 109.73 (15) | C23—C21—P2 | 111.7 (2) |
C7—P1—Ir1 | 99.55 (10) | C22—C21—P2 | 112.6 (2) |
C9—P1—Ir1 | 116.13 (11) | C21—C22—H22A | 109.5 |
C13—P1—Ir1 | 121.36 (11) | C21—C22—H22B | 109.5 |
C8—P2—C21 | 104.29 (14) | H22A—C22—H22B | 109.5 |
C8—P2—C17 | 105.67 (15) | C21—C22—H22C | 109.5 |
C21—P2—C17 | 108.52 (15) | H22A—C22—H22C | 109.5 |
C8—P2—Ir1 | 99.45 (10) | H22B—C22—H22C | 109.5 |
C21—P2—Ir1 | 125.06 (11) | C21—C23—H23A | 109.5 |
C17—P2—Ir1 | 111.51 (10) | C21—C23—H23B | 109.5 |
Ir2—Cl1—Ir1 | 97.43 (3) | H23A—C23—H23B | 109.5 |
Ir2—Cl2—Ir1 | 94.60 (2) | C21—C23—H23C | 109.5 |
C6—C1—C2 | 117.0 (3) | H23A—C23—H23C | 109.5 |
C6—C1—Ir1 | 121.3 (2) | H23B—C23—H23C | 109.5 |
C2—C1—Ir1 | 121.5 (2) | C21—C24—H24A | 109.5 |
C3—C2—C1 | 120.9 (3) | C21—C24—H24B | 109.5 |
C3—C2—C7 | 121.4 (3) | H24A—C24—H24B | 109.5 |
C1—C2—C7 | 117.6 (3) | C21—C24—H24C | 109.5 |
C4—C3—C2 | 120.6 (3) | H24A—C24—H24C | 109.5 |
C4—C3—H3 | 119.7 | H24B—C24—H24C | 109.5 |
C2—C3—H3 | 119.7 | C26—C25—C32 | 123.4 (3) |
C5—C4—C3 | 119.3 (3) | C26—C25—Ir2 | 69.71 (19) |
C5—C4—H4 | 120.4 | C32—C25—Ir2 | 114.2 (2) |
C3—C4—H4 | 120.4 | C26—C25—H25 | 107 |
C6—C5—C4 | 120.7 (3) | C32—C25—H25 | 120 |
C6—C5—H5 | 119.7 | Ir2—C25—H25 | 111 |
C4—C5—H5 | 119.7 | C25—C26—C27 | 125.2 (3) |
C5—C6—C1 | 121.2 (3) | C25—C26—Ir2 | 71.04 (19) |
C5—C6—C8 | 120.5 (3) | C27—C26—Ir2 | 111.0 (2) |
C1—C6—C8 | 118.1 (3) | C25—C26—H26 | 113 |
C2—C7—P1 | 109.1 (2) | C27—C26—H26 | 117 |
C2—C7—H7A | 109.9 | Ir2—C26—H26 | 106 |
P1—C7—H7A | 109.9 | C26—C27—C28 | 112.4 (3) |
C2—C7—H7B | 109.9 | C26—C27—H27A | 109.1 |
P1—C7—H7B | 109.9 | C28—C27—H27A | 109.1 |
H7A—C7—H7B | 108.3 | C26—C27—H27B | 109.1 |
C6—C8—P2 | 107.1 (2) | C28—C27—H27B | 109.1 |
C6—C8—H8A | 110.3 | H27A—C27—H27B | 107.9 |
P2—C8—H8A | 110.3 | C29—C28—C27 | 111.3 (3) |
C6—C8—H8B | 110.3 | C29—C28—H28A | 109.4 |
P2—C8—H8B | 110.3 | C27—C28—H28A | 109.4 |
H8A—C8—H8B | 108.5 | C29—C28—H28B | 109.4 |
C12—C9—C10 | 107.9 (3) | C27—C28—H28B | 109.4 |
C12—C9—C11 | 107.3 (3) | H28A—C28—H28B | 108.0 |
C10—C9—C11 | 109.8 (3) | C30—C29—C28 | 123.7 (3) |
C12—C9—P1 | 109.5 (2) | C30—C29—Ir2 | 69.85 (18) |
C10—C9—P1 | 112.2 (2) | C28—C29—Ir2 | 113.4 (2) |
C11—C9—P1 | 110.0 (2) | C30—C29—H29 | 117 |
C9—C10—H10A | 109.5 | C28—C29—H29 | 114 |
C9—C10—H10B | 109.5 | Ir2—C29—H29 | 107 |
H10A—C10—H10B | 109.5 | C29—C30—C31 | 124.3 (3) |
C9—C10—H10C | 109.5 | C29—C30—Ir2 | 70.88 (19) |
H10A—C10—H10C | 109.5 | C31—C30—Ir2 | 112.0 (2) |
H10B—C10—H10C | 109.5 | C29—C30—H30 | 116 |
C9—C11—H11A | 109.5 | C31—C30—H30 | 116 |
C9—C11—H11B | 109.5 | Ir2—C30—H30 | 104 |
H11A—C11—H11B | 109.5 | C30—C31—C32 | 112.0 (3) |
C9—C11—H11C | 109.5 | C30—C31—H31A | 109.2 |
H11A—C11—H11C | 109.5 | C32—C31—H31A | 109.2 |
H11B—C11—H11C | 109.5 | C30—C31—H31B | 109.2 |
C9—C12—H12A | 109.5 | C32—C31—H31B | 109.2 |
C9—C12—H12B | 109.5 | H31A—C31—H31B | 107.9 |
H12A—C12—H12B | 109.5 | C25—C32—C31 | 111.3 (3) |
C9—C12—H12C | 109.5 | C25—C32—H32A | 109.4 |
H12A—C12—H12C | 109.5 | C31—C32—H32A | 109.4 |
H12B—C12—H12C | 109.5 | C25—C32—H32B | 109.4 |
C15—C13—C14 | 108.4 (3) | C31—C32—H32B | 109.4 |
C15—C13—C16 | 108.6 (3) | H32A—C32—H32B | 108.0 |
C14—C13—C16 | 107.8 (3) | C33i—C33—C34 | 114.8 (6) |
C15—C13—P1 | 110.9 (2) | C33i—C33—H33A | 108.6 |
C14—C13—P1 | 115.2 (2) | C34—C33—H33A | 108.6 |
C16—C13—P1 | 105.8 (2) | C33i—C33—H33B | 108.6 |
C13—C14—H14A | 109.5 | C34—C33—H33B | 108.6 |
C13—C14—H14B | 109.5 | H33A—C33—H33B | 107.5 |
H14A—C14—H14B | 109.5 | C33—C34—C35 | 114.7 (5) |
C13—C14—H14C | 109.5 | C33—C34—H34A | 108.6 |
H14A—C14—H14C | 109.5 | C35—C34—H34A | 108.6 |
H14B—C14—H14C | 109.5 | C33—C34—H34B | 108.6 |
C13—C15—H15A | 109.5 | C35—C34—H34B | 108.6 |
C13—C15—H15B | 109.5 | H34A—C34—H34B | 107.6 |
H15A—C15—H15B | 109.5 | C34—C35—H35A | 109.5 |
C13—C15—H15C | 109.5 | C34—C35—H35B | 109.5 |
H15A—C15—H15C | 109.5 | H35A—C35—H35B | 109.5 |
H15B—C15—H15C | 109.5 | C34—C35—H35C | 109.5 |
C13—C16—H16A | 109.5 | H35A—C35—H35C | 109.5 |
C13—C16—H16B | 109.5 | H35B—C35—H35C | 109.5 |
C1—Ir1—P1—C7 | −21.72 (14) | C7—P1—C13—C15 | 172.9 (2) |
P2—Ir1—P1—C7 | 21.31 (14) | C9—P1—C13—C15 | −77.1 (3) |
Cl1—Ir1—P1—C7 | 161.47 (11) | Ir1—P1—C13—C15 | 63.0 (3) |
Cl2—Ir1—P1—C7 | −117.50 (11) | C7—P1—C13—C14 | −63.5 (3) |
C1—Ir1—P1—C9 | −132.26 (15) | C9—P1—C13—C14 | 46.5 (3) |
P2—Ir1—P1—C9 | −89.23 (14) | Ir1—P1—C13—C14 | −173.5 (2) |
Cl1—Ir1—P1—C9 | 50.94 (12) | C7—P1—C13—C16 | 55.4 (2) |
Cl2—Ir1—P1—C9 | 131.96 (12) | C9—P1—C13—C16 | 165.4 (2) |
C1—Ir1—P1—C13 | 90.06 (15) | Ir1—P1—C13—C16 | −54.5 (2) |
P2—Ir1—P1—C13 | 133.09 (14) | C8—P2—C17—C20 | 49.1 (3) |
Cl1—Ir1—P1—C13 | −86.74 (13) | C21—P2—C17—C20 | 160.4 (2) |
Cl2—Ir1—P1—C13 | −5.72 (13) | Ir1—P2—C17—C20 | −58.0 (2) |
C1—Ir1—P2—C8 | −28.64 (14) | C8—P2—C17—C18 | −70.5 (3) |
P1—Ir1—P2—C8 | −71.93 (13) | C21—P2—C17—C18 | 40.9 (3) |
Cl1—Ir1—P2—C8 | 148.12 (11) | Ir1—P2—C17—C18 | −177.6 (2) |
Cl2—Ir1—P2—C8 | 67.31 (11) | C8—P2—C17—C19 | 167.2 (2) |
C1—Ir1—P2—C21 | −143.63 (16) | C21—P2—C17—C19 | −81.4 (2) |
P1—Ir1—P2—C21 | 173.07 (13) | Ir1—P2—C17—C19 | 60.1 (2) |
Cl1—Ir1—P2—C21 | 33.13 (13) | C8—P2—C21—C24 | −80.4 (2) |
Cl2—Ir1—P2—C21 | −47.69 (13) | C17—P2—C21—C24 | 167.4 (2) |
C1—Ir1—P2—C17 | 82.46 (15) | Ir1—P2—C21—C24 | 32.3 (3) |
P1—Ir1—P2—C17 | 39.16 (15) | C8—P2—C21—C23 | 162.1 (2) |
Cl1—Ir1—P2—C17 | −100.78 (12) | C17—P2—C21—C23 | 49.9 (3) |
Cl2—Ir1—P2—C17 | 178.40 (12) | Ir1—P2—C21—C23 | −85.2 (2) |
C26—Ir2—Cl1—Ir1 | −144.88 (10) | C8—P2—C21—C22 | 37.5 (3) |
C30—Ir2—Cl1—Ir1 | 97.6 (3) | C17—P2—C21—C22 | −74.8 (3) |
C25—Ir2—Cl1—Ir1 | 176.11 (10) | Ir1—P2—C21—C22 | 150.15 (19) |
C29—Ir2—Cl1—Ir1 | −79.7 (3) | C30—Ir2—C25—C26 | −115.3 (2) |
Cl2—Ir2—Cl1—Ir1 | 10.20 (3) | C29—Ir2—C25—C26 | −76.8 (2) |
P1—Ir1—Cl1—Ir2 | 89.10 (3) | Cl1—Ir2—C25—C26 | 84.27 (18) |
P2—Ir1—Cl1—Ir2 | −104.44 (3) | Cl2—Ir2—C25—C26 | 176.9 (3) |
Cl2—Ir1—Cl1—Ir2 | −9.60 (3) | C26—Ir2—C25—C32 | 118.5 (3) |
C26—Ir2—Cl2—Ir1 | 72.0 (2) | C30—Ir2—C25—C32 | 3.2 (2) |
C30—Ir2—Cl2—Ir1 | −170.05 (9) | C29—Ir2—C25—C32 | 41.7 (2) |
C25—Ir2—Cl2—Ir1 | −103.5 (4) | Cl1—Ir2—C25—C32 | −157.2 (2) |
C29—Ir2—Cl2—Ir1 | 150.63 (9) | Cl2—Ir2—C25—C32 | −64.6 (5) |
Cl1—Ir2—Cl2—Ir1 | −9.82 (3) | C32—C25—C26—C27 | −3.5 (5) |
C1—Ir1—Cl2—Ir2 | −170.55 (9) | Ir2—C25—C26—C27 | 102.8 (3) |
P1—Ir1—Cl2—Ir2 | −86.25 (3) | C32—C25—C26—Ir2 | −106.2 (3) |
P2—Ir1—Cl2—Ir2 | 107.59 (3) | C30—Ir2—C26—C25 | 65.1 (2) |
Cl1—Ir1—Cl2—Ir2 | 9.45 (2) | C29—Ir2—C26—C25 | 100.6 (2) |
P1—Ir1—C1—C6 | −171.6 (3) | Cl1—Ir2—C26—C25 | −97.25 (18) |
P2—Ir1—C1—C6 | 22.8 (2) | Cl2—Ir2—C26—C25 | −178.25 (16) |
Cl2—Ir1—C1—C6 | −72.5 (2) | C30—Ir2—C26—C27 | −56.4 (3) |
P1—Ir1—C1—C2 | 12.5 (2) | C25—Ir2—C26—C27 | −121.4 (3) |
P2—Ir1—C1—C2 | −153.1 (3) | C29—Ir2—C26—C27 | −20.9 (2) |
Cl2—Ir1—C1—C2 | 111.6 (2) | Cl1—Ir2—C26—C27 | 141.3 (2) |
C6—C1—C2—C3 | 6.2 (4) | Cl2—Ir2—C26—C27 | 60.3 (3) |
Ir1—C1—C2—C3 | −177.7 (2) | C25—C26—C27—C28 | −46.6 (4) |
C6—C1—C2—C7 | −170.3 (3) | Ir2—C26—C27—C28 | 34.5 (3) |
Ir1—C1—C2—C7 | 5.7 (4) | C26—C27—C28—C29 | −31.2 (4) |
C1—C2—C3—C4 | −3.0 (5) | C27—C28—C29—C30 | 94.2 (4) |
C7—C2—C3—C4 | 173.4 (3) | C27—C28—C29—Ir2 | 13.6 (4) |
C2—C3—C4—C5 | −1.6 (5) | C26—Ir2—C29—C30 | −115.0 (2) |
C3—C4—C5—C6 | 2.8 (5) | C25—Ir2—C29—C30 | −76.6 (2) |
C4—C5—C6—C1 | 0.6 (5) | Cl1—Ir2—C29—C30 | 178.6 (2) |
C4—C5—C6—C8 | −175.7 (3) | Cl2—Ir2—C29—C30 | 89.89 (18) |
C2—C1—C6—C5 | −5.0 (4) | C26—Ir2—C29—C28 | 4.0 (2) |
Ir1—C1—C6—C5 | 178.9 (2) | C30—Ir2—C29—C28 | 119.0 (3) |
C2—C1—C6—C8 | 171.4 (3) | C25—Ir2—C29—C28 | 42.4 (3) |
Ir1—C1—C6—C8 | −4.7 (4) | Cl1—Ir2—C29—C28 | −62.4 (4) |
C3—C2—C7—P1 | 157.5 (3) | Cl2—Ir2—C29—C28 | −151.1 (2) |
C1—C2—C7—P1 | −26.0 (4) | C28—C29—C30—C31 | −1.3 (5) |
C9—P1—C7—C2 | 150.2 (2) | Ir2—C29—C30—C31 | 104.1 (3) |
C13—P1—C7—C2 | −95.3 (2) | C28—C29—C30—Ir2 | −105.3 (3) |
Ir1—P1—C7—C2 | 30.2 (2) | C26—Ir2—C30—C29 | 65.4 (2) |
C5—C6—C8—P2 | 153.6 (3) | C25—Ir2—C30—C29 | 100.8 (2) |
C1—C6—C8—P2 | −22.8 (3) | Cl1—Ir2—C30—C29 | −178.6 (2) |
C21—P2—C8—C6 | 164.0 (2) | Cl2—Ir2—C30—C29 | −92.26 (18) |
C17—P2—C8—C6 | −81.7 (2) | C26—Ir2—C30—C31 | −54.9 (3) |
Ir1—P2—C8—C6 | 33.9 (2) | C25—Ir2—C30—C31 | −19.5 (2) |
C7—P1—C9—C12 | −82.2 (3) | C29—Ir2—C30—C31 | −120.2 (3) |
C13—P1—C9—C12 | 168.2 (2) | Cl1—Ir2—C30—C31 | 61.2 (4) |
Ir1—P1—C9—C12 | 25.9 (3) | Cl2—Ir2—C30—C31 | 147.5 (2) |
C7—P1—C9—C10 | 37.6 (3) | C29—C30—C31—C32 | −49.0 (5) |
C13—P1—C9—C10 | −72.0 (3) | Ir2—C30—C31—C32 | 32.3 (4) |
Ir1—P1—C9—C10 | 145.6 (2) | C26—C25—C32—C31 | 94.2 (4) |
C7—P1—C9—C11 | 160.1 (2) | Ir2—C25—C32—C31 | 13.3 (4) |
C13—P1—C9—C11 | 50.5 (3) | C30—C31—C32—C25 | −29.3 (4) |
Ir1—P1—C9—C11 | −91.9 (2) | C33i—C33—C34—C35 | 177.6 (6) |
Symmetry code: (i) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···Cl1 | 0.98 | 2.93 | 3.785 (4) | 147 |
C15—H15C···Cl2 | 0.98 | 2.80 | 3.628 (4) | 143 |
C16—H16A···Cl2 | 0.98 | 2.66 | 3.551 (4) | 152 |
C24—H24B···Cl2 | 0.98 | 2.79 | 3.295 (3) | 113 |
C24—H24C···Cl1 | 0.98 | 2.91 | 3.782 (3) | 149 |
C24—H24B···Cl2 | 0.98 | 2.79 | 3.295 (3) | 113 |
C26—H26···Cl1 | 0.94 | 2.79 | 3.165 (3) | 104.7 |
C27—H27B···Cl1ii | 0.99 | 2.81 | 3.659 (3) | 144 |
C30—H30···Cl2 | 0.87 | 2.93 | 3.264 (3) | 104.7 |
C32—H32A···Cl1ii | 0.99 | 2.90 | 3.865 (3) | 166 |
Symmetry code: (ii) −x+2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ir2(C8H12)(C24H44P2)Cl2]·0.5C6H14 |
Mr | 1001.09 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 14.8424 (7), 11.6735 (5), 22.0589 (10) |
β (°) | 99.416 (1) |
V (Å3) | 3770.5 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.30 |
Crystal size (mm) | 0.19 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS in SAINT-Plus; Bruker, 2003) |
Tmin, Tmax | 0.361, 0.558 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 42778, 11498, 10259 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.716 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.062, 1.00 |
No. of reflections | 11498 |
No. of parameters | 383 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.04, −1.03 |
Computer programs: SMART (Bruker, 2005), SMART, SAINT-Plus (Bruker,2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2003), SHELXTL.
Ir1—C1 | 2.012 (3) | Ir2—C26 | 2.090 (3) |
Ir1—P1 | 2.326 (1) | Ir2—C30 | 2.100 (3) |
Ir1—P2 | 2.328 (1) | Ir2—C25 | 2.108 (3) |
Ir1—Cl1 | 2.507 (1) | Ir2—C29 | 2.113 (3) |
Ir1—Cl2 | 2.591 (1) | Ir2—Cl1 | 2.383 (1) |
Ir1—H1 | 1.59 | Ir2—Cl2 | 2.407 (1) |
C1—Ir1—P1 | 83.27 (9) | P2—Ir1—Cl2 | 96.29 (3) |
C1—Ir1—P2 | 81.21 (9) | Cl1—Ir1—Cl2 | 79.98 (2) |
P1—Ir1—P2 | 158.83 (3) | C1—Ir1—H1 | 87 |
C1—Ir1—Cl1 | 176.79 (9) | P1—Ir1—H1 | 79 |
P1—Ir1—Cl1 | 97.23 (3) | P2—Ir1—H1 | 86 |
P2—Ir1—Cl1 | 99.07 (3) | Cl1—Ir1—H1 | 96 |
C1—Ir1—Cl2 | 96.80 (9) | Cl2—Ir1—H1 | 176 |
P1—Ir1—Cl2 | 99.77 (3) | Cl1—Ir2—Cl2 | 86.33 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···Cl1 | 0.98 | 2.93 | 3.785 (4) | 147.1 |
C15—H15C···Cl2 | 0.98 | 2.80 | 3.628 (4) | 143.1 |
C16—H16A···Cl2 | 0.98 | 2.66 | 3.551 (4) | 151.6 |
C24—H24B···Cl2 | 0.98 | 2.79 | 3.295 (3) | 112.5 |
C24—H24C···Cl1 | 0.98 | 2.91 | 3.782 (3) | 148.5 |
C24—H24B···Cl2 | 0.98 | 2.79 | 3.295 (3) | 112.5 |
C26—H26···Cl1 | 0.94 | 2.79 | 3.165 (3) | 104.7 |
C27—H27B···Cl1i | 0.99 | 2.81 | 3.659 (3) | 143.9 |
C30—H30···Cl2 | 0.87 | 2.93 | 3.264 (3) | 104.7 |
C32—H32A···Cl1i | 0.99 | 2.90 | 3.865 (3) | 166.0 |
Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
(tBuPCP)Ir complex | Ir—C(aryl) | Ir—P1 | Ir—P2 | Ir—Cl |
IrI complexes | ||||
(PCP)Ir(NH3)a | 2.013 (4) | 2.2737 (14) | 2.2610 (13) | |
(PCP)Ir(CO)b | 2.102 (8) | 2.298 (2) | 2.291 (2) | |
(PCP)IrN≡NIr(PCP)c | 2.0534 (18) | 2.2989 (5) | 2.3028 (5) | |
2.0511 (18) | 2.29855) | 2.3001 (5) | ||
(PCP)IrN2c | 2.0445 | 2.2891 | 2.2921 | |
IrIII complexes | ||||
(PCP)Ir(H)(NHPh)a | 2.049 (2) | 2.2917 (14) | 2.3429 (11) | |
(PCP)Ir(H)(NHPh)(CO)a | 2.077 (2) | 2.3422 (6) | 2.3338 (5) | |
(PCP)Ir(H)(NH2)(CNtBu)a | 2.077 (4) | 2.3075 (11) | 2.3111 (12) | |
(PCP)Ir(H)(κ2-O2COH)d | 2.04 (2) | 2.321 (5) | 2.331 (5) | |
(PCP)Ir(H)[C(O)OH]d | 2.07 (2) | 2.323 (5) | 2.291 (6) | |
(PCP)Ir(HgPh)Cle | 2.027 (3) | 2.3238 (8) | 2.3068 (8) | 2.4599 (7) |
(PCP)Ir(H)(κ2-O,C-nitrophenyl)f | 2.028 | 2.3266 | 2.3307 | |
(PCP)Ir(H)(κ2-O,C-acetylphenyl)f | 2.0261 (17) | 2.3209 (5) | 2.3079 (5) | |
(PCP)Ir(H)(κ2-O,O-NO2CH2)g | 2.0283 (17) | 2.3117 (5) | 2.3185 (5) | |
(PCP)Ir(H)(κ1-O-ONOCH2)g | 2.042 (6) | 2.3325 (16) | 2.3349 (16) | |
(PCP)Ir(H)(CO)(CH2NO2)g | 2.091 (3) | 2.3447 (9) | 2.3499 (9) | |
(PCP)Ir(H)(CH2NO2)(CNC6H11)g | 2.090 (2) | 2.3374 (5) | 2.3399 (5) | |
(PCP)IrH2h | 2.124 (13) | 2.308 (2) | 2.308 (2) | |
(PCP)Ir(H)(OH)i | 2.01 (2) | 2.304 (4) | 2.303 (4) | |
(PCP)IrI[C(O)CH3]j | 2.076 (11) | 2.354 (3) | 2.370 (3) | |
trans-(PCP)Ir(H)(CH3)(CO)j | 2.095 (3) | 2.3215 (9) | 2.3246 (9) | |
cis-(PCP)Ir(H)(CH3)(CO)j | 2.095 (5) | 2.3256 (12) | 2.3316 (11) | |
cis-(PCP)Ir(H)(CH2CH2CH3)(CO)j | 2.121 (2) | 2.3403 (6) | 2.3403 (6) | |
(PCP)Ir(η2-PhCCCHCHPh)k | 2.072 (2) | 2.3054 (6) | 2.3272 (7) | |
(PCP)Ir(H)(CCPh)k | 2.062 | 2.294 | 2.293 | |
(PCP)Ir(CCPh)(PHCCH2)(CO)k | 2.0901 (18) | 2.3876 (5) | 2.4317 (5) | |
(PCP)Ir[C(H)═C(H)Ph]Clk | 2.0303 (18) | 2.3405 (5) | 2.3361 (5) | 2.4628 (4) |
(PCP)Ir[C(H)═C(H)Ph](CO)Clk | 2.0478 (15) | 2.4115 (4) | 2.3817 (4) | 2.4812 (4) |
(PCP)Ir[C(H)═C(H)PH](CCC6H4CH3)(CO)k | 2.090 (4) | 2.3878 (11) | 2.3683 (11) | |
(PCP)Ir(CCPh)[C(Me)C(H)Ph]k | 2.068 (9) | 2.344 (2) | 2.328 (2) | |
(PCP)Ir(CCPh)[PhC(H)CC(H)C(H)Ph](CO)k | 2.092 (3) | 2.4194 (7) | 2.4136 (7) | |
trans-(PCP)Ir(H)(CH3)(CNC6H11)l | 2.078 | 2.3035 | 2.3075 | |
trans-(PCP)Ir(H)(CH3)(CNtBu)l | 2.081 (2) | 2.3065 (6) | 2.3067 (6) | |
cis-(PCP)Ir(H)(CH3)(CNC2H5)l | 2.0962 (19) | 2.3062 (5) | 2.3064 (5) | |
para-NO2-(PCP)IrHClm | 2.015 (3) | 2.3138 (12) | 2.3111 (12) | 2.4395 (9) |
References and notes: (a) Kanzelberger et al. (2003); (b) Morales-Morales, Redon et al. (2001); (c) Ghosh et al. (2006). The asymmetric unit cell of (PCP)IrN2 consisted of four individual molecules. The values shown here are averaged and standard deviations have been omitted. (d) Lee et al. (2003); (e) Zhang et al. (2001); (f) Zhang, Kanzelberger et al. (2004). The unit cell of (PCP)Ir(H)(κ2-O,C-nitrophenyl) consisted of two inequivalent molecules. The values shown here are averaged and standard deviations have been omitted. (g) Zhang et al. (2006); (h) Gupta et al. (1997); (i) Morales-Morales, Lee et al. (2001); (j) Kanzelberger (2004); (k) Ghosh et al. (2007). The unit cell of (PCP)Ir(H)(CCPh) contained two inequivalent molecules. The values shown here are averaged and standard deviations have been omitted. (l) Zhang et al. (2005). trans-(PCP)Ir(H)(CH3)(CNC6H11) was found for two different phases. The values shown here are averaged and standard deviations have been omitted. (m) Grimm et al. (2000). |
There has been great interest in recent years in the development of pincer complexes (Albrecht & van Koten, 2001; Singleton, 2003; Van der Boom & Milstein, 2003), i.e. complexes of tridentate meridionally bound ligands (Moulton & Shaw, 1976). Derivatives of the pincer complex (tBuPCP)IrH2 [tBuPCP is κ3-2,6-(tBu2PCH2)2C6H3] (Gupta et al., 1996) have proven highly effective as catalysts for the dehydrogenation of alkanes (Gupta et al., 1996, 1997; Xu et al., 1997; Liu et al., 1999; Zhu et al., 2004; Goldman et al., 2006). The synthetic precursor to (tBuPCP)IrH2 (Gupta et al., 1996) is (tBuPCP)IrHCl (Moulton & Shaw, 1976). We have previously reported the hexanuclear iridium η4-2,5-cyclooctadiene complex [(COD)Ir]2{η6-[κ4-C6H2(CH2PtBu2)2] Ir2H2Cl3}2 (COD is 1,5-cyclooctadiene), which has been observed as a by-product of the synthesis of the (tBuPCP)IrHCl complex (Zhang, Emge et al., 2004). Here, we report another such by-product, an orange–red material that has been identified as (tBuPCP)IrH(µ2Cl)2Ir(COD), which was isolated as the hexane hemisolvate, (I).
Complex (I) (Fig. 1) is best viewed as the di(chloride-bridged) mixed-valence addition product of (PCP)IrHCl (Moulton & Shaw, 1976) and `(COD)IrCl'. The latter can be viewed as a monomeric unit of the dimer [Ir(COD)Cl]2, which has been crystallographically characterized previously (Cotton et al., 1986). The hydride was found in this complex using electron difference maps. The Ir—H distance, which is known from neutron diffraction measurements to be 1.60 Å (Eckert et al., 1995; Bau et al., 1993, 1984; Garlaschelli et al., 1985) and found on difference Fourier maps here at 1.60 Å, refines to a much shorter distance (~1.37 Å), but still along the difference Fourier map Ir—H vector, because of the close proximity to the metal atom (Z = 77). In such cases, it is preferable to restrain the distance to 1.60 Å, as was done here, using the SHELXL97 command `DFIX 1.60. 01' (Sheldrick, 1997).
The pincer-bound atom Ir1 is best considered as being formally in the +3 oxidation state. The Ir1—C1 distance (Table 1) is similar to the Ir—C distance found in other PCP complexes of either IrI or IrIII (Table 2). The Ir—P bond lengths (average 2.327 Å; Table 1) are consistent with the Ir—P bond lengths in reported PCP complexes of IrIII (Table 2), but somewhat outside the range reported for PCP complexes of IrI (2.27–2.30 Å; Table 2). As in other (PCP)Ir complexes, the P—Ir—P angle is decidedly not linear (Gupta et al., 1997; Zhang et al., 2005, 2006; Ghosh et al., 2007). Both P atoms are bent away from the Cl ligand cis to the PCP aryl C—Ir bond, as seen by the corresponding P1—Ir1—Cl2 and P2—Ir1—Cl2 angles given in Table 1. The COD-bound atom Ir2 is formally in the +1 oxidation state and can be viewed as approximately square planar if one considers the centers of the coordinating C—C double bonds as single coordination points.
The Ir(COD)Cl2 portion of (I) has a geometry consistent with either Ir(COD)Cl2 part of [Ir(COD)Cl]2. However, presumably due to the steric bulk of the tBuPCP ligand, the considerable folding about the Cl···Cl vector observed in [Ir(COD)Cl]2 is not present in compound (I). The dihedral angle between the Cl2—Ir1 and Cl2— Ir2 portions of the central Ir2Cl2 group is only 13.04 (4)°, compared with the 86° dihedral angle in [Ir(COD)Cl]2 (Cotton et al., 1986). This gives rise to a significantly greater Ir···Ir distance: in [Ir(COD)Cl]2 this distance is 2.910 (1) Å, while in complex (I) the value is 3.6754 (2) Å.
The Ir—Cl bond lengths for the trivalent atom Ir1 are noticeably longer (average 2.55 Å) than those for the monovalent atom Ir2 (average 2.40 Å) or those found in the [Ir(COD)Cl]2 dimer (average 2.40 Å) (Cotton et al., 1986). As seen in Table 1, the specific values of the Ir2—Cl distances are fairly similar. The two Ir1—Cl distances, however, are substantially different, with the bond to the Cl atom trans to the strong trans-influence hydride ligand being substantially longer than that trans to the PCP aryl C atom. Not surprisingly, the Ir1—Cl distances in (I) are longer than the Ir—Cl distances in (PCP)Ir complexes with terminal chloride ligands (Table 2).
The geometries of both weaker and significant C—H···Cl interactions are described in Table 3, where it is shown that the intramolecular Cl···H distances are as short as 2.66 Å from atom Cl2 to the PCP methyl atom H16A and as short as 2.79 Å from atom Cl1 to the COD methylenyl atom H26. There are two weak intermolecular (COD) C—H···Cl2 interactions (last two entries in Table 3). The hexane solvate molecule lies across the inversion center at y = 1/2 in a channel that propagates along the crystallographic b axis. As a result, each solvate molecule is surrounded by the methyl and methylenyl groups of six Ir2 dimer complexes. The packing of the Ir dimer complexes and the hexane solvate molecules yields only long C—H···H—C contacts (>2.54 Å) and the nearest Cl atom to any H atom on the hexane solvent is quite remote (>5 Å).