Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801008704/tk6026sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801008704/tk6026Isup2.hkl |
CCDC reference: 170740
The N,N'-bis(2,6-diisopropylphenyl)-1,2-ethanediimine ligand (L) was prepared by a modification of a published procedure (tom Dieck & Dietrich, 1984). Methanoic acid (88%, 0.5 ml, 11.5 mmol) and an aqueous solution of glyoxal (40%, 4.6 ml, 39.0 mmol) were successively added to a vigorously stirred suspension of 2,6-diisopropylaniline (14.9 ml, 79 mmol) and freshly dehydrated sodium sulfate (25 g) in CH2Cl2 (100 ml). After 5 min, a further amount of sodium sulfate (25 g) was added, and the reaction mixture was stirred at room temperature for 1 d. The mixture was filtered and the solid extracted with CH2Cl2 (3 x15 ml). The combined organic material was evaporated in vacuo, and the residue recrystallized from ethanol at 293 K; yield 10.3 g, 70%, m.p.376 K.
Dichloro(N,N'-bis(2,6-diisopropylphenyl)-1,2-ethanediimine-N,N')palladium, (I) was prepared by a modification of a published procedure (van der Poel et al., 1980). To a stirred solution of PdCl2(PhCN)2 (0.41 g, 1.07 mmol) (Anderson & Lin, 1990) in CH2Cl2 (50 ml) was added L (0.46 g, 1.22 mmol) at room temperature. After 2 h the reaction mixture was concentrated under vacuo to 5 ml and hexane (15 ml) added to complete the precipitation of the the title compound. This was washed with hexane (3 x 10 ml) and dried in vacuo, yield 0.54 g, 98%, m.p. 551 K (dec). Suitable crystals were obtained from acetone solution. Analysis: Found: C, 56.06, H, 6.85; N, 5.19. Calculated for C26H36Cl2N2Pd: C, 56.64; H, 6.56; N, 5.06%. 1H NMR (200 MHz, CD2Cl2): δ: 1.23(d, 12H, J 6.8 Hz, Me), 1.45(d, 12H, J 6.8 Hz, Me), 3.25(sept, 4H, J 6.8 Hz, Me2CH), 7.27–7.48(m 6H, aryl), 8.15(s, 2H, CH=N).
In the final stages of the refinement one reflection, -2 0 1, showing particularly poor agreement was suppressed. The H atoms were introduced in calculated positions with C—H and Uiso 0.95 Å and 1.2 times Ueq of the non-H to which they are attached (1.00 Å for tertiary C—H and for methyl H 0.98 Å and 1.5 times Ueq).
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecule of 1 showing the atom labels (Farrugia, 1997). Non-H are shown as 50% ellipsoids and H as open circles. |
C26H36Cl2N2Pd | F(000) = 1144 |
Mr = 553.87 | Dx = 1.341 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71073 Å |
a = 13.7198 (1) Å | Cell parameters from 26074 reflections |
b = 15.3812 (2) Å | θ = 2.9–27.5° |
c = 13.8702 (2) Å | µ = 0.89 mm−1 |
β = 110.3873 (5)° | T = 150 K |
V = 2743.64 (6) Å3 | Block, orange |
Z = 4 | 0.30 × 0.20 × 0.20 mm |
Enraf Nonius Kappa CCD area detector diffractometer | 6279 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 5446 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ and ω scans to fill the Ewald sphere | h = −17→17 |
Absorption correction: multi-scan SORTAV (Blessing, 1995, 1997) | k = −19→19 |
Tmin = 0.673, Tmax = 0.767 | l = −17→18 |
42903 measured reflections |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0398P)2 + 0.8819P] where P = (Fo2 + 2Fc2)/3 |
6279 reflections | (Δ/σ)max = 0.001 |
288 parameters | Δρmax = 0.78 e Å−3 |
0 restraints | Δρmin = −0.90 e Å−3 |
C26H36Cl2N2Pd | V = 2743.64 (6) Å3 |
Mr = 553.87 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 13.7198 (1) Å | µ = 0.89 mm−1 |
b = 15.3812 (2) Å | T = 150 K |
c = 13.8702 (2) Å | 0.30 × 0.20 × 0.20 mm |
β = 110.3873 (5)° |
Enraf Nonius Kappa CCD area detector diffractometer | 6279 independent reflections |
Absorption correction: multi-scan SORTAV (Blessing, 1995, 1997) | 5446 reflections with I > 2σ(I) |
Tmin = 0.673, Tmax = 0.767 | Rint = 0.064 |
42903 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.78 e Å−3 |
6279 reflections | Δρmin = −0.90 e Å−3 |
288 parameters |
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. H in calculated positions and refined with a riding model. One reflection, -2 0 1, showing particularly bad agreement omitted. |
x | y | z | Uiso*/Ueq | ||
Pd | 0.612176 (9) | 0.225029 (8) | 0.290130 (10) | 0.01836 (6) | |
Cl1 | 0.77240 (4) | 0.28007 (3) | 0.38150 (4) | 0.02746 (11) | |
Cl2 | 0.68248 (3) | 0.11819 (3) | 0.22089 (4) | 0.02953 (11) | |
N1 | 0.53593 (11) | 0.31897 (9) | 0.33622 (11) | 0.0206 (3) | |
N2 | 0.46306 (11) | 0.18643 (10) | 0.21974 (11) | 0.0205 (3) | |
C1 | 0.43682 (14) | 0.31157 (12) | 0.30210 (14) | 0.0225 (4) | |
H1 | 0.3929 | 0.3523 | 0.3186 | 0.027* | |
C2 | 0.39570 (14) | 0.23646 (12) | 0.23614 (15) | 0.0227 (4) | |
H2 | 0.3232 | 0.2253 | 0.2070 | 0.027* | |
C3 | 0.58259 (13) | 0.39569 (11) | 0.39318 (14) | 0.0214 (4) | |
C4 | 0.62921 (14) | 0.38883 (12) | 0.49982 (14) | 0.0240 (4) | |
C5 | 0.67100 (15) | 0.46461 (13) | 0.55253 (16) | 0.0299 (4) | |
H5 | 0.7003 | 0.4637 | 0.6255 | 0.036* | |
C6 | 0.67074 (16) | 0.54114 (13) | 0.50074 (17) | 0.0341 (5) | |
H6 | 0.7001 | 0.5921 | 0.5384 | 0.041* | |
C7 | 0.62821 (16) | 0.54458 (13) | 0.39465 (17) | 0.0320 (5) | |
H7 | 0.6306 | 0.5975 | 0.3602 | 0.038* | |
C8 | 0.58203 (14) | 0.47178 (12) | 0.33766 (15) | 0.0260 (4) | |
C9 | 0.63350 (15) | 0.30219 (13) | 0.55356 (15) | 0.0273 (4) | |
H9 | 0.6288 | 0.2558 | 0.5016 | 0.033* | |
C10 | 0.5410 (2) | 0.28990 (17) | 0.5888 (2) | 0.0477 (6) | |
H10A | 0.5428 | 0.3344 | 0.6399 | 0.071* | |
H10B | 0.5445 | 0.2321 | 0.6196 | 0.071* | |
H10C | 0.4764 | 0.2953 | 0.5297 | 0.071* | |
C11 | 0.73590 (19) | 0.28819 (16) | 0.64243 (19) | 0.0448 (6) | |
H11A | 0.7940 | 0.2942 | 0.6173 | 0.067* | |
H11B | 0.7367 | 0.2298 | 0.6710 | 0.067* | |
H11C | 0.7426 | 0.3316 | 0.6961 | 0.067* | |
C12 | 0.53502 (16) | 0.47515 (14) | 0.22028 (16) | 0.0329 (5) | |
H12 | 0.5192 | 0.4140 | 0.1953 | 0.039* | |
C13 | 0.4337 (2) | 0.5247 (2) | 0.1841 (2) | 0.0652 (8) | |
H13A | 0.4469 | 0.5859 | 0.2043 | 0.098* | |
H13B | 0.3862 | 0.4998 | 0.2155 | 0.098* | |
H13C | 0.4024 | 0.5207 | 0.1091 | 0.098* | |
C14 | 0.6102 (2) | 0.5121 (2) | 0.1719 (2) | 0.0657 (9) | |
H14A | 0.5771 | 0.5121 | 0.0968 | 0.099* | |
H14B | 0.6731 | 0.4763 | 0.1916 | 0.099* | |
H14C | 0.6287 | 0.5718 | 0.1961 | 0.099* | |
C15 | 0.42556 (13) | 0.11318 (12) | 0.15163 (14) | 0.0224 (4) | |
C16 | 0.42388 (15) | 0.03194 (13) | 0.19458 (15) | 0.0261 (4) | |
C17 | 0.38161 (17) | −0.03591 (14) | 0.12665 (17) | 0.0342 (5) | |
H17 | 0.3766 | −0.0921 | 0.1530 | 0.041* | |
C18 | 0.34683 (18) | −0.02313 (15) | 0.02186 (17) | 0.0402 (5) | |
H18 | 0.3179 | −0.0704 | −0.0231 | 0.048* | |
C19 | 0.35369 (17) | 0.05750 (15) | −0.01823 (16) | 0.0369 (5) | |
H19 | 0.3311 | 0.0648 | −0.0907 | 0.044* | |
C20 | 0.39305 (15) | 0.12845 (13) | 0.04545 (15) | 0.0281 (4) | |
C21 | 0.46761 (16) | 0.01495 (13) | 0.30958 (15) | 0.0299 (4) | |
H21 | 0.5003 | 0.0700 | 0.3443 | 0.036* | |
C22 | 0.38379 (18) | −0.01118 (16) | 0.35314 (18) | 0.0406 (5) | |
H22A | 0.3335 | 0.0363 | 0.3427 | 0.061* | |
H22B | 0.4161 | −0.0231 | 0.4269 | 0.061* | |
H22C | 0.3480 | −0.0635 | 0.3178 | 0.061* | |
C23 | 0.55257 (17) | −0.05454 (16) | 0.33385 (18) | 0.0407 (5) | |
H23A | 0.5217 | −0.1103 | 0.3045 | 0.061* | |
H23B | 0.5857 | −0.0604 | 0.4086 | 0.061* | |
H23C | 0.6048 | −0.0375 | 0.3040 | 0.061* | |
C24 | 0.3999 (2) | 0.21771 (14) | 0.00139 (17) | 0.0367 (5) | |
H24 | 0.4397 | 0.2565 | 0.0597 | 0.044* | |
C25 | 0.2920 (3) | 0.2568 (2) | −0.0492 (3) | 0.0636 (8) | |
H25A | 0.2985 | 0.3155 | −0.0740 | 0.095* | |
H25B | 0.2566 | 0.2598 | 0.0010 | 0.095* | |
H25C | 0.2516 | 0.2203 | −0.1073 | 0.095* | |
C26 | 0.4583 (2) | 0.21448 (18) | −0.0742 (2) | 0.0518 (7) | |
H26A | 0.5283 | 0.1911 | −0.0395 | 0.078* | |
H26B | 0.4635 | 0.2733 | −0.0993 | 0.078* | |
H26C | 0.4207 | 0.1770 | −0.1324 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd | 0.01454 (9) | 0.01930 (9) | 0.02050 (9) | 0.00002 (4) | 0.00517 (6) | −0.00211 (5) |
Cl1 | 0.0162 (2) | 0.0299 (3) | 0.0344 (3) | −0.00308 (16) | 0.00648 (18) | −0.00687 (19) |
Cl2 | 0.0217 (2) | 0.0316 (3) | 0.0355 (3) | 0.00201 (18) | 0.01033 (19) | −0.0109 (2) |
N1 | 0.0208 (7) | 0.0187 (8) | 0.0212 (8) | −0.0005 (6) | 0.0062 (6) | −0.0008 (6) |
N2 | 0.0197 (7) | 0.0209 (8) | 0.0198 (7) | −0.0011 (6) | 0.0055 (6) | −0.0016 (6) |
C1 | 0.0204 (9) | 0.0213 (9) | 0.0256 (9) | 0.0001 (7) | 0.0078 (7) | −0.0024 (7) |
C2 | 0.0171 (9) | 0.0275 (10) | 0.0231 (9) | −0.0030 (7) | 0.0065 (7) | −0.0021 (8) |
C3 | 0.0170 (8) | 0.0195 (9) | 0.0269 (9) | 0.0004 (6) | 0.0066 (7) | −0.0047 (7) |
C4 | 0.0196 (9) | 0.0246 (9) | 0.0261 (10) | 0.0017 (7) | 0.0056 (7) | −0.0023 (8) |
C5 | 0.0276 (10) | 0.0291 (10) | 0.0271 (10) | 0.0009 (8) | 0.0020 (8) | −0.0083 (8) |
C6 | 0.0287 (10) | 0.0237 (10) | 0.0432 (13) | −0.0034 (8) | 0.0039 (9) | −0.0119 (9) |
C7 | 0.0313 (11) | 0.0195 (9) | 0.0417 (12) | −0.0014 (8) | 0.0083 (9) | 0.0003 (8) |
C8 | 0.0225 (9) | 0.0231 (9) | 0.0304 (10) | 0.0002 (7) | 0.0066 (8) | 0.0001 (8) |
C9 | 0.0275 (10) | 0.0271 (10) | 0.0248 (10) | 0.0003 (8) | 0.0059 (8) | −0.0016 (8) |
C10 | 0.0429 (14) | 0.0492 (15) | 0.0579 (16) | 0.0027 (11) | 0.0264 (13) | 0.0133 (12) |
C11 | 0.0409 (14) | 0.0429 (13) | 0.0395 (14) | −0.0001 (10) | 0.0002 (11) | 0.0107 (10) |
C12 | 0.0355 (11) | 0.0316 (11) | 0.0284 (11) | −0.0040 (8) | 0.0071 (9) | 0.0034 (9) |
C13 | 0.0470 (16) | 0.097 (2) | 0.0394 (15) | 0.0215 (15) | −0.0005 (12) | 0.0078 (15) |
C14 | 0.0515 (17) | 0.103 (3) | 0.0402 (15) | −0.0163 (16) | 0.0134 (12) | 0.0181 (16) |
C15 | 0.0164 (8) | 0.0231 (9) | 0.0243 (9) | −0.0011 (7) | 0.0028 (7) | −0.0063 (7) |
C16 | 0.0233 (9) | 0.0249 (10) | 0.0273 (10) | −0.0016 (7) | 0.0051 (8) | −0.0041 (8) |
C17 | 0.0374 (12) | 0.0231 (10) | 0.0371 (12) | −0.0047 (8) | 0.0065 (9) | −0.0062 (9) |
C18 | 0.0432 (13) | 0.0340 (12) | 0.0360 (12) | −0.0035 (10) | 0.0042 (10) | −0.0168 (10) |
C19 | 0.0405 (12) | 0.0391 (12) | 0.0235 (10) | 0.0029 (9) | 0.0015 (9) | −0.0091 (9) |
C20 | 0.0270 (10) | 0.0303 (10) | 0.0231 (10) | 0.0033 (8) | 0.0038 (8) | −0.0021 (8) |
C21 | 0.0331 (11) | 0.0244 (10) | 0.0280 (10) | −0.0040 (8) | 0.0052 (8) | 0.0008 (8) |
C22 | 0.0392 (13) | 0.0456 (14) | 0.0384 (13) | 0.0029 (10) | 0.0152 (10) | 0.0018 (11) |
C23 | 0.0317 (12) | 0.0469 (13) | 0.0405 (13) | 0.0044 (10) | 0.0090 (9) | 0.0118 (11) |
C24 | 0.0508 (14) | 0.0325 (12) | 0.0246 (11) | 0.0058 (9) | 0.0102 (10) | 0.0029 (9) |
C25 | 0.067 (2) | 0.0621 (17) | 0.069 (2) | 0.0348 (15) | 0.0334 (16) | 0.0289 (16) |
C26 | 0.0567 (17) | 0.0558 (16) | 0.0497 (16) | 0.0100 (12) | 0.0269 (13) | 0.0116 (12) |
Pd—N1 | 2.0142 (15) | C13—H13B | 0.9800 |
Pd—N2 | 2.0248 (14) | C13—H13C | 0.9800 |
Pd—Cl2 | 2.2799 (5) | C14—H14A | 0.9800 |
Pd—Cl1 | 2.2834 (5) | C14—H14B | 0.9800 |
N1—C1 | 1.280 (2) | C14—H14C | 0.9800 |
N1—C3 | 1.440 (2) | C15—C16 | 1.388 (3) |
N2—C2 | 1.282 (2) | C15—C20 | 1.402 (3) |
N2—C15 | 1.445 (2) | C16—C17 | 1.390 (3) |
C1—C2 | 1.460 (3) | C16—C21 | 1.518 (3) |
C1—H1 | 0.9500 | C17—C18 | 1.377 (3) |
C2—H2 | 0.9500 | C17—H17 | 0.9500 |
C3—C4 | 1.396 (3) | C18—C19 | 1.376 (3) |
C3—C8 | 1.400 (3) | C18—H18 | 0.9500 |
C4—C5 | 1.389 (3) | C19—C20 | 1.389 (3) |
C4—C9 | 1.518 (3) | C19—H19 | 0.9500 |
C5—C6 | 1.378 (3) | C20—C24 | 1.519 (3) |
C5—H5 | 0.9500 | C21—C22 | 1.527 (3) |
C6—C7 | 1.382 (3) | C21—C23 | 1.530 (3) |
C6—H6 | 0.9500 | C21—H21 | 1.0000 |
C7—C8 | 1.390 (3) | C22—H22A | 0.9800 |
C7—H7 | 0.9500 | C22—H22B | 0.9800 |
C8—C12 | 1.529 (3) | C22—H22C | 0.9800 |
C9—C10 | 1.522 (3) | C23—H23A | 0.9800 |
C9—C11 | 1.527 (3) | C23—H23B | 0.9800 |
C9—H9 | 1.0000 | C23—H23C | 0.9800 |
C10—H10A | 0.9800 | C24—C25 | 1.524 (4) |
C10—H10B | 0.9800 | C24—C26 | 1.526 (3) |
C10—H10C | 0.9800 | C24—H24 | 1.0000 |
C11—H11A | 0.9800 | C25—H25A | 0.9800 |
C11—H11B | 0.9800 | C25—H25B | 0.9800 |
C11—H11C | 0.9800 | C25—H25C | 0.9800 |
C12—C13 | 1.510 (3) | C26—H26A | 0.9800 |
C12—C14 | 1.523 (3) | C26—H26B | 0.9800 |
C12—H12 | 1.0000 | C26—H26C | 0.9800 |
C13—H13A | 0.9800 | ||
N1—Pd—N2 | 79.29 (6) | C12—C13—H13C | 109.5 |
N1—Pd—Cl2 | 173.44 (4) | H13A—C13—H13C | 109.5 |
N2—Pd—Cl2 | 95.17 (4) | H13B—C13—H13C | 109.5 |
N1—Pd—Cl1 | 93.66 (4) | C12—C14—H14A | 109.5 |
N2—Pd—Cl1 | 172.75 (4) | C12—C14—H14B | 109.5 |
Cl2—Pd—Cl1 | 91.963 (17) | H14A—C14—H14B | 109.5 |
C1—N1—C3 | 119.19 (15) | C12—C14—H14C | 109.5 |
C1—N1—Pd | 114.91 (12) | H14A—C14—H14C | 109.5 |
C3—N1—Pd | 125.54 (11) | H14B—C14—H14C | 109.5 |
C2—N2—C15 | 118.00 (15) | C16—C15—C20 | 123.71 (17) |
C2—N2—Pd | 114.08 (12) | C16—C15—N2 | 118.47 (16) |
C15—N2—Pd | 127.86 (11) | C20—C15—N2 | 117.82 (16) |
N1—C1—C2 | 115.54 (16) | C15—C16—C17 | 116.76 (18) |
N1—C1—H1 | 122.2 | C15—C16—C21 | 123.11 (17) |
C2—C1—H1 | 122.2 | C17—C16—C21 | 120.11 (18) |
N2—C2—C1 | 116.18 (16) | C18—C17—C16 | 121.2 (2) |
N2—C2—H2 | 121.9 | C18—C17—H17 | 119.4 |
C1—C2—H2 | 121.9 | C16—C17—H17 | 119.4 |
C4—C3—C8 | 123.98 (17) | C19—C18—C17 | 120.5 (2) |
C4—C3—N1 | 118.12 (16) | C19—C18—H18 | 119.7 |
C8—C3—N1 | 117.85 (16) | C17—C18—H18 | 119.7 |
C5—C4—C3 | 116.55 (18) | C18—C19—C20 | 121.2 (2) |
C5—C4—C9 | 122.68 (17) | C18—C19—H19 | 119.4 |
C3—C4—C9 | 120.77 (17) | C20—C19—H19 | 119.4 |
C6—C5—C4 | 121.10 (19) | C19—C20—C15 | 116.56 (19) |
C6—C5—H5 | 119.4 | C19—C20—C24 | 121.27 (18) |
C4—C5—H5 | 119.4 | C15—C20—C24 | 122.17 (18) |
C5—C6—C7 | 120.73 (19) | C16—C21—C22 | 112.61 (17) |
C5—C6—H6 | 119.6 | C16—C21—C23 | 110.07 (17) |
C7—C6—H6 | 119.6 | C22—C21—C23 | 110.49 (17) |
C6—C7—C8 | 120.96 (19) | C16—C21—H21 | 107.8 |
C6—C7—H7 | 119.5 | C22—C21—H21 | 107.8 |
C8—C7—H7 | 119.5 | C23—C21—H21 | 107.8 |
C7—C8—C3 | 116.54 (18) | C21—C22—H22A | 109.5 |
C7—C8—C12 | 121.19 (18) | C21—C22—H22B | 109.5 |
C3—C8—C12 | 122.26 (17) | H22A—C22—H22B | 109.5 |
C4—C9—C10 | 111.88 (17) | C21—C22—H22C | 109.5 |
C4—C9—C11 | 112.79 (17) | H22A—C22—H22C | 109.5 |
C10—C9—C11 | 111.0 (2) | H22B—C22—H22C | 109.5 |
C4—C9—H9 | 106.9 | C21—C23—H23A | 109.5 |
C10—C9—H9 | 106.9 | C21—C23—H23B | 109.5 |
C11—C9—H9 | 106.9 | H23A—C23—H23B | 109.5 |
C9—C10—H10A | 109.5 | C21—C23—H23C | 109.5 |
C9—C10—H10B | 109.5 | H23A—C23—H23C | 109.5 |
H10A—C10—H10B | 109.5 | H23B—C23—H23C | 109.5 |
C9—C10—H10C | 109.5 | C20—C24—C25 | 110.8 (2) |
H10A—C10—H10C | 109.5 | C20—C24—C26 | 111.60 (19) |
H10B—C10—H10C | 109.5 | C25—C24—C26 | 110.8 (2) |
C9—C11—H11A | 109.5 | C20—C24—H24 | 107.8 |
C9—C11—H11B | 109.5 | C25—C24—H24 | 107.8 |
H11A—C11—H11B | 109.5 | C26—C24—H24 | 107.8 |
C9—C11—H11C | 109.5 | C24—C25—H25A | 109.5 |
H11A—C11—H11C | 109.5 | C24—C25—H25B | 109.5 |
H11B—C11—H11C | 109.5 | H25A—C25—H25B | 109.5 |
C13—C12—C14 | 110.6 (2) | C24—C25—H25C | 109.5 |
C13—C12—C8 | 111.64 (19) | H25A—C25—H25C | 109.5 |
C14—C12—C8 | 112.51 (18) | H25B—C25—H25C | 109.5 |
C13—C12—H12 | 107.3 | C24—C26—H26A | 109.5 |
C14—C12—H12 | 107.3 | C24—C26—H26B | 109.5 |
C8—C12—H12 | 107.3 | H26A—C26—H26B | 109.5 |
C12—C13—H13A | 109.5 | C24—C26—H26C | 109.5 |
C12—C13—H13B | 109.5 | H26A—C26—H26C | 109.5 |
H13A—C13—H13B | 109.5 | H26B—C26—H26C | 109.5 |
N2—Pd—N1—C1 | −0.30 (13) | C5—C4—C9—C11 | −38.1 (3) |
Cl1—Pd—N1—C1 | −178.56 (13) | C3—C4—C9—C11 | 141.58 (19) |
N2—Pd—N1—C3 | −173.32 (15) | C7—C8—C12—C13 | −73.6 (3) |
Cl1—Pd—N1—C3 | 8.41 (14) | C3—C8—C12—C13 | 107.5 (2) |
N1—Pd—N2—C2 | 0.29 (13) | C7—C8—C12—C14 | 51.4 (3) |
Cl2—Pd—N2—C2 | −176.15 (13) | C3—C8—C12—C14 | −127.5 (2) |
N1—Pd—N2—C15 | 177.36 (15) | C2—N2—C15—C16 | −98.9 (2) |
Cl2—Pd—N2—C15 | 0.92 (15) | Pd—N2—C15—C16 | 84.2 (2) |
C3—N1—C1—C2 | 173.76 (16) | C2—N2—C15—C20 | 81.3 (2) |
Pd—N1—C1—C2 | 0.3 (2) | Pd—N2—C15—C20 | −95.69 (18) |
C15—N2—C2—C1 | −177.63 (16) | C20—C15—C16—C17 | −3.8 (3) |
Pd—N2—C2—C1 | −0.3 (2) | N2—C15—C16—C17 | 176.32 (17) |
N1—C1—C2—N2 | 0.0 (3) | C20—C15—C16—C21 | 174.76 (18) |
C1—N1—C3—C4 | 104.4 (2) | N2—C15—C16—C21 | −5.1 (3) |
Pd—N1—C3—C4 | −82.89 (19) | C15—C16—C17—C18 | 2.3 (3) |
C1—N1—C3—C8 | −78.2 (2) | C21—C16—C17—C18 | −176.3 (2) |
Pd—N1—C3—C8 | 94.59 (18) | C16—C17—C18—C19 | 0.4 (4) |
C8—C3—C4—C5 | 4.3 (3) | C17—C18—C19—C20 | −1.8 (4) |
N1—C3—C4—C5 | −178.36 (16) | C18—C19—C20—C15 | 0.4 (3) |
C8—C3—C4—C9 | −175.39 (17) | C18—C19—C20—C24 | −179.5 (2) |
N1—C3—C4—C9 | 1.9 (3) | C16—C15—C20—C19 | 2.5 (3) |
C3—C4—C5—C6 | −3.3 (3) | N2—C15—C20—C19 | −177.63 (17) |
C9—C4—C5—C6 | 176.43 (19) | C16—C15—C20—C24 | −177.60 (19) |
C4—C5—C6—C7 | 0.4 (3) | N2—C15—C20—C24 | 2.3 (3) |
C5—C6—C7—C8 | 1.9 (3) | C15—C16—C21—C22 | 114.8 (2) |
C6—C7—C8—C3 | −0.9 (3) | C17—C16—C21—C22 | −66.7 (2) |
C6—C7—C8—C12 | −179.89 (19) | C15—C16—C21—C23 | −121.5 (2) |
C4—C3—C8—C7 | −2.3 (3) | C17—C16—C21—C23 | 57.1 (2) |
N1—C3—C8—C7 | −179.58 (16) | C19—C20—C24—C25 | 70.4 (3) |
C4—C3—C8—C12 | 176.70 (17) | C15—C20—C24—C25 | −109.4 (2) |
N1—C3—C8—C12 | −0.6 (3) | C19—C20—C24—C26 | −53.5 (3) |
C5—C4—C9—C10 | 87.9 (2) | C15—C20—C24—C26 | 126.6 (2) |
C3—C4—C9—C10 | −92.4 (2) |
Experimental details
Crystal data | |
Chemical formula | C26H36Cl2N2Pd |
Mr | 553.87 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 150 |
a, b, c (Å) | 13.7198 (1), 15.3812 (2), 13.8702 (2) |
β (°) | 110.3873 (5) |
V (Å3) | 2743.64 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.89 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Enraf Nonius Kappa CCD area detector diffractometer |
Absorption correction | Multi-scan SORTAV (Blessing, 1995, 1997) |
Tmin, Tmax | 0.673, 0.767 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 42903, 6279, 5446 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.075, 1.08 |
No. of reflections | 6279 |
No. of parameters | 288 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.78, −0.90 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
(I) | (II) | (III) | |
Pd—X | 2.2834 (5) | 2.300 (4) | 2.033 (5) |
Pd—Y | 2.2799 (5) | 2.020 (11) | 2.023 (6) |
Pd—N1 | 2.0142 (15) | 2.033 (9) | 2.133 (4) |
Pd—N2 | 2.0248 (14) | 2.208 (9) | 2.145 (4) |
N1—C1 | 1.280 (2) | 1.315 (16) | 1.317 (6) |
C1—C2 | 1.460 (3) | 1.434 (17) | 1.366 (8) |
C2—N2 | 1.282 (2) | 1.262 (18) | 1.297 (6) |
X—Pd—N1 | 93.66 (4) | 99.9 (3) | 100.17 (19) |
X—Pd—N2 | 172.75 (4) | 174.9 (3) | 174.3 (2) |
Y—Pd—N1 | 173.44 (4) | 170.4 (5) | 174.97 (19) |
Y—Pd—N2 | 95.17 (4) | 94.3 (4) | 99.6 (2) |
N1—Pd—N2 | 79.29 (6) | 76.2 (4) | 74.81 (15) |
X—Pd—Y | 91.963 (17) | 89.7 (4) | 85.5 (2) |
Pd—N1—C1 | 114.91 (12) | 117.6 (8) | 114.2 (3) |
N1—C1—C2 | 115.54 (16) | 115.3 (12) | 118.2 (4) |
C1—C2—N2 | 116.18 (16) | 119.5 (11) | 118.1 (4) |
C2—N2—Pd | 114.08 (12) | 111.3 (8) | 114.7 (3) |
Atom labels are primarily those of (I) with X = Cl1 and Y = Cl2, X = Cl, Y = Me for (II) and X = Y = Me for (III). Data for (II) and (III) from Tempel et al., 2000. |
[It is suggested that sch1.eps, the chemical structural drawing specific to (I) be used solely for the contents page and that sch2.eps, a more generalized representation of (I), (II) and (III) (or something like it) be used in association with the text.]
α-Diimines, RN═CR'—CR'═NR, have been widely used as ligands in transition metal complexes (van Koten & Vrieze, 1982; Vonzelewsky et al., 1994; Paw et al., 1998, Kaes et al., 2000; Farrell & Vlcek, 2000; van Slageren et al., 2000; Hicks et al., 2001). Several of the α-diimine complexes have found application as catalysts. For example, cationic palladium and nickel(II) complexes of bulky aryl-substituted α-diimines, ArN═CR—CR═NAr', have been shown to be excellent polymerization catalysts for ethylene and α-alkenes (Gottfried & Brookhart, 2001; Ittel et al., 2000; Tempel et al., 2000; Liimatta et al., 2001; Mecking, 2001; Albietz et al., 2000).
Selected geometric parameters of the title complex, (I), are shown in Table 1, along with data for two previously reported related compounds, chloro[N,N'-bis(2,6-diisopropylphenyl)-1,2-ethanediimine-N,N']methylpalladium, (II), and [N,N'-bis(2,6-diisopropylphenyl)-2,3-butanediimine-N,N']dimethylpalladium, (III) (Tempel et al., 2000).
Compound (I) (Fig. 1) has a square planar geometry, with a distortion mainly arising from the small, 79.29 (6)°, bite angle, N(1)—Pd—N(2), of the chelating diimine ligand. Distortions from square planar geometry in (I) are also indicated by the torsional angles, Cl(2)—Pd—N(1)—C(1) = 32.4 (5) and Cl(1)—Pd—N(2)—C(2) = 14.1 (4)°. The diimine bite angle in (I), although much less than the ideal value of 90°, is noticeably larger than those in (II) [76.2 (4)°] and (III) [74.81 (15)°], other neutral Pd(II) diimine complexes, as well as those in the Pd(0) complexes, [η2-(E)-but-2-enedinitrile](N,N'-diphenyl-1,7,7- trimethylbicyclo[2.2.1]heptane-2,3-diimine-N,N')palladium(0) [77.31 (9)°] (Ellis & Spek, 2001) and [bis((2,6-diisopropylphenyl)imino)acenaphthene](maleic anhydride)palladium(0) [77.78 (19)°] (van Asselt et al., 1994). The diimine bite angle in the cationic complex, [(2,6-bis-diisopropyl-N-(2- pyridinylmethylene)phenylamine)methyl(acetonitrile)palladium] [B(3,5-(CF3)2C6H3)4] [78.8 (2)°] (Meneghetti et al., 1999) is however similar to that in (I). The angles between the plane of the –Pd—N(1)—C(1)—C(2)—N(2)- ring in (I) and the aryl ring planes are 80.66 (5)° [C3—C8] and 82.73 (6)° [C15—C21]. Thus, as in other similar complexes, the bulky isopropyl substituents effectively block approaches to the Pd atom from axial directions. A small degree of electron delocalization in the diimine ligand in (I) is indicated by the bond lengths, N(1)—C(1) = 1.280 (2), C(1)—C(2) = 1.460 (3) and C(2)—N(2) = 1.282 (2) Å. More delocalization in the N═C—C═N fragments of the ligands is apparent in (II) and (III). The bond lengths in (I) are only slightly different from those in the free ligand, [N,N'-bis(2,6-diisopropylphenyl)-1,2-ethanediimine], for which N—C = 1.265 (4) and C—C = 1.467 (4) Å (Laine et al., 1999).