Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026621/is2170sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026621/is2170Isup2.hkl |
CCDC reference: 654710
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.012 Å
- R factor = 0.040
- wR factor = 0.126
- Data-to-parameter ratio = 21.2
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Ir1 - Br1 .. 28.14 su PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Ir1 - Br2 .. 30.00 su
Alert level C PLAT128_ALERT_4_C Non-standard setting of Space group P21/c .... P21/a PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 11
Alert level G ABSTM02_ALERT_3_G The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.294 0.406 Tmin and Tmax expected: 0.249 0.406 RR = 1.180 Please check that your absorption correction is appropriate.
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Affandi et al. (1988); Attar et al. (1990); Farrugia (1997); Harder et al. (1991); Hayashi et al. (1983); Kessler et al. (1993); Le Bras et al. (1997); Matsuura et al. (1992); Meehan et al. (1997).
The title complex, (I), was obtained as a by-product from the reaction mixture of [Cp*IrCl2]2, Ph2PC6H4Br (Harder et al., 1991) and nBuLi in THF (which was aimed to prepare [Cp*IrCl(Ph2PC6H4)]), together with the corresponding (bromo)(chloro) and dicholoro complexes, [Cp*IrBrCl(PhPC12H8)].CH2Cl2 (II) and [Cp*IrCl2(PhPC12H8)].CH2Cl2 (III), respectively. The resulting red powdery product was recrystallized from a mixture of dichloromethane and methanol, affording red prismatic crystals. Although the crystal structure analyzed was consistent with the dibromo complex (I), the elemental analyses and the NMR spectra of the bulk sample fit well to the 4:4:1 mixture of the dibromo (I), (bromo)(chloro) (II) and dichloro (III) complexes. Anal. Found: C 43.59, H 3.79%. Calcd for C28H28(Br/Cl)2IrP.CH2Cl2: C 43.44, H 3.77%. 1H NMR (399.7 MHz, 303 K, CD2Cl2): δ 1.34 (d, J = 2.4 Hz, Cp*; I), 1.30 (d, J = 2.4 Hz, Cp*; II), 1.26 (d, J = 2.4 Hz, Cp*; III), 7.22–8.20 (m, Ph—PC12H8). 31P{1H} NMR (202.4 MHz, 303 K, CD2Cl2): δ -17.78 (s; I), -14.64 (s; II), -11.34 (s; III).
The H atoms were located geometrically and constrained to ride on their parent atoms with C—H = 0.95–0.99 Å with Uiso(H) = 1.2Ueq(C). The highest peak and deepest hole in the difference Fourier map are located 0.42 and 0.38 Å, respectively, from atoms Ir1 and Br1.
A large number of iridium(III) phosphine complexes has been characterized by X-ray analysis, while the structural study of the analogous phosphole complexes is limited. In fact, there has been no reports on the crystal structures of iridum(III) phosphole complexes, and only one paper describing the phosphole complex of iridium(I) (Hayashi et al., 1983). Here, we report the crystal structure of iridium(III) complex containing 5-phenyldibenzophosphole, [Cp*IrBr2(PhPC12H8)].CH2Cl2 (Cp* = η5-C5Me5), (I). A perspective drawing of (I) is shown in Fig. 1. The structural parameters of the 5-phenyldibenzophosphole moiety are comparable to those of free ligand (Meehan et al., 1997) and of the other metal complexes (Affandi et al., 1988; Attar et al., 1990; Matsuura et al., 1992; Kessler et al., 1993). The Ir—P bond is 2.2828 (15) Å, which is shorter by 0.04 Å than that of [Cp*IrCl2(PPh3)] (2.324 (3) Å; Le Bras et al., 1997). This would be due to the steric compactness of 5-phenyldibenzophosphole than PPh3. The dibenzophosphole moiety is nearly planar; the P atom is deviated by only 0.081 (7) Å from the least-square plane defined by biphenyl group. In the crystal, the dibenzophosphole planes in the neighboring molecules are stacked with each other (Fig. 2); the closest C···C distances between the planes are ~3.9 Å.
For related literature, see: Affandi et al. (1988); Attar et al. (1990); Farrugia (1997); Harder et al. (1991); Hayashi et al. (1983); Kessler et al. (1993); Le Bras et al. (1997); Matsuura et al. (1992); Meehan et al. (1997).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[IrBr2(C10H15)(C18H13P)]·CH2Cl2 | F(000) = 1600 |
Mr = 832.42 | Dx = 1.882 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2yab | Cell parameters from 17738 reflections |
a = 11.0793 (5) Å | θ = 3.2–27.4° |
b = 23.3836 (10) Å | µ = 7.52 mm−1 |
c = 12.8133 (5) Å | T = 200 K |
β = 117.746 (1)° | Block, red |
V = 2937.9 (2) Å3 | 0.22 × 0.16 × 0.12 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 6708 independent reflections |
Radiation source: fine-focus sealed tube | 6185 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
ω scans | h = −14→14 |
Absorption correction: numerical (ABSCOR; Higashi, 1999) | k = −30→30 |
Tmin = 0.294, Tmax = 0.406 | l = −16→16 |
28567 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.126 | w = 1/[σ2(Fo2) + (0.0587P)2 + 23.6384P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
6708 reflections | Δρmax = 1.76 e Å−3 |
317 parameters | Δρmin = −2.74 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00141 (19) |
[IrBr2(C10H15)(C18H13P)]·CH2Cl2 | V = 2937.9 (2) Å3 |
Mr = 832.42 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 11.0793 (5) Å | µ = 7.52 mm−1 |
b = 23.3836 (10) Å | T = 200 K |
c = 12.8133 (5) Å | 0.22 × 0.16 × 0.12 mm |
β = 117.746 (1)° |
Rigaku R-AXIS RAPID diffractometer | 6708 independent reflections |
Absorption correction: numerical (ABSCOR; Higashi, 1999) | 6185 reflections with I > 2σ(I) |
Tmin = 0.294, Tmax = 0.406 | Rint = 0.045 |
28567 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0587P)2 + 23.6384P] where P = (Fo2 + 2Fc2)/3 |
6708 reflections | Δρmax = 1.76 e Å−3 |
317 parameters | Δρmin = −2.74 e Å−3 |
x | y | z | Uiso*/Ueq | ||
Ir1 | 0.59098 (2) | 0.358232 (9) | 0.903861 (19) | 0.02182 (11) | |
Br1 | 0.67400 (9) | 0.43878 (4) | 1.04905 (7) | 0.0467 (2) | |
Br2 | 0.83164 (8) | 0.32885 (4) | 0.96032 (8) | 0.0465 (2) | |
Cl1 | −0.1229 (3) | 0.68037 (15) | 0.6740 (3) | 0.0792 (8) | |
Cl2 | 0.1036 (4) | 0.67924 (19) | 0.6196 (4) | 0.1039 (13) | |
P1 | 0.60296 (15) | 0.41650 (6) | 0.76603 (13) | 0.0222 (3) | |
C1 | 0.4956 (7) | 0.2768 (3) | 0.8362 (7) | 0.0324 (14) | |
C2 | 0.3938 (6) | 0.3206 (3) | 0.7905 (6) | 0.0275 (12) | |
C3 | 0.3896 (7) | 0.3487 (3) | 0.8888 (6) | 0.0272 (12) | |
C4 | 0.4822 (7) | 0.3181 (3) | 0.9943 (6) | 0.0318 (14) | |
C5 | 0.5475 (7) | 0.2743 (3) | 0.9627 (7) | 0.0360 (15) | |
C6 | 0.5320 (9) | 0.2348 (3) | 0.7667 (9) | 0.051 (2) | |
H6A | 0.4914 | 0.1975 | 0.7665 | 0.061* | |
H6B | 0.6314 | 0.2309 | 0.8028 | 0.061* | |
H6C | 0.4970 | 0.2484 | 0.6855 | 0.061* | |
C7 | 0.2987 (7) | 0.3322 (3) | 0.6636 (6) | 0.0383 (16) | |
H7A | 0.3451 | 0.3242 | 0.6161 | 0.046* | |
H7B | 0.2706 | 0.3725 | 0.6540 | 0.046* | |
H7C | 0.2181 | 0.3077 | 0.6374 | 0.046* | |
C8 | 0.2938 (8) | 0.3953 (3) | 0.8842 (7) | 0.0401 (16) | |
H8A | 0.2522 | 0.4130 | 0.8059 | 0.048* | |
H8B | 0.3445 | 0.4242 | 0.9440 | 0.048* | |
H8C | 0.2223 | 0.3790 | 0.8997 | 0.048* | |
C9 | 0.5046 (9) | 0.3308 (4) | 1.1176 (7) | 0.0470 (19) | |
H9A | 0.5943 | 0.3165 | 1.1751 | 0.056* | |
H9B | 0.4336 | 0.3120 | 1.1305 | 0.056* | |
H9C | 0.5005 | 0.3722 | 1.1274 | 0.056* | |
C10 | 0.6511 (9) | 0.2319 (4) | 1.0427 (9) | 0.054 (2) | |
H10A | 0.6936 | 0.2463 | 1.1238 | 0.065* | |
H10B | 0.7212 | 0.2263 | 1.0174 | 0.065* | |
H10C | 0.6060 | 0.1953 | 1.0391 | 0.065* | |
C11 | 0.7462 (6) | 0.4656 (3) | 0.8101 (5) | 0.0259 (12) | |
C12 | 0.7382 (8) | 0.5204 (3) | 0.8489 (6) | 0.0338 (14) | |
H12 | 0.6588 | 0.5320 | 0.8537 | 0.041* | |
C13 | 0.8465 (8) | 0.5581 (3) | 0.8804 (6) | 0.0392 (16) | |
H13 | 0.8408 | 0.5955 | 0.9070 | 0.047* | |
C14 | 0.9620 (8) | 0.5419 (3) | 0.8734 (6) | 0.0449 (19) | |
H14 | 1.0355 | 0.5680 | 0.8951 | 0.054* | |
C15 | 0.9707 (7) | 0.4882 (4) | 0.8351 (7) | 0.0423 (17) | |
H15 | 1.0507 | 0.4773 | 0.8304 | 0.051* | |
C16 | 0.8643 (7) | 0.4492 (3) | 0.8029 (6) | 0.0333 (14) | |
H16 | 0.8713 | 0.4121 | 0.7764 | 0.040* | |
C17 | 0.4560 (7) | 0.4607 (3) | 0.6799 (6) | 0.0280 (12) | |
C18 | 0.3897 (8) | 0.4989 (3) | 0.7191 (7) | 0.0367 (15) | |
H18 | 0.4214 | 0.5050 | 0.8010 | 0.044* | |
C19 | 0.2749 (9) | 0.5281 (4) | 0.6349 (8) | 0.051 (2) | |
H19 | 0.2288 | 0.5547 | 0.6599 | 0.061* | |
C20 | 0.2282 (9) | 0.5183 (4) | 0.5150 (8) | 0.054 (2) | |
H20 | 0.1508 | 0.5386 | 0.4589 | 0.065* | |
C21 | 0.2930 (8) | 0.4794 (3) | 0.4762 (7) | 0.0433 (17) | |
H21 | 0.2591 | 0.4727 | 0.3942 | 0.052* | |
C22 | 0.4073 (7) | 0.4502 (3) | 0.5573 (6) | 0.0310 (13) | |
C23 | 0.4847 (7) | 0.4055 (3) | 0.5328 (6) | 0.0320 (14) | |
C24 | 0.4606 (9) | 0.3845 (4) | 0.4231 (6) | 0.0458 (19) | |
H24 | 0.3896 | 0.4001 | 0.3528 | 0.055* | |
C25 | 0.5406 (11) | 0.3410 (4) | 0.4178 (7) | 0.053 (2) | |
H25 | 0.5241 | 0.3272 | 0.3426 | 0.064* | |
C26 | 0.6434 (10) | 0.3167 (4) | 0.5166 (7) | 0.049 (2) | |
H26 | 0.6960 | 0.2863 | 0.5093 | 0.059* | |
C27 | 0.6702 (8) | 0.3370 (3) | 0.6280 (6) | 0.0357 (15) | |
H27 | 0.7406 | 0.3205 | 0.6976 | 0.043* | |
C28 | 0.5904 (7) | 0.3823 (3) | 0.6347 (5) | 0.0275 (12) | |
C29 | 0.0387 (14) | 0.6521 (6) | 0.7106 (13) | 0.090 (4) | |
H29A | 0.1023 | 0.6615 | 0.7937 | 0.109* | |
H29B | 0.0323 | 0.6100 | 0.7031 | 0.109* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ir1 | 0.02293 (15) | 0.02034 (14) | 0.02187 (15) | 0.00001 (8) | 0.01015 (10) | 0.00051 (8) |
Br1 | 0.0534 (5) | 0.0449 (4) | 0.0441 (4) | −0.0071 (3) | 0.0247 (4) | −0.0091 (3) |
Br2 | 0.0401 (4) | 0.0448 (4) | 0.0530 (5) | 0.0051 (3) | 0.0204 (4) | 0.0048 (3) |
Cl1 | 0.0736 (18) | 0.100 (2) | 0.0667 (16) | 0.0096 (16) | 0.0346 (14) | 0.0189 (15) |
Cl2 | 0.091 (2) | 0.131 (3) | 0.107 (3) | 0.032 (2) | 0.060 (2) | 0.052 (2) |
P1 | 0.0242 (7) | 0.0215 (7) | 0.0199 (7) | −0.0004 (5) | 0.0093 (6) | 0.0001 (5) |
C1 | 0.032 (3) | 0.020 (3) | 0.047 (4) | −0.005 (2) | 0.020 (3) | −0.004 (3) |
C2 | 0.025 (3) | 0.027 (3) | 0.029 (3) | −0.008 (2) | 0.011 (2) | −0.003 (2) |
C3 | 0.026 (3) | 0.024 (3) | 0.032 (3) | −0.003 (2) | 0.015 (3) | −0.002 (2) |
C4 | 0.032 (3) | 0.036 (3) | 0.031 (3) | −0.009 (3) | 0.017 (3) | 0.003 (3) |
C5 | 0.033 (3) | 0.026 (3) | 0.050 (4) | −0.003 (3) | 0.020 (3) | 0.011 (3) |
C6 | 0.048 (5) | 0.037 (4) | 0.075 (6) | −0.009 (3) | 0.035 (4) | −0.021 (4) |
C7 | 0.033 (4) | 0.047 (4) | 0.026 (3) | −0.016 (3) | 0.007 (3) | −0.002 (3) |
C8 | 0.037 (4) | 0.037 (4) | 0.057 (5) | 0.001 (3) | 0.030 (4) | −0.004 (3) |
C9 | 0.048 (4) | 0.065 (5) | 0.031 (4) | −0.015 (4) | 0.021 (3) | 0.001 (4) |
C10 | 0.040 (4) | 0.047 (5) | 0.068 (6) | 0.002 (4) | 0.020 (4) | 0.027 (4) |
C11 | 0.028 (3) | 0.027 (3) | 0.020 (3) | −0.004 (2) | 0.008 (2) | 0.003 (2) |
C12 | 0.040 (4) | 0.029 (3) | 0.029 (3) | −0.003 (3) | 0.013 (3) | 0.001 (3) |
C13 | 0.050 (4) | 0.029 (3) | 0.031 (3) | −0.013 (3) | 0.013 (3) | −0.003 (3) |
C14 | 0.046 (4) | 0.044 (4) | 0.030 (3) | −0.020 (3) | 0.006 (3) | 0.008 (3) |
C15 | 0.027 (3) | 0.057 (5) | 0.037 (4) | −0.004 (3) | 0.010 (3) | 0.010 (3) |
C16 | 0.032 (3) | 0.033 (3) | 0.032 (3) | 0.001 (3) | 0.012 (3) | 0.007 (3) |
C17 | 0.029 (3) | 0.025 (3) | 0.031 (3) | 0.003 (2) | 0.014 (3) | 0.002 (2) |
C18 | 0.038 (4) | 0.035 (3) | 0.039 (4) | 0.008 (3) | 0.019 (3) | 0.006 (3) |
C19 | 0.046 (4) | 0.049 (5) | 0.060 (5) | 0.024 (4) | 0.026 (4) | 0.016 (4) |
C20 | 0.043 (4) | 0.060 (5) | 0.052 (5) | 0.021 (4) | 0.016 (4) | 0.025 (4) |
C21 | 0.040 (4) | 0.047 (4) | 0.032 (4) | 0.006 (3) | 0.008 (3) | 0.011 (3) |
C22 | 0.034 (3) | 0.031 (3) | 0.026 (3) | 0.000 (3) | 0.012 (3) | 0.008 (3) |
C23 | 0.037 (3) | 0.033 (3) | 0.025 (3) | −0.007 (3) | 0.013 (3) | 0.001 (3) |
C24 | 0.062 (5) | 0.050 (4) | 0.023 (3) | −0.008 (4) | 0.017 (3) | −0.001 (3) |
C25 | 0.082 (7) | 0.052 (5) | 0.030 (4) | 0.001 (5) | 0.030 (4) | −0.009 (4) |
C26 | 0.072 (6) | 0.044 (4) | 0.041 (4) | 0.007 (4) | 0.034 (4) | −0.007 (3) |
C27 | 0.047 (4) | 0.036 (3) | 0.029 (3) | 0.003 (3) | 0.022 (3) | −0.003 (3) |
C28 | 0.035 (3) | 0.026 (3) | 0.021 (3) | −0.003 (2) | 0.013 (2) | −0.001 (2) |
C29 | 0.081 (9) | 0.100 (9) | 0.087 (9) | 0.032 (7) | 0.037 (7) | 0.046 (8) |
Ir1—C1 | 2.155 (6) | C10—H10B | 0.9800 |
Ir1—C3 | 2.160 (6) | C10—H10C | 0.9800 |
Ir1—C2 | 2.169 (6) | C11—C12 | 1.393 (9) |
Ir1—C4 | 2.231 (6) | C11—C16 | 1.406 (10) |
Ir1—C5 | 2.233 (6) | C12—C13 | 1.389 (10) |
Ir1—P1 | 2.2829 (15) | C12—H12 | 0.9500 |
Ir1—Br1 | 2.5022 (8) | C13—C14 | 1.376 (12) |
Ir1—Br2 | 2.5118 (8) | C13—H13 | 0.9500 |
Cl1—C29 | 1.756 (13) | C14—C15 | 1.369 (12) |
Cl2—C29 | 1.748 (14) | C14—H14 | 0.9500 |
P1—C17 | 1.807 (6) | C15—C16 | 1.391 (10) |
P1—C28 | 1.809 (6) | C15—H15 | 0.9500 |
P1—C11 | 1.823 (6) | C16—H16 | 0.9500 |
C1—C2 | 1.431 (9) | C17—C18 | 1.389 (9) |
C1—C5 | 1.447 (10) | C17—C22 | 1.426 (9) |
C1—C6 | 1.502 (10) | C18—C19 | 1.405 (10) |
C2—C3 | 1.440 (9) | C18—H18 | 0.9500 |
C2—C7 | 1.495 (9) | C19—C20 | 1.394 (13) |
C3—C4 | 1.450 (9) | C19—H19 | 0.9500 |
C3—C8 | 1.502 (9) | C20—C21 | 1.387 (12) |
C4—C5 | 1.416 (10) | C20—H20 | 0.9500 |
C4—C9 | 1.510 (10) | C21—C22 | 1.386 (10) |
C5—C10 | 1.504 (10) | C21—H21 | 0.9500 |
C6—H6A | 0.9800 | C22—C23 | 1.476 (10) |
C6—H6B | 0.9800 | C23—C24 | 1.393 (10) |
C6—H6C | 0.9800 | C23—C28 | 1.396 (9) |
C7—H7A | 0.9800 | C24—C25 | 1.370 (13) |
C7—H7B | 0.9800 | C24—H24 | 0.9500 |
C7—H7C | 0.9800 | C25—C26 | 1.371 (13) |
C8—H8A | 0.9800 | C25—H25 | 0.9500 |
C8—H8B | 0.9800 | C26—C27 | 1.399 (10) |
C8—H8C | 0.9800 | C26—H26 | 0.9500 |
C9—H9A | 0.9800 | C27—C28 | 1.408 (10) |
C9—H9B | 0.9800 | C27—H27 | 0.9500 |
C9—H9C | 0.9800 | C29—H29A | 0.9900 |
C10—H10A | 0.9800 | C29—H29B | 0.9900 |
C1—Ir1—C3 | 65.2 (2) | C3—C8—H8B | 109.5 |
C1—Ir1—C2 | 38.7 (2) | H8A—C8—H8B | 109.5 |
C3—Ir1—C2 | 38.9 (2) | C3—C8—H8C | 109.5 |
C1—Ir1—C4 | 63.6 (3) | H8A—C8—H8C | 109.5 |
C3—Ir1—C4 | 38.5 (2) | H8B—C8—H8C | 109.5 |
C2—Ir1—C4 | 63.7 (2) | C4—C9—H9A | 109.5 |
C1—Ir1—C5 | 38.5 (3) | C4—C9—H9B | 109.5 |
C3—Ir1—C5 | 64.1 (2) | H9A—C9—H9B | 109.5 |
C2—Ir1—C5 | 63.9 (3) | C4—C9—H9C | 109.5 |
C4—Ir1—C5 | 37.0 (3) | H9A—C9—H9C | 109.5 |
C1—Ir1—P1 | 114.2 (2) | H9B—C9—H9C | 109.5 |
C3—Ir1—P1 | 114.97 (18) | C5—C10—H10A | 109.5 |
C2—Ir1—P1 | 97.34 (17) | C5—C10—H10B | 109.5 |
C4—Ir1—P1 | 153.27 (19) | H10A—C10—H10B | 109.5 |
C5—Ir1—P1 | 152.2 (2) | C5—C10—H10C | 109.5 |
C1—Ir1—Br1 | 154.99 (19) | H10A—C10—H10C | 109.5 |
C3—Ir1—Br1 | 98.68 (17) | H10B—C10—H10C | 109.5 |
C2—Ir1—Br1 | 135.27 (18) | C12—C11—C16 | 119.3 (6) |
C4—Ir1—Br1 | 91.78 (18) | C12—C11—P1 | 120.0 (5) |
C5—Ir1—Br1 | 118.2 (2) | C16—C11—P1 | 120.7 (5) |
P1—Ir1—Br1 | 89.56 (4) | C13—C12—C11 | 119.9 (7) |
C1—Ir1—Br2 | 97.47 (18) | C13—C12—H12 | 120.1 |
C3—Ir1—Br2 | 155.72 (17) | C11—C12—H12 | 120.1 |
C2—Ir1—Br2 | 133.26 (18) | C14—C13—C12 | 120.6 (7) |
C4—Ir1—Br2 | 119.53 (18) | C14—C13—H13 | 119.7 |
C5—Ir1—Br2 | 91.69 (18) | C12—C13—H13 | 119.7 |
P1—Ir1—Br2 | 87.13 (4) | C15—C14—C13 | 119.9 (7) |
Br1—Ir1—Br2 | 91.05 (3) | C15—C14—H14 | 120.0 |
C17—P1—C28 | 91.6 (3) | C13—C14—H14 | 120.0 |
C17—P1—C11 | 103.6 (3) | C14—C15—C16 | 121.0 (8) |
C28—P1—C11 | 104.2 (3) | C14—C15—H15 | 119.5 |
C17—P1—Ir1 | 117.0 (2) | C16—C15—H15 | 119.5 |
C28—P1—Ir1 | 116.6 (2) | C15—C16—C11 | 119.2 (7) |
C11—P1—Ir1 | 119.48 (19) | C15—C16—H16 | 120.4 |
C2—C1—C5 | 108.2 (6) | C11—C16—H16 | 120.4 |
C2—C1—C6 | 127.2 (7) | C18—C17—C22 | 121.1 (6) |
C5—C1—C6 | 124.2 (7) | C18—C17—P1 | 128.6 (5) |
C2—C1—Ir1 | 71.2 (3) | C22—C17—P1 | 110.3 (5) |
C5—C1—Ir1 | 73.7 (4) | C17—C18—C19 | 118.5 (7) |
C6—C1—Ir1 | 126.9 (5) | C17—C18—H18 | 120.7 |
C1—C2—C3 | 108.0 (6) | C19—C18—H18 | 120.7 |
C1—C2—C7 | 126.7 (6) | C20—C19—C18 | 120.4 (8) |
C3—C2—C7 | 125.1 (6) | C20—C19—H19 | 119.8 |
C1—C2—Ir1 | 70.1 (4) | C18—C19—H19 | 119.8 |
C3—C2—Ir1 | 70.2 (3) | C21—C20—C19 | 120.9 (7) |
C7—C2—Ir1 | 129.4 (4) | C21—C20—H20 | 119.5 |
C2—C3—C4 | 107.0 (6) | C19—C20—H20 | 119.5 |
C2—C3—C8 | 127.3 (6) | C22—C21—C20 | 120.0 (7) |
C4—C3—C8 | 125.1 (6) | C22—C21—H21 | 120.0 |
C2—C3—Ir1 | 70.9 (4) | C20—C21—H21 | 120.0 |
C4—C3—Ir1 | 73.4 (4) | C21—C22—C17 | 119.1 (7) |
C8—C3—Ir1 | 127.6 (5) | C21—C22—C23 | 127.5 (7) |
C5—C4—C3 | 108.9 (6) | C17—C22—C23 | 113.3 (6) |
C5—C4—C9 | 125.8 (7) | C24—C23—C28 | 119.4 (7) |
C3—C4—C9 | 125.3 (7) | C24—C23—C22 | 127.3 (7) |
C5—C4—Ir1 | 71.6 (4) | C28—C23—C22 | 113.3 (6) |
C3—C4—Ir1 | 68.1 (3) | C25—C24—C23 | 119.1 (7) |
C9—C4—Ir1 | 126.5 (5) | C25—C24—H24 | 120.4 |
C4—C5—C1 | 107.6 (6) | C23—C24—H24 | 120.4 |
C4—C5—C10 | 127.7 (8) | C24—C25—C26 | 122.8 (7) |
C1—C5—C10 | 124.7 (7) | C24—C25—H25 | 118.6 |
C4—C5—Ir1 | 71.4 (4) | C26—C25—H25 | 118.6 |
C1—C5—Ir1 | 67.8 (3) | C25—C26—C27 | 119.4 (8) |
C10—C5—Ir1 | 126.5 (5) | C25—C26—H26 | 120.3 |
C1—C6—H6A | 109.5 | C27—C26—H26 | 120.3 |
C1—C6—H6B | 109.5 | C26—C27—C28 | 118.5 (7) |
H6A—C6—H6B | 109.5 | C26—C27—H27 | 120.8 |
C1—C6—H6C | 109.5 | C28—C27—H27 | 120.8 |
H6A—C6—H6C | 109.5 | C23—C28—C27 | 120.9 (6) |
H6B—C6—H6C | 109.5 | C23—C28—P1 | 111.4 (5) |
C2—C7—H7A | 109.5 | C27—C28—P1 | 127.7 (5) |
C2—C7—H7B | 109.5 | Cl2—C29—Cl1 | 111.7 (6) |
H7A—C7—H7B | 109.5 | Cl2—C29—H29A | 109.3 |
C2—C7—H7C | 109.5 | Cl1—C29—H29A | 109.3 |
H7A—C7—H7C | 109.5 | Cl2—C29—H29B | 109.3 |
H7B—C7—H7C | 109.5 | Cl1—C29—H29B | 109.3 |
C3—C8—H8A | 109.5 | H29A—C29—H29B | 107.9 |
C1—Ir1—P1—C17 | 85.8 (3) | C2—Ir1—C4—C5 | 80.8 (4) |
C3—Ir1—P1—C17 | 13.1 (3) | P1—Ir1—C4—C5 | 129.3 (4) |
C2—Ir1—P1—C17 | 49.4 (3) | Br1—Ir1—C4—C5 | −138.1 (4) |
C4—Ir1—P1—C17 | 6.8 (5) | Br2—Ir1—C4—C5 | −45.9 (4) |
C5—Ir1—P1—C17 | 94.5 (5) | C1—Ir1—C4—C3 | −82.6 (4) |
Br1—Ir1—P1—C17 | −86.2 (2) | C2—Ir1—C4—C3 | −39.3 (4) |
Br2—Ir1—P1—C17 | −177.3 (2) | C5—Ir1—C4—C3 | −120.1 (6) |
C1—Ir1—P1—C28 | −21.1 (3) | P1—Ir1—C4—C3 | 9.2 (6) |
C3—Ir1—P1—C28 | −93.8 (3) | Br1—Ir1—C4—C3 | 101.7 (4) |
C2—Ir1—P1—C28 | −57.5 (3) | Br2—Ir1—C4—C3 | −166.0 (3) |
C4—Ir1—P1—C28 | −100.1 (5) | C1—Ir1—C4—C9 | 158.8 (8) |
C5—Ir1—P1—C28 | −12.4 (5) | C3—Ir1—C4—C9 | −118.5 (8) |
Br1—Ir1—P1—C28 | 166.9 (2) | C2—Ir1—C4—C9 | −157.8 (8) |
Br2—Ir1—P1—C28 | 75.8 (2) | C5—Ir1—C4—C9 | 121.4 (9) |
C1—Ir1—P1—C11 | −147.9 (3) | P1—Ir1—C4—C9 | −109.3 (7) |
C3—Ir1—P1—C11 | 139.4 (3) | Br1—Ir1—C4—C9 | −16.8 (7) |
C2—Ir1—P1—C11 | 175.7 (3) | Br2—Ir1—C4—C9 | 75.4 (7) |
C4—Ir1—P1—C11 | 133.1 (5) | C3—C4—C5—C1 | −0.4 (7) |
C5—Ir1—P1—C11 | −139.2 (5) | C9—C4—C5—C1 | 179.4 (6) |
Br1—Ir1—P1—C11 | 40.0 (2) | Ir1—C4—C5—C1 | −58.4 (4) |
Br2—Ir1—P1—C11 | −51.0 (2) | C3—C4—C5—C10 | −179.8 (7) |
C3—Ir1—C1—C2 | 37.3 (4) | C9—C4—C5—C10 | 0.0 (11) |
C4—Ir1—C1—C2 | 80.2 (4) | Ir1—C4—C5—C10 | 122.2 (7) |
C5—Ir1—C1—C2 | 116.3 (6) | C3—C4—C5—Ir1 | 58.0 (4) |
P1—Ir1—C1—C2 | −70.2 (4) | C9—C4—C5—Ir1 | −122.2 (7) |
Br1—Ir1—C1—C2 | 90.6 (6) | C2—C1—C5—C4 | −2.6 (7) |
Br2—Ir1—C1—C2 | −160.4 (4) | C6—C1—C5—C4 | −175.5 (6) |
C3—Ir1—C1—C5 | −79.0 (4) | Ir1—C1—C5—C4 | 60.6 (5) |
C2—Ir1—C1—C5 | −116.3 (6) | C2—C1—C5—C10 | 176.8 (6) |
C4—Ir1—C1—C5 | −36.1 (4) | C6—C1—C5—C10 | 4.0 (11) |
P1—Ir1—C1—C5 | 173.5 (3) | Ir1—C1—C5—C10 | −119.9 (7) |
Br1—Ir1—C1—C5 | −25.7 (7) | C2—C1—C5—Ir1 | −63.3 (4) |
Br2—Ir1—C1—C5 | 83.3 (4) | C6—C1—C5—Ir1 | 123.9 (7) |
C3—Ir1—C1—C6 | 160.2 (8) | C1—Ir1—C5—C4 | −118.8 (6) |
C2—Ir1—C1—C6 | 122.9 (9) | C3—Ir1—C5—C4 | −36.8 (4) |
C4—Ir1—C1—C6 | −156.9 (8) | C2—Ir1—C5—C4 | −80.2 (4) |
C5—Ir1—C1—C6 | −120.8 (9) | P1—Ir1—C5—C4 | −131.7 (4) |
P1—Ir1—C1—C6 | 52.6 (7) | Br1—Ir1—C5—C4 | 49.2 (4) |
Br1—Ir1—C1—C6 | −146.5 (6) | Br2—Ir1—C5—C4 | 141.3 (4) |
Br2—Ir1—C1—C6 | −37.6 (7) | C3—Ir1—C5—C1 | 82.0 (4) |
C5—C1—C2—C3 | 4.7 (7) | C2—Ir1—C5—C1 | 38.6 (4) |
C6—C1—C2—C3 | 177.2 (7) | C4—Ir1—C5—C1 | 118.8 (6) |
Ir1—C1—C2—C3 | −60.3 (4) | P1—Ir1—C5—C1 | −12.9 (7) |
C5—C1—C2—C7 | −170.2 (6) | Br1—Ir1—C5—C1 | 168.0 (3) |
C6—C1—C2—C7 | 2.3 (11) | Br2—Ir1—C5—C1 | −99.9 (4) |
Ir1—C1—C2—C7 | 124.9 (6) | C1—Ir1—C5—C10 | 117.6 (9) |
C5—C1—C2—Ir1 | 64.9 (4) | C3—Ir1—C5—C10 | −160.4 (8) |
C6—C1—C2—Ir1 | −122.5 (7) | C2—Ir1—C5—C10 | 156.2 (8) |
C3—Ir1—C2—C1 | −118.7 (5) | C4—Ir1—C5—C10 | −123.6 (9) |
C4—Ir1—C2—C1 | −79.8 (4) | P1—Ir1—C5—C10 | 104.7 (8) |
C5—Ir1—C2—C1 | −38.4 (4) | Br1—Ir1—C5—C10 | −74.4 (8) |
P1—Ir1—C2—C1 | 120.1 (4) | Br2—Ir1—C5—C10 | 17.7 (8) |
Br1—Ir1—C2—C1 | −143.1 (3) | C17—P1—C11—C12 | 43.0 (6) |
Br2—Ir1—C2—C1 | 27.1 (5) | C28—P1—C11—C12 | 138.2 (5) |
C1—Ir1—C2—C3 | 118.7 (5) | Ir1—P1—C11—C12 | −89.4 (5) |
C4—Ir1—C2—C3 | 38.9 (4) | C17—P1—C11—C16 | −135.5 (5) |
C5—Ir1—C2—C3 | 80.3 (4) | C28—P1—C11—C16 | −40.3 (6) |
P1—Ir1—C2—C3 | −121.2 (3) | Ir1—P1—C11—C16 | 92.1 (5) |
Br1—Ir1—C2—C3 | −24.4 (5) | C16—C11—C12—C13 | −0.3 (9) |
Br2—Ir1—C2—C3 | 145.8 (3) | P1—C11—C12—C13 | −178.8 (5) |
C1—Ir1—C2—C7 | −121.6 (8) | C11—C12—C13—C14 | 0.2 (10) |
C3—Ir1—C2—C7 | 119.7 (8) | C12—C13—C14—C15 | 0.0 (11) |
C4—Ir1—C2—C7 | 158.6 (7) | C13—C14—C15—C16 | −0.1 (11) |
C5—Ir1—C2—C7 | −160.0 (7) | C14—C15—C16—C11 | 0.0 (10) |
P1—Ir1—C2—C7 | −1.5 (7) | C12—C11—C16—C15 | 0.2 (9) |
Br1—Ir1—C2—C7 | 95.3 (6) | P1—C11—C16—C15 | 178.7 (5) |
Br2—Ir1—C2—C7 | −94.5 (6) | C28—P1—C17—C18 | 175.0 (7) |
C1—C2—C3—C4 | −4.8 (7) | C11—P1—C17—C18 | −79.9 (7) |
C7—C2—C3—C4 | 170.1 (6) | Ir1—P1—C17—C18 | 53.9 (7) |
Ir1—C2—C3—C4 | −65.0 (4) | C28—P1—C17—C22 | −2.6 (5) |
C1—C2—C3—C8 | −176.6 (6) | C11—P1—C17—C22 | 102.4 (5) |
C7—C2—C3—C8 | −1.6 (10) | Ir1—P1—C17—C22 | −123.8 (4) |
Ir1—C2—C3—C8 | 123.2 (7) | C22—C17—C18—C19 | −1.5 (11) |
C1—C2—C3—Ir1 | 60.2 (4) | P1—C17—C18—C19 | −178.9 (6) |
C7—C2—C3—Ir1 | −124.8 (6) | C17—C18—C19—C20 | 0.8 (13) |
C1—Ir1—C3—C2 | −37.2 (4) | C18—C19—C20—C21 | 0.5 (14) |
C4—Ir1—C3—C2 | −115.2 (5) | C19—C20—C21—C22 | −1.0 (14) |
C5—Ir1—C3—C2 | −79.9 (4) | C20—C21—C22—C17 | 0.3 (11) |
P1—Ir1—C3—C2 | 69.3 (4) | C20—C21—C22—C23 | 176.6 (8) |
Br1—Ir1—C3—C2 | 162.9 (3) | C18—C17—C22—C21 | 1.0 (10) |
Br2—Ir1—C3—C2 | −84.6 (5) | P1—C17—C22—C21 | 178.8 (6) |
C1—Ir1—C3—C4 | 78.1 (4) | C18—C17—C22—C23 | −175.8 (6) |
C2—Ir1—C3—C4 | 115.2 (5) | P1—C17—C22—C23 | 2.0 (7) |
C5—Ir1—C3—C4 | 35.4 (4) | C21—C22—C23—C24 | 1.8 (12) |
P1—Ir1—C3—C4 | −175.5 (3) | C17—C22—C23—C24 | 178.3 (7) |
Br1—Ir1—C3—C4 | −81.9 (4) | C21—C22—C23—C28 | −176.5 (7) |
Br2—Ir1—C3—C4 | 30.7 (6) | C17—C22—C23—C28 | 0.0 (8) |
C1—Ir1—C3—C8 | −160.1 (7) | C28—C23—C24—C25 | 0.6 (12) |
C2—Ir1—C3—C8 | −122.9 (8) | C22—C23—C24—C25 | −177.6 (8) |
C4—Ir1—C3—C8 | 121.8 (8) | C23—C24—C25—C26 | 0.6 (15) |
C5—Ir1—C3—C8 | 157.2 (7) | C24—C25—C26—C27 | −0.8 (15) |
P1—Ir1—C3—C8 | −53.6 (7) | C25—C26—C27—C28 | −0.4 (13) |
Br1—Ir1—C3—C8 | 40.0 (6) | C24—C23—C28—C27 | −1.8 (10) |
Br2—Ir1—C3—C8 | 152.5 (5) | C22—C23—C28—C27 | 176.7 (6) |
C2—C3—C4—C5 | 3.2 (7) | C24—C23—C28—P1 | 179.6 (6) |
C8—C3—C4—C5 | 175.2 (6) | C22—C23—C28—P1 | −2.0 (7) |
Ir1—C3—C4—C5 | −60.1 (5) | C26—C27—C28—C23 | 1.7 (11) |
C2—C3—C4—C9 | −176.6 (6) | C26—C27—C28—P1 | −179.9 (6) |
C8—C3—C4—C9 | −4.6 (10) | C17—P1—C28—C23 | 2.6 (5) |
Ir1—C3—C4—C9 | 120.1 (7) | C11—P1—C28—C23 | −101.9 (5) |
C2—C3—C4—Ir1 | 63.4 (4) | Ir1—P1—C28—C23 | 124.1 (4) |
C8—C3—C4—Ir1 | −124.7 (6) | C17—P1—C28—C27 | −175.9 (7) |
C1—Ir1—C4—C5 | 37.5 (4) | C11—P1—C28—C27 | 79.6 (7) |
C3—Ir1—C4—C5 | 120.1 (6) | Ir1—P1—C28—C27 | −54.4 (7) |
Experimental details
Crystal data | |
Chemical formula | [IrBr2(C10H15)(C18H13P)]·CH2Cl2 |
Mr | 832.42 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 200 |
a, b, c (Å) | 11.0793 (5), 23.3836 (10), 12.8133 (5) |
β (°) | 117.746 (1) |
V (Å3) | 2937.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.52 |
Crystal size (mm) | 0.22 × 0.16 × 0.12 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Numerical (ABSCOR; Higashi, 1999) |
Tmin, Tmax | 0.294, 0.406 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28567, 6708, 6185 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.126, 1.08 |
No. of reflections | 6708 |
No. of parameters | 317 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0587P)2 + 23.6384P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.76, −2.74 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Rigaku/MSC, 2004), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
Ir1—C1 | 2.155 (6) | Ir1—Br1 | 2.5022 (8) |
Ir1—C3 | 2.160 (6) | Ir1—Br2 | 2.5118 (8) |
Ir1—C2 | 2.169 (6) | P1—C17 | 1.807 (6) |
Ir1—C4 | 2.231 (6) | P1—C28 | 1.809 (6) |
Ir1—C5 | 2.233 (6) | P1—C11 | 1.823 (6) |
Ir1—P1 | 2.2829 (15) | ||
P1—Ir1—Br1 | 89.56 (4) | C28—P1—C11 | 104.2 (3) |
P1—Ir1—Br2 | 87.13 (4) | C17—P1—Ir1 | 117.0 (2) |
Br1—Ir1—Br2 | 91.05 (3) | C28—P1—Ir1 | 116.6 (2) |
C17—P1—C28 | 91.6 (3) | C11—P1—Ir1 | 119.48 (19) |
C17—P1—C11 | 103.6 (3) |
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A large number of iridium(III) phosphine complexes has been characterized by X-ray analysis, while the structural study of the analogous phosphole complexes is limited. In fact, there has been no reports on the crystal structures of iridum(III) phosphole complexes, and only one paper describing the phosphole complex of iridium(I) (Hayashi et al., 1983). Here, we report the crystal structure of iridium(III) complex containing 5-phenyldibenzophosphole, [Cp*IrBr2(PhPC12H8)].CH2Cl2 (Cp* = η5-C5Me5), (I). A perspective drawing of (I) is shown in Fig. 1. The structural parameters of the 5-phenyldibenzophosphole moiety are comparable to those of free ligand (Meehan et al., 1997) and of the other metal complexes (Affandi et al., 1988; Attar et al., 1990; Matsuura et al., 1992; Kessler et al., 1993). The Ir—P bond is 2.2828 (15) Å, which is shorter by 0.04 Å than that of [Cp*IrCl2(PPh3)] (2.324 (3) Å; Le Bras et al., 1997). This would be due to the steric compactness of 5-phenyldibenzophosphole than PPh3. The dibenzophosphole moiety is nearly planar; the P atom is deviated by only 0.081 (7) Å from the least-square plane defined by biphenyl group. In the crystal, the dibenzophosphole planes in the neighboring molecules are stacked with each other (Fig. 2); the closest C···C distances between the planes are ~3.9 Å.