
Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680300429X/na6193sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S160053680300429X/na6193Isup2.hkl |
CCDC reference: 209884
The precursor (NH4)3[IrCl6]H2O and two equivalents of 4,4'-dimethyl-2,2'-bipyridine were suspended in ethylene glycol. Under a purging nitrogen atmosphere, the suspension was subjected to reflux for 15 min under microwave irradiation with a frequency of 2450 MHz to activate the OH group of ethylene glycol, and then cooled to room temperature. The saturated aqueous solution of KPF6 was added to the brown solution. Air-stable yellow single crystals were obtained by recrystallization from acetonitrile (Yoshikawa et al., 2000).
All H atoms bonded to C atoms were placed at calculated positions, with isotropic displacement parameters.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
![]() | Fig. 1. The molecular structure of (I), showing ellipsoids at the 50% probability level. |
[IrCl2(C24H24N4)2]PF6 | Dx = 1.835 Mg m−3 |
Mr = 776.57 | Mo Kα radiation, λ = 0.7107 Å |
Monoclinic, P21/n | Cell parameters from 25815 reflections |
a = 7.8114 (2) Å | θ = 1.5–30.5° |
b = 21.6075 (7) Å | µ = 5.07 mm−1 |
c = 16.6606 (5) Å | T = 296 K |
β = 91.4634 (7)° | Platelet, yellow |
V = 2811.1 (1) Å3 | 0.80 × 0.10 × 0.02 mm |
Z = 4 |
Rigaku RAXIS-RAPID imaging plate diffractometer | 6274 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.068 |
ω scans | θmax = 30.5° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −9→11 |
Tmin = 0.552, Tmax = 0.904 | k = −30→30 |
32401 measured reflections | l = −23→23 |
8462 independent reflections |
Refinement on F2 | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.053 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.126 | (Δ/σ)max = −0.003 |
S = 1.41 | Δρmax = 2.81 e Å−3 |
6274 reflections | Δρmin = −2.53 e Å−3 |
343 parameters |
[IrCl2(C24H24N4)2]PF6 | V = 2811.1 (1) Å3 |
Mr = 776.57 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.8114 (2) Å | µ = 5.07 mm−1 |
b = 21.6075 (7) Å | T = 296 K |
c = 16.6606 (5) Å | 0.80 × 0.10 × 0.02 mm |
β = 91.4634 (7)° |
Rigaku RAXIS-RAPID imaging plate diffractometer | 8462 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 6274 reflections with I > 2σ(I) |
Tmin = 0.552, Tmax = 0.904 | Rint = 0.068 |
32401 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 343 parameters |
wR(F2) = 0.126 | H-atom parameters not refined |
S = 1.41 | Δρmax = 2.81 e Å−3 |
6274 reflections | Δρmin = −2.53 e Å−3 |
Refinement. Refinement using reflections with F2 > -10.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Ir1 | 0.75103 (2) | 0.09645 (1) | 0.68643 (1) | 0.03194 (8) | |
Cl1 | 0.927 (2) | 0.1849 (3) | 0.6777 (5) | 0.326 (5) | |
Cl2 | 0.8864 (2) | 0.05412 (9) | 0.57419 (9) | 0.0502 (4) | |
P1 | 0.9986 (3) | −0.14521 (8) | 0.8504 (1) | 0.0510 (4) | |
F1 | 0.8195 (9) | −0.1717 (4) | 0.8311 (5) | 0.132 (3) | |
F2 | 0.9897 (7) | −0.1778 (2) | 0.9370 (3) | 0.081 (1) | |
F3 | 1.1789 (9) | −0.1184 (4) | 0.8734 (5) | 0.144 (3) | |
F4 | 1.0012 (8) | −0.1116 (3) | 0.7664 (3) | 0.083 (2) | |
F5 | 0.917 (1) | −0.0856 (3) | 0.8853 (4) | 0.133 (3) | |
F6 | 1.081 (1) | −0.2044 (3) | 0.8160 (4) | 0.123 (3) | |
N1 | 0.6018 (6) | 0.0139 (2) | 0.6873 (3) | 0.037 (1) | |
N2 | 0.5546 (6) | 0.1182 (2) | 0.6089 (3) | 0.037 (1) | |
N3 | 0.6511 (6) | 0.1313 (2) | 0.7872 (3) | 0.038 (1) | |
N4 | 0.9320 (5) | 0.0702 (2) | 0.7687 (3) | 0.0332 (10) | |
C1 | 0.6333 (7) | −0.0368 (3) | 0.7319 (4) | 0.041 (1) | |
C2 | 0.5429 (9) | −0.0898 (3) | 0.7226 (5) | 0.050 (2) | |
C3 | 0.4145 (8) | −0.0939 (3) | 0.6625 (4) | 0.043 (1) | |
C4 | 0.3798 (7) | −0.0409 (3) | 0.6179 (4) | 0.040 (1) | |
C5 | 0.4745 (7) | 0.0124 (3) | 0.6317 (3) | 0.033 (1) | |
C6 | 0.4458 (7) | 0.0709 (3) | 0.5875 (3) | 0.033 (1) | |
C7 | 0.3169 (8) | 0.0789 (3) | 0.5300 (4) | 0.040 (1) | |
C8 | 0.2917 (8) | 0.1355 (3) | 0.4930 (4) | 0.045 (1) | |
C9 | 0.3964 (9) | 0.1836 (3) | 0.5179 (4) | 0.051 (2) | |
C10 | 0.5244 (9) | 0.1736 (3) | 0.5737 (4) | 0.048 (2) | |
C11 | 0.3162 (10) | −0.1533 (3) | 0.6481 (5) | 0.061 (2) | |
C12 | 0.1496 (9) | 0.1438 (4) | 0.4313 (5) | 0.058 (2) | |
C13 | 0.5026 (7) | 0.1622 (3) | 0.7926 (4) | 0.047 (2) | |
C14 | 0.4442 (9) | 0.1843 (4) | 0.8639 (5) | 0.061 (2) | |
C15 | 0.5330 (8) | 0.1750 (3) | 0.9339 (4) | 0.049 (2) | |
C16 | 0.6897 (8) | 0.1425 (3) | 0.9291 (4) | 0.047 (1) | |
C17 | 0.7441 (7) | 0.1218 (3) | 0.8554 (4) | 0.034 (1) | |
C18 | 0.9062 (7) | 0.0876 (3) | 0.8449 (4) | 0.034 (1) | |
C19 | 1.0224 (7) | 0.0738 (3) | 0.9065 (4) | 0.040 (1) | |
C20 | 1.1728 (7) | 0.0420 (3) | 0.8898 (4) | 0.044 (1) | |
C21 | 1.1951 (7) | 0.0243 (3) | 0.8114 (4) | 0.042 (1) | |
C22 | 1.0769 (8) | 0.0389 (3) | 0.7529 (4) | 0.042 (1) | |
C23 | 0.472 (1) | 0.1964 (5) | 1.0131 (6) | 0.078 (3) | |
C24 | 1.2991 (9) | 0.0245 (4) | 0.9547 (5) | 0.060 (2) | |
H1 | 0.7216 | −0.0347 | 0.7736 | 0.0412* | |
H2 | 0.5665 | −0.1259 | 0.7558 | 0.0503* | |
H3 | 0.2903 | −0.0412 | 0.5773 | 0.0403* | |
H4 | 0.2424 | 0.0449 | 0.5182 | 0.0401* | |
H5 | 0.3809 | 0.2245 | 0.4949 | 0.0506* | |
H6 | 0.5960 | 0.2075 | 0.5900 | 0.0482* | |
H7 | 0.3927 | −0.1858 | 0.6338 | 0.0608* | |
H8 | 0.2344 | −0.1477 | 0.6050 | 0.0608* | |
H9 | 0.2578 | −0.1650 | 0.6950 | 0.0608* | |
H10 | 0.1644 | 0.1165 | 0.3868 | 0.0585* | |
H11 | 0.0413 | 0.1371 | 0.4533 | 0.0585* | |
H12 | 0.1524 | 0.1858 | 0.4103 | 0.0585* | |
H13 | 0.4421 | 0.1714 | 0.7416 | 0.0473* | |
H14 | 0.3364 | 0.2060 | 0.8643 | 0.0611* | |
H15 | 0.7586 | 0.1373 | 0.9764 | 0.0470* | |
H16 | 1.0015 | 0.0874 | 0.9596 | 0.0400* | |
H17 | 1.2977 | 0.0007 | 0.7989 | 0.0424* | |
H18 | 1.0964 | 0.0271 | 0.6977 | 0.0424* | |
H19 | 0.3730 | 0.2164 | 1.0069 | 0.0782* | |
H20 | 0.5607 | 0.2221 | 1.0387 | 0.0782* | |
H21 | 0.4628 | 0.1601 | 1.0475 | 0.0782* | |
H22 | 1.2612 | 0.0406 | 1.0061 | 0.0604* | |
H23 | 1.4070 | 0.0422 | 0.9446 | 0.0604* | |
H24 | 1.3085 | −0.0189 | 0.9593 | 0.0604* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ir1 | 0.0286 (1) | 0.0367 (1) | 0.0303 (1) | −0.00082 (9) | −0.00345 (7) | −0.0027 (1) |
Cl1 | 0.59 (2) | 0.148 (5) | 0.253 (8) | 0.008 (7) | 0.168 (9) | 0.067 (5) |
Cl2 | 0.0390 (7) | 0.077 (1) | 0.0342 (7) | −0.0007 (8) | 0.0019 (6) | −0.0120 (7) |
P1 | 0.062 (1) | 0.0464 (10) | 0.0441 (10) | 0.0031 (8) | −0.0082 (8) | 0.0011 (8) |
F1 | 0.095 (4) | 0.182 (7) | 0.116 (5) | −0.053 (5) | −0.043 (4) | 0.036 (5) |
F2 | 0.121 (4) | 0.067 (3) | 0.054 (3) | −0.005 (3) | −0.013 (3) | 0.014 (2) |
F3 | 0.109 (5) | 0.149 (6) | 0.169 (8) | −0.067 (5) | −0.076 (5) | 0.075 (6) |
F4 | 0.110 (4) | 0.087 (3) | 0.053 (3) | 0.019 (3) | 0.005 (3) | 0.013 (2) |
F5 | 0.246 (10) | 0.076 (4) | 0.078 (4) | 0.066 (5) | 0.042 (5) | 0.007 (3) |
F6 | 0.194 (7) | 0.068 (4) | 0.110 (5) | 0.045 (4) | 0.057 (5) | 0.009 (3) |
N1 | 0.033 (2) | 0.045 (3) | 0.034 (2) | 0.000 (2) | 0.000 (2) | −0.001 (2) |
N2 | 0.036 (2) | 0.041 (2) | 0.034 (2) | 0.003 (2) | −0.005 (2) | −0.002 (2) |
N3 | 0.036 (2) | 0.039 (3) | 0.038 (3) | 0.001 (2) | −0.003 (2) | −0.003 (2) |
N4 | 0.023 (2) | 0.042 (3) | 0.034 (2) | 0.000 (2) | −0.002 (2) | −0.006 (2) |
C1 | 0.034 (3) | 0.047 (3) | 0.042 (3) | 0.001 (3) | −0.007 (2) | 0.004 (3) |
C2 | 0.051 (4) | 0.040 (3) | 0.060 (4) | 0.001 (3) | −0.001 (3) | 0.008 (3) |
C3 | 0.042 (3) | 0.040 (3) | 0.048 (4) | 0.000 (3) | 0.004 (3) | −0.006 (3) |
C4 | 0.036 (3) | 0.048 (3) | 0.036 (3) | 0.002 (3) | −0.002 (2) | −0.002 (3) |
C5 | 0.029 (2) | 0.040 (3) | 0.031 (3) | 0.007 (2) | 0.006 (2) | −0.002 (2) |
C6 | 0.029 (2) | 0.041 (3) | 0.031 (3) | 0.003 (2) | 0.000 (2) | −0.004 (2) |
C7 | 0.037 (3) | 0.047 (3) | 0.036 (3) | 0.002 (3) | −0.004 (2) | −0.007 (3) |
C8 | 0.038 (3) | 0.062 (4) | 0.033 (3) | 0.011 (3) | −0.007 (2) | −0.004 (3) |
C9 | 0.050 (3) | 0.053 (4) | 0.047 (4) | 0.010 (3) | −0.011 (3) | 0.010 (3) |
C10 | 0.058 (4) | 0.039 (3) | 0.046 (4) | −0.002 (3) | −0.016 (3) | 0.001 (3) |
C11 | 0.061 (4) | 0.045 (4) | 0.078 (5) | −0.014 (3) | 0.006 (4) | −0.004 (4) |
C12 | 0.049 (4) | 0.080 (5) | 0.046 (4) | 0.012 (4) | −0.014 (3) | 0.008 (4) |
C13 | 0.032 (3) | 0.050 (4) | 0.059 (4) | 0.010 (3) | −0.005 (3) | −0.010 (3) |
C14 | 0.046 (4) | 0.062 (5) | 0.076 (5) | 0.013 (3) | 0.012 (4) | −0.018 (4) |
C15 | 0.045 (3) | 0.045 (4) | 0.058 (4) | 0.008 (3) | 0.006 (3) | −0.013 (3) |
C16 | 0.046 (3) | 0.056 (4) | 0.039 (3) | 0.001 (3) | −0.002 (3) | −0.006 (3) |
C17 | 0.029 (2) | 0.035 (3) | 0.038 (3) | 0.001 (2) | 0.000 (2) | −0.005 (2) |
C18 | 0.036 (3) | 0.035 (3) | 0.032 (3) | 0.001 (2) | −0.001 (2) | −0.006 (2) |
C19 | 0.034 (3) | 0.051 (3) | 0.035 (3) | 0.000 (3) | −0.006 (2) | −0.002 (3) |
C20 | 0.034 (3) | 0.047 (3) | 0.050 (4) | 0.001 (3) | −0.010 (3) | 0.005 (3) |
C21 | 0.030 (2) | 0.052 (4) | 0.045 (3) | 0.008 (3) | −0.004 (2) | −0.002 (3) |
C22 | 0.037 (3) | 0.048 (3) | 0.042 (3) | 0.005 (3) | −0.002 (3) | −0.009 (3) |
C23 | 0.075 (5) | 0.099 (7) | 0.061 (5) | 0.016 (5) | 0.013 (4) | −0.024 (5) |
C24 | 0.049 (4) | 0.070 (5) | 0.062 (5) | 0.010 (4) | −0.022 (3) | 0.005 (4) |
Ir1—Cl1 | 2.360 (9) | C8—C12 | 1.505 (9) |
Ir1—Cl2 | 2.356 (2) | C9—C10 | 1.365 (10) |
Ir1—N1 | 2.131 (5) | C9—H5 | 0.970 |
Ir1—N2 | 2.036 (5) | C10—H6 | 0.956 |
Ir1—N3 | 2.015 (5) | C11—H7 | 0.956 |
Ir1—N4 | 2.024 (4) | C11—H8 | 0.957 |
P1—F1 | 1.538 (7) | C11—H9 | 0.949 |
P1—F2 | 1.610 (5) | C12—H10 | 0.957 |
P1—F3 | 1.561 (8) | C12—H11 | 0.943 |
P1—F4 | 1.577 (5) | C12—H12 | 0.973 |
P1—F5 | 1.558 (7) | C13—C14 | 1.37 (1) |
P1—F6 | 1.548 (7) | C13—H13 | 0.983 |
N1—C1 | 1.344 (8) | C14—C15 | 1.36 (1) |
N1—C5 | 1.341 (7) | C14—H14 | 0.964 |
N2—C6 | 1.371 (7) | C15—C16 | 1.416 (9) |
N2—C10 | 1.350 (8) | C15—C23 | 1.49 (1) |
N3—C13 | 1.344 (8) | C16—C17 | 1.385 (9) |
N3—C17 | 1.349 (8) | C16—H15 | 0.948 |
N4—C18 | 1.345 (8) | C17—C18 | 1.480 (8) |
N4—C22 | 1.351 (8) | C18—C19 | 1.385 (8) |
C1—C2 | 1.352 (9) | C19—C20 | 1.395 (9) |
C1—H1 | 0.967 | C19—H16 | 0.951 |
C2—C3 | 1.40 (1) | C20—C21 | 1.376 (9) |
C2—H2 | 0.971 | C20—C24 | 1.493 (10) |
C3—C4 | 1.387 (9) | C21—C22 | 1.363 (9) |
C3—C11 | 1.513 (10) | C21—H17 | 0.977 |
C4—C5 | 1.385 (8) | C22—H18 | 0.969 |
C4—H3 | 0.961 | C23—H19 | 0.893 |
C5—C6 | 1.479 (8) | C23—H20 | 0.974 |
C6—C7 | 1.383 (8) | C23—H21 | 0.976 |
C7—C8 | 1.382 (10) | C24—H22 | 0.976 |
C7—H4 | 0.954 | C24—H23 | 0.945 |
C8—C9 | 1.380 (10) | C24—H24 | 0.943 |
Cl2···C7i | 3.502 (6) | F4···C12v | 3.539 (9) |
F1···C23ii | 3.54 (1) | F5···C24iv | 3.45 (1) |
F2···C9iii | 3.208 (9) | F5···C19iv | 3.498 (9) |
F2···C10iii | 3.217 (8) | F6···C10iii | 3.327 (9) |
F2···C16iv | 3.397 (8) | F6···C13iii | 3.457 (9) |
F2···C19iv | 3.445 (8) | F6···C11i | 3.56 (1) |
F3···C16iv | 3.46 (1) | C4···C7v | 3.557 (9) |
F4···C11i | 3.32 (1) | ||
Cl1—Ir1—Cl2 | 89.5 (2) | C7—C8—C9 | 117.2 (6) |
Cl1—Ir1—N1 | 175.9 (3) | C7—C8—C12 | 120.3 (6) |
Cl1—Ir1—N2 | 101.7 (3) | C9—C8—C12 | 122.5 (6) |
Cl1—Ir1—N3 | 89.3 (3) | C8—C9—C10 | 120.3 (6) |
Cl1—Ir1—N4 | 82.6 (3) | C8—C9—H5 | 120.0 |
Cl2—Ir1—N1 | 86.4 (1) | C10—C9—H5 | 119.7 |
Cl2—Ir1—N2 | 86.1 (1) | N2—C10—C9 | 123.5 (6) |
Cl2—Ir1—N3 | 175.8 (1) | N2—C10—H6 | 117.5 |
Cl2—Ir1—N4 | 96.2 (1) | C9—C10—H6 | 119.0 |
N1—Ir1—N2 | 78.1 (2) | C3—C11—H7 | 110.2 |
N1—Ir1—N3 | 94.8 (2) | C3—C11—H8 | 109.8 |
N1—Ir1—N4 | 97.7 (2) | C3—C11—H9 | 110.4 |
N2—Ir1—N3 | 98.1 (2) | H7—C11—H8 | 108.4 |
N2—Ir1—N4 | 175.1 (2) | H7—C11—H9 | 109.1 |
N3—Ir1—N4 | 79.6 (2) | H8—C11—H9 | 109.0 |
F1—P1—F2 | 87.9 (4) | C8—C12—H10 | 110.7 |
F1—P1—F3 | 177.8 (5) | C8—C12—H11 | 111.7 |
F1—P1—F4 | 91.1 (4) | C8—C12—H12 | 109.5 |
F1—P1—F5 | 90.3 (5) | H10—C12—H11 | 109.5 |
F1—P1—F6 | 90.0 (4) | H10—C12—H12 | 107.1 |
F2—P1—F3 | 90.1 (4) | H11—C12—H12 | 108.2 |
F2—P1—F4 | 177.7 (3) | N3—C13—C14 | 122.7 (6) |
F2—P1—F5 | 89.9 (3) | N3—C13—H13 | 116.1 |
F2—P1—F6 | 89.9 (3) | C14—C13—H13 | 121.1 |
F3—P1—F4 | 90.8 (4) | C13—C14—C15 | 121.3 (7) |
F3—P1—F5 | 88.7 (5) | C13—C14—H14 | 119.1 |
F3—P1—F6 | 91.0 (4) | C15—C14—H14 | 119.6 |
F4—P1—F5 | 88.0 (3) | C14—C15—C16 | 116.7 (7) |
F4—P1—F6 | 92.2 (3) | C14—C15—C23 | 123.4 (7) |
F5—P1—F6 | 179.6 (4) | C16—C15—C23 | 119.9 (7) |
Ir1—N1—C1 | 126.4 (4) | C15—C16—C17 | 119.7 (6) |
Ir1—N1—C5 | 114.3 (4) | C15—C16—H15 | 119.1 |
C1—N1—C5 | 118.9 (5) | C17—C16—H15 | 121.2 |
Ir1—N2—C6 | 116.4 (4) | N3—C17—C16 | 121.9 (5) |
Ir1—N2—C10 | 126.9 (4) | N3—C17—C18 | 114.9 (5) |
C6—N2—C10 | 116.6 (5) | C16—C17—C18 | 123.2 (5) |
Ir1—N3—C13 | 126.6 (4) | N4—C18—C17 | 113.5 (5) |
Ir1—N3—C17 | 115.7 (4) | N4—C18—C19 | 121.9 (5) |
C13—N3—C17 | 117.8 (5) | C17—C18—C19 | 124.6 (5) |
Ir1—N4—C18 | 116.3 (4) | C18—C19—C20 | 119.9 (6) |
Ir1—N4—C22 | 125.6 (4) | C18—C19—H16 | 119.9 |
C18—N4—C22 | 118.1 (5) | C20—C19—H16 | 120.2 |
N1—C1—C2 | 122.6 (6) | C19—C20—C21 | 116.9 (6) |
N1—C1—H1 | 118.5 | C19—C20—C24 | 121.6 (6) |
C2—C1—H1 | 118.9 | C21—C20—C24 | 121.3 (6) |
C1—C2—C3 | 119.8 (6) | C20—C21—C22 | 121.0 (6) |
C1—C2—H2 | 121.6 | C20—C21—H17 | 118.1 |
C3—C2—H2 | 118.6 | C22—C21—H17 | 120.8 |
C2—C3—C4 | 117.3 (6) | N4—C22—C21 | 122.2 (6) |
C2—C3—C11 | 121.1 (6) | N4—C22—H18 | 118.0 |
C4—C3—C11 | 121.6 (6) | C21—C22—H18 | 119.8 |
C3—C4—C5 | 120.0 (5) | C15—C23—H19 | 110.0 |
C3—C4—H3 | 120.2 | C15—C23—H20 | 109.2 |
C5—C4—H3 | 119.8 | C15—C23—H21 | 107.6 |
N1—C5—C4 | 121.3 (5) | H19—C23—H20 | 112.3 |
N1—C5—C6 | 115.0 (5) | H19—C23—H21 | 112.2 |
C4—C5—C6 | 123.7 (5) | H20—C23—H21 | 105.4 |
N2—C6—C5 | 115.1 (5) | C20—C24—H22 | 109.6 |
N2—C6—C7 | 121.5 (5) | C20—C24—H23 | 110.1 |
C5—C6—C7 | 123.4 (5) | C20—C24—H24 | 111.0 |
C6—C7—C8 | 120.8 (6) | H22—C24—H23 | 107.7 |
C6—C7—H4 | 118.4 | H22—C24—H24 | 107.8 |
C8—C7—H4 | 120.7 | H23—C24—H24 | 110.5 |
Ir1—N1—C1—C2 | −172.6 (5) | C2—C3—C11—H7 | −60.5 |
Ir1—N1—C1—H1 | 9.7 | C2—C3—C11—H8 | −179.8 |
Ir1—N1—C5—C4 | 171.8 (4) | C2—C3—C11—H9 | 60.1 |
Ir1—N1—C5—C6 | −7.8 (6) | C3—C2—C1—H1 | −180.0 |
Ir1—N2—C6—C5 | 7.2 (6) | C3—C4—C5—C6 | −179.7 (6) |
Ir1—N2—C6—C7 | −174.3 (4) | C4—C3—C2—H2 | 177.8 |
Ir1—N2—C10—C9 | 175.3 (5) | C4—C3—C11—H7 | 120.5 |
Ir1—N2—C10—H6 | −5.8 | C4—C3—C11—H8 | 1.2 |
Ir1—N3—C13—C14 | 180.0 (5) | C4—C3—C11—H9 | −118.9 |
Ir1—N3—C13—H13 | −5.4 | C4—C5—C6—C7 | 2.6 (9) |
Ir1—N3—C17—C16 | −179.1 (5) | C5—N1—C1—H1 | −177.0 |
Ir1—N3—C17—C18 | 0.5 (6) | C5—C4—C3—C11 | −178.8 (6) |
Ir1—N4—C18—C17 | 1.7 (6) | C5—C6—N2—C10 | −175.4 (5) |
Ir1—N4—C18—C19 | −178.5 (4) | C5—C6—C7—C8 | 177.2 (6) |
Ir1—N4—C22—C21 | 178.2 (5) | C5—C6—C7—H4 | 0.1 |
Ir1—N4—C22—H18 | −1.1 | C6—N2—C10—C9 | −1.7 (9) |
Cl1—Ir1—N1—C1 | 93 (3) | C6—N2—C10—H6 | 177.1 |
Cl1—Ir1—N1—C5 | −79 (3) | C6—C5—C4—H3 | 0.5 |
Cl1—Ir1—N2—C6 | 167.2 (4) | C6—C7—C8—C9 | −2.0 (9) |
Cl1—Ir1—N2—C10 | −9.8 (6) | C6—C7—C8—C12 | −179.2 (6) |
Cl1—Ir1—N3—C13 | 98.2 (6) | C7—C6—N2—C10 | 3.1 (8) |
Cl1—Ir1—N3—C17 | −82.3 (5) | C7—C8—C9—C10 | 3.4 (10) |
Cl1—Ir1—N4—C18 | 89.4 (5) | C7—C8—C9—H5 | −178.1 |
Cl1—Ir1—N4—C22 | −88.4 (5) | C7—C8—C12—H10 | −60.3 |
Cl2—Ir1—N1—C1 | 95.7 (5) | C7—C8—C12—H11 | 62.0 |
Cl2—Ir1—N1—C5 | −77.9 (4) | C7—C8—C12—H12 | −178.2 |
Cl2—Ir1—N2—C6 | 78.5 (4) | C8—C9—C10—H6 | 179.6 |
Cl2—Ir1—N2—C10 | −98.5 (5) | C9—C8—C7—H4 | 175.0 |
Cl2—Ir1—N3—C13 | 171 (1) | C9—C8—C12—H10 | 122.6 |
Cl2—Ir1—N3—C17 | −9 (2) | C9—C8—C12—H11 | −115.0 |
Cl2—Ir1—N4—C18 | 178.1 (4) | C9—C8—C12—H12 | 4.8 |
Cl2—Ir1—N4—C22 | 0.3 (5) | C10—C9—C8—C12 | −179.5 (6) |
N1—Ir1—N2—C6 | −8.6 (4) | C11—C3—C2—H2 | −1.2 |
N1—Ir1—N2—C10 | 174.4 (6) | C11—C3—C4—H3 | 1.0 |
N1—Ir1—N3—C13 | −82.2 (5) | C12—C8—C7—H4 | −2.2 |
N1—Ir1—N3—C17 | 97.3 (4) | C12—C8—C9—H5 | −0.9 |
N1—Ir1—N4—C18 | −94.7 (4) | C13—N3—C17—C16 | 0.4 (9) |
N1—Ir1—N4—C22 | 87.5 (5) | C13—N3—C17—C18 | −180.0 (5) |
N1—C1—C2—C3 | 2 (1) | C13—C14—C15—C16 | 1 (1) |
N1—C1—C2—H2 | −179.2 | C13—C14—C15—C23 | −178.1 (7) |
N1—C5—C4—C3 | 0.8 (9) | C14—C13—N3—C17 | 0.5 (9) |
N1—C5—C4—H3 | −179.0 | C14—C15—C16—C17 | −0.2 (10) |
N1—C5—C6—N2 | 0.7 (7) | C14—C15—C16—H15 | 176.3 |
N1—C5—C6—C7 | −177.8 (5) | C14—C15—C23—H19 | −1.3 |
N2—Ir1—N1—C1 | −177.5 (5) | C14—C15—C23—H20 | −125.0 |
N2—Ir1—N1—C5 | 8.9 (4) | C14—C15—C23—H21 | 121.1 |
N2—Ir1—N3—C13 | −3.5 (5) | C15—C14—C13—H13 | −175.7 |
N2—Ir1—N3—C17 | 176.0 (4) | C15—C16—C17—C18 | 179.9 (6) |
N2—Ir1—N4—C18 | −63 (2) | C16—C15—C14—H14 | 179.6 |
N2—Ir1—N4—C22 | 118 (2) | C16—C15—C23—H19 | 179.5 |
N2—C6—C5—C4 | −178.9 (5) | C16—C15—C23—H20 | 55.8 |
N2—C6—C7—C8 | −1.2 (9) | C16—C15—C23—H21 | −58.0 |
N2—C6—C7—H4 | −178.3 | C16—C17—C18—C19 | −1.6 (9) |
N2—C10—C9—C8 | −1 (1) | C17—N3—C13—H13 | 175.2 |
N2—C10—C9—H5 | 179.9 | C17—C16—C15—C23 | 179.0 (7) |
N3—Ir1—N1—C1 | −80.2 (5) | C17—C18—N4—C22 | 179.7 (5) |
N3—Ir1—N1—C5 | 106.2 (4) | C17—C18—C19—C20 | −179.0 (6) |
N3—Ir1—N2—C6 | −101.8 (4) | C17—C18—C19—H16 | −1.5 |
N3—Ir1—N2—C10 | 81.1 (5) | C18—N4—C22—C21 | 0.4 (9) |
N3—Ir1—N4—C18 | −1.2 (4) | C18—N4—C22—H18 | −178.9 |
N3—Ir1—N4—C22 | −179.0 (5) | C18—C17—C16—H15 | 3.4 |
N3—C13—C14—C15 | −1 (1) | C18—C19—C20—C21 | −1.7 (9) |
N3—C13—C14—H14 | −179.8 | C18—C19—C20—C24 | −178.1 (6) |
N3—C17—C16—C15 | −0.5 (10) | C19—C18—N4—C22 | −0.5 (8) |
N3—C17—C16—H15 | −177.0 | C19—C20—C21—C22 | 1.6 (10) |
N3—C17—C18—N4 | −1.4 (7) | C19—C20—C21—H17 | −177.9 |
N3—C17—C18—C19 | 178.8 (6) | C19—C20—C24—H22 | −3.0 |
N4—Ir1—N1—C1 | −0.1 (5) | C19—C20—C24—H23 | −121.2 |
N4—Ir1—N1—C5 | −173.7 (4) | C19—C20—C24—H24 | 116.0 |
N4—Ir1—N2—C6 | −40 (2) | C20—C21—C22—H18 | 178.3 |
N4—Ir1—N2—C10 | 142 (2) | C21—C20—C19—H16 | −179.3 |
N4—Ir1—N3—C13 | −179.2 (5) | C21—C20—C24—H22 | −179.3 |
N4—Ir1—N3—C17 | 0.3 (4) | C21—C20—C24—H23 | 62.5 |
N4—C18—C17—C16 | 178.2 (6) | C21—C20—C24—H24 | −60.3 |
N4—C18—C19—C20 | 1.2 (9) | C22—C21—C20—C24 | 178.1 (6) |
N4—C18—C19—H16 | 178.8 | C23—C15—C14—H14 | 0.4 |
N4—C22—C21—C20 | −1.1 (10) | C23—C15—C16—H15 | −4.5 |
N4—C22—C21—H17 | 178.5 | C24—C20—C19—H16 | 4.3 |
C1—N1—C5—C4 | −2.2 (8) | C24—C20—C21—H17 | −1.4 |
C1—N1—C5—C6 | 178.1 (5) | H1—C1—C2—H2 | −1.5 |
C1—C2—C3—C4 | −3 (1) | H5—C9—C10—H6 | 1.0 |
C1—C2—C3—C11 | 177.3 (7) | H13—C13—C14—H14 | 5.8 |
C2—C1—N1—C5 | 0.7 (9) | H17—C21—C22—H18 | −2.2 |
C2—C3—C4—C5 | 2.2 (9) | H17—C21—C22—H18 | −2.2 |
C2—C3—C4—H3 | −178.0 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z+2; (iii) −x+3/2, y−1/2, −z+3/2; (iv) −x+2, −y, −z+2; (v) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [IrCl2(C24H24N4)2]PF6 |
Mr | 776.57 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 7.8114 (2), 21.6075 (7), 16.6606 (5) |
β (°) | 91.4634 (7) |
V (Å3) | 2811.1 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.07 |
Crystal size (mm) | 0.80 × 0.10 × 0.02 |
Data collection | |
Diffractometer | Rigaku RAXIS-RAPID imaging plate diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.552, 0.904 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32401, 8462, 6274 |
Rint | 0.068 |
(sin θ/λ)max (Å−1) | 0.714 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.126, 1.41 |
No. of reflections | 6274 |
No. of parameters | 343 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 2.81, −2.53 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), TEXSAN.
Ir1—Cl1 | 2.360 (9) | Ir1—N2 | 2.036 (5) |
Ir1—Cl2 | 2.356 (2) | Ir1—N3 | 2.015 (5) |
Ir1—N1 | 2.131 (5) | Ir1—N4 | 2.024 (4) |
Cl1—Ir1—Cl2 | 89.5 (2) | Cl2—Ir1—N4 | 96.2 (1) |
Cl1—Ir1—N1 | 175.9 (3) | N1—Ir1—N2 | 78.1 (2) |
Cl1—Ir1—N2 | 101.7 (3) | N1—Ir1—N3 | 94.8 (2) |
Cl1—Ir1—N3 | 89.3 (3) | N1—Ir1—N4 | 97.7 (2) |
Cl1—Ir1—N4 | 82.6 (3) | N2—Ir1—N3 | 98.1 (2) |
Cl2—Ir1—N1 | 86.4 (1) | N2—Ir1—N4 | 175.1 (2) |
Cl2—Ir1—N2 | 86.1 (1) | N3—Ir1—N4 | 79.6 (2) |
Cl2—Ir1—N3 | 175.8 (1) |
Transition metals in particular iridium polypyridine complexes have received much interest on account of their intense emission properties. Theses iridium complexes exhibit a very intense emission at around 532 nm, originating from 3LC (ligand-centered charge transfer) state in acetonitrile solution even at room temperature. Recent research in this area has been focused on trials to replace bipyridine ligands with other polypyridine ligands. However, the difficulties of the synthesis precluded further work along these lines. To our knowledge, no structure of an iridium complex with the 4,4'-dimethyl-2,2'-bipyridine ligand (dmbpy) has been reported previously.
In this paper, we report the synthesis and crystal structure of a mononuclear iridium compound, viz. [IrCl2(dmbpy)2]PF6, (I),whose crystal structure consists of a discrete [IrCl2(dmbpy)2]+ cation and a hexafluorophosphate anion. As illustrated in Fig. 1, the IrIII atom is located in a distorted octahedral environment by two dmbpy ligands and two chloride anions. The Ir—N bond lengths are in the range 2.015 (5)–2.131 (5) Å. Three trans angles are in the range 175.1 (2)–175.9 (3) Å. It is coordinated by four N atoms from a pair of cis-related chelating dmbpy ligands and two Cl atoms [Ir—Cl1 2.360 (9) Å and Ir—Cl2 2.356 (2) Å]. The equatorial plane is formed by atoms Cl1, N1, N2 and N4, with the largest deviation from the mean plane being 0.035 (4) Å and the Ir atom being 0.013 (3) Å out of this plane. The axial positions are occupied by the fourth dmbpy N atom and another Cl atom. Atom Cl1 has a particularly high anisotropic displacement coefficients, probably indicative of some disorder. Each dmbpy ligand is planar, the mean deviation from the best planes is 0.024 (6) Å. The dihedral angle between dmbpy planes is 79.7 (1) Å. The two Cl ligands were coordinated in a cis fasion, but PF6- was not coordinated to the iridium metal atom. The average length of the Ir—N bonds is 2.052 (5) Å and the average of the N1—Ir—N2 and N3—Ir—N4 ligand angles is 78.9 (2)°, which compare well with the values published for Ir(bpy)3(ClO4)3 (bpy = 2,2'-bipyridine; Hazell & Gronbaek Hazell, 1984) of 2.026 Å and 79.1°. No hydrogen-bond interactions exist in the crystal packing.