Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101014147/gd1166sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101014147/gd1166Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101014147/gd1166IIsup3.hkl |
CCDC references: 180134; 180135
Compound (I) was prepared by reaction of di-µ-acetato-bis({5-(dimethylamino)- 2-[N-(4-methoxyphenyl)iminomethyl]phenyl}palladium(II)) with N-(4-methoxyphenyl)-4-nitrosalicylaldimine and compound (II) was prepared by reaction of di-µ-acetato-bis({2-[N-(4-methoxyphenyliminomethyl)-5-nitrophenyl}- palladium(II)) with N-(4-methoxyphenyl)-4-(diethylamino)salicylaldimine. In both cases, a molar ratio of 2:1 of imine and dinuclear complex was used. Reactions were performed at room temperature for 1 h in CH2Cl2/ethanol solvent. Melting points: 568 K (decomposition) for (I) and 584 K (decomposition) for (II). Analysis for (I): Pd 16.9% calculated, 16.6% found; for (II): Pd 16.1% calculated, 15.9% found. UV-vis λmax/nm: 421 in ethyl acetate (µ = 1.78 D) and 425 in dimethylformamide (DMF) (µ = 3.82 D) for (I); 358 in ethyl acetate and 362 in DMF for (II). Crystals suitable for single-crystal X-ray diffraction analysis were obtained by slow evaporation from chloroform for (I) and from dichloromethane–hexane for (II).
All H atoms were stereochemically positioned. For all H atoms were refined as riding, with Uiso equal to Ueq of the carrier atom, and C—H distances in the range 0.93–0.97 Å. For (I), symmetry-equivalent reflections were not merged. The total of 8378 reflections includes 3634 Friedel pairs. The Flack (1983) parameter was refined with TWIN and BASF instructions (and MERG 0) according to the SHELX97 manual. For (II), systematically absent reflections corresponding to lattice centering were not collected.
For both compounds, data collection: MACH3 Software (Nonius, 1996); cell refinement: CELLDIM (Nonius, 1996); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1999).
C30H28N4O5Pd | Dx = 1.554 Mg m−3 |
Mr = 630.96 | Mo Kα radiation, λ = 0.71069 Å |
Orthorhombic, Pca21 | Cell parameters from 24 reflections |
a = 24.41 (2) Å | θ = 8.2–9.5° |
b = 14.479 (6) Å | µ = 0.74 mm−1 |
c = 7.630 (4) Å | T = 293 K |
V = 2697 (3) Å3 | Prism, orange |
Z = 4 | 0.5 × 0.1 × 0.04 mm |
F(000) = 1288 |
Enraf Nonius MACH 3 diffractometer | 4033 reflections with I > 2σ(I) |
Radiation source: Enraf Nonius FR590 | Rint = 0.054 |
Graphite monochromator | θmax = 30.0°, θmin = 2.2° |
ω/θ scans | h = −34→34 |
Absorption correction: ψ scan (North et al., 1968) | k = −20→20 |
Tmin = 0.939, Tmax = 1.000 | l = −10→10 |
8378 measured reflections | 2 standard reflections every 120 min |
7823 independent reflections | intensity decay: 2% |
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)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.124 | w = 1/[σ2(Fo2) + (0.0375P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max = 0.002 |
7823 reflections | Δρmax = 0.51 e Å−3 |
361 parameters | Δρmin = −0.51 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.11 (5) |
C30H28N4O5Pd | V = 2697 (3) Å3 |
Mr = 630.96 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 24.41 (2) Å | µ = 0.74 mm−1 |
b = 14.479 (6) Å | T = 293 K |
c = 7.630 (4) Å | 0.5 × 0.1 × 0.04 mm |
Enraf Nonius MACH 3 diffractometer | 4033 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.054 |
Tmin = 0.939, Tmax = 1.000 | 2 standard reflections every 120 min |
8378 measured reflections | intensity decay: 2% |
7823 independent reflections |
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.124 | Δρmax = 0.51 e Å−3 |
S = 0.96 | Δρmin = −0.51 e Å−3 |
7823 reflections | Absolute structure: Flack (1983) |
361 parameters | Absolute structure parameter: 0.11 (5) |
1 restraint |
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. A refinement against 4189 reflections obtained after merging symmetry equivalent as well as Friedel pairs gave R1=0.044 and wR2=0.1026. |
x | y | z | Uiso*/Ueq | ||
Pd1 | 0.616634 (15) | 0.11843 (3) | 0.96592 (8) | 0.03391 (10) | |
N1 | 0.5971 (2) | −0.2610 (4) | 0.9101 (7) | 0.0427 (15) | |
N2 | 0.5503 (2) | 0.1601 (4) | 0.8246 (7) | 0.0372 (13) | |
N3 | 0.6830 (2) | 0.0804 (3) | 1.1150 (7) | 0.0352 (13) | |
N4 | 0.7755 (3) | 0.4763 (4) | 0.8129 (10) | 0.0589 (18) | |
O1 | 0.4959 (2) | 0.5209 (4) | 0.6418 (8) | 0.0567 (15) | |
O2 | 0.6597 (2) | −0.2247 (4) | 1.5478 (7) | 0.0699 (17) | |
O3 | 0.64339 (17) | 0.2523 (3) | 0.9993 (8) | 0.0435 (15) | |
O4 | 0.7377 (3) | 0.5254 (4) | 0.7743 (12) | 0.098 (3) | |
O5 | 0.8229 (3) | 0.4973 (4) | 0.8010 (11) | 0.092 (2) | |
C1 | 0.6467 (3) | −0.2767 (5) | 1.0032 (13) | 0.063 (3) | |
H1A | 0.6538 | −0.3419 | 1.0089 | 0.063* | |
H1B | 0.6435 | −0.2524 | 1.1198 | 0.063* | |
H1C | 0.6764 | −0.2465 | 0.9437 | 0.063* | |
C2 | 0.5711 (3) | −0.3411 (5) | 0.8309 (11) | 0.059 (2) | |
H2A | 0.5906 | −0.3959 | 0.8642 | 0.059* | |
H2B | 0.5717 | −0.3349 | 0.7057 | 0.059* | |
H2C | 0.5339 | −0.3453 | 0.8706 | 0.059* | |
C3 | 0.5768 (3) | −0.1744 (4) | 0.8809 (9) | 0.0359 (15) | |
C4 | 0.5275 (3) | −0.1625 (5) | 0.7908 (10) | 0.0465 (18) | |
H4 | 0.5079 | −0.2140 | 0.7539 | 0.046* | |
C5 | 0.5080 (3) | −0.0773 (5) | 0.7566 (10) | 0.0421 (17) | |
H5 | 0.4753 | −0.0711 | 0.6952 | 0.042* | |
C6 | 0.5357 (2) | 0.0017 (5) | 0.8114 (9) | 0.0369 (15) | |
C7 | 0.5855 (2) | −0.0066 (4) | 0.9073 (8) | 0.0349 (15) | |
C8 | 0.6045 (2) | −0.0956 (4) | 0.9397 (11) | 0.0353 (18) | |
H8 | 0.6368 | −0.1030 | 1.0028 | 0.035* | |
C9 | 0.5194 (3) | 0.0930 (5) | 0.7731 (10) | 0.0459 (19) | |
H9 | 0.4872 | 0.1045 | 0.7120 | 0.046* | |
C10 | 0.5350 (3) | 0.2520 (5) | 0.7830 (9) | 0.0402 (16) | |
C11 | 0.4829 (3) | 0.2853 (5) | 0.8182 (9) | 0.0399 (16) | |
H11 | 0.4576 | 0.2468 | 0.8727 | 0.040* | |
C12 | 0.4674 (3) | 0.3744 (5) | 0.7747 (9) | 0.0423 (16) | |
H12 | 0.4322 | 0.3953 | 0.7983 | 0.042* | |
C13 | 0.5060 (3) | 0.4326 (5) | 0.6940 (10) | 0.0430 (17) | |
C14 | 0.5587 (3) | 0.4010 (5) | 0.6648 (9) | 0.0454 (18) | |
H14 | 0.5846 | 0.4398 | 0.6140 | 0.045* | |
C15 | 0.5728 (3) | 0.3127 (5) | 0.7107 (10) | 0.0478 (18) | |
H15 | 0.6087 | 0.2928 | 0.6929 | 0.048* | |
C16 | 0.4435 (3) | 0.5578 (5) | 0.6581 (12) | 0.060 (2) | |
H16A | 0.4433 | 0.6199 | 0.6143 | 0.060* | |
H16B | 0.4329 | 0.5578 | 0.7793 | 0.060* | |
H16C | 0.4181 | 0.5210 | 0.5920 | 0.060* | |
C17 | 0.6924 (3) | −0.3035 (5) | 1.5296 (12) | 0.071 (3) | |
H17A | 0.6803 | −0.3500 | 1.6106 | 0.071* | |
H17B | 0.7298 | −0.2879 | 1.5536 | 0.071* | |
H17C | 0.6893 | −0.3266 | 1.4121 | 0.071* | |
C18 | 0.6700 (3) | −0.1506 (5) | 1.4428 (11) | 0.0394 (17) | |
C19 | 0.6321 (2) | −0.0802 (4) | 1.4508 (16) | 0.0448 (16) | |
H19 | 0.6030 | −0.0837 | 1.5293 | 0.045* | |
C20 | 0.6373 (3) | −0.0054 (5) | 1.3437 (9) | 0.0393 (15) | |
H20 | 0.6108 | 0.0407 | 1.3465 | 0.039* | |
C21 | 0.6812 (2) | 0.0028 (4) | 1.2311 (8) | 0.0334 (14) | |
C22 | 0.7210 (3) | −0.0645 (4) | 1.2281 (9) | 0.0389 (16) | |
H22 | 0.7514 | −0.0584 | 1.1555 | 0.039* | |
C23 | 0.7150 (3) | −0.1425 (5) | 1.3362 (9) | 0.0426 (17) | |
H23 | 0.7415 | −0.1885 | 1.3356 | 0.043* | |
C24 | 0.7292 (3) | 0.1255 (4) | 1.1039 (8) | 0.0350 (14) | |
H24 | 0.7593 | 0.0993 | 1.1599 | 0.035* | |
C25 | 0.7386 (2) | 0.2120 (4) | 1.0135 (8) | 0.0350 (16) | |
C26 | 0.6947 (2) | 0.2730 (4) | 0.9774 (15) | 0.0367 (13) | |
C27 | 0.7097 (3) | 0.3618 (4) | 0.9140 (8) | 0.0422 (18) | |
H27 | 0.6827 | 0.4055 | 0.8925 | 0.042* | |
C28 | 0.7624 (3) | 0.3833 (5) | 0.8848 (9) | 0.0456 (16) | |
C29 | 0.8052 (3) | 0.3229 (5) | 0.9187 (8) | 0.048 (2) | |
H29 | 0.8414 | 0.3393 | 0.8962 | 0.048* | |
C30 | 0.7925 (2) | 0.2395 (4) | 0.9852 (14) | 0.0441 (18) | |
H30 | 0.8207 | 0.1989 | 1.0133 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.02889 (16) | 0.03758 (19) | 0.03525 (19) | −0.0010 (2) | −0.0037 (4) | 0.0009 (5) |
N1 | 0.054 (3) | 0.040 (3) | 0.035 (4) | −0.011 (3) | −0.009 (3) | 0.003 (2) |
N2 | 0.034 (3) | 0.043 (3) | 0.035 (3) | 0.004 (3) | −0.007 (2) | 0.005 (3) |
N3 | 0.034 (3) | 0.030 (3) | 0.042 (3) | 0.000 (2) | 0.000 (3) | −0.002 (2) |
N4 | 0.072 (5) | 0.038 (4) | 0.067 (5) | −0.012 (3) | 0.003 (4) | −0.001 (4) |
O1 | 0.056 (3) | 0.042 (3) | 0.072 (4) | 0.002 (3) | −0.010 (3) | 0.006 (3) |
O2 | 0.095 (4) | 0.052 (3) | 0.063 (4) | 0.011 (3) | 0.019 (3) | 0.020 (3) |
O3 | 0.038 (2) | 0.037 (2) | 0.055 (5) | −0.0030 (18) | −0.005 (3) | −0.008 (3) |
O4 | 0.089 (6) | 0.050 (3) | 0.155 (8) | −0.003 (4) | −0.026 (5) | 0.036 (5) |
O5 | 0.083 (4) | 0.054 (3) | 0.139 (7) | −0.020 (3) | 0.032 (5) | 0.010 (4) |
C1 | 0.059 (5) | 0.050 (4) | 0.079 (9) | −0.005 (4) | −0.006 (5) | −0.003 (5) |
C2 | 0.085 (6) | 0.043 (4) | 0.049 (5) | −0.017 (4) | −0.002 (4) | 0.006 (4) |
C3 | 0.036 (3) | 0.039 (4) | 0.032 (3) | −0.006 (3) | 0.008 (3) | 0.004 (3) |
C4 | 0.049 (4) | 0.050 (4) | 0.040 (4) | −0.008 (4) | −0.010 (4) | −0.010 (4) |
C5 | 0.033 (3) | 0.059 (5) | 0.034 (4) | −0.004 (3) | −0.004 (3) | −0.007 (4) |
C6 | 0.033 (3) | 0.051 (4) | 0.026 (3) | 0.002 (3) | 0.000 (3) | −0.004 (3) |
C7 | 0.029 (3) | 0.041 (4) | 0.034 (4) | −0.001 (3) | 0.000 (2) | −0.001 (3) |
C8 | 0.035 (3) | 0.047 (3) | 0.023 (5) | −0.009 (2) | −0.005 (3) | 0.006 (3) |
C9 | 0.033 (4) | 0.067 (5) | 0.038 (4) | 0.002 (3) | −0.010 (3) | 0.001 (4) |
C10 | 0.036 (4) | 0.047 (4) | 0.038 (4) | −0.004 (3) | −0.008 (3) | 0.004 (3) |
C11 | 0.034 (3) | 0.048 (4) | 0.038 (4) | −0.004 (3) | 0.002 (3) | 0.007 (3) |
C12 | 0.032 (3) | 0.050 (4) | 0.045 (4) | 0.002 (3) | 0.001 (3) | −0.001 (4) |
C13 | 0.048 (4) | 0.044 (4) | 0.038 (4) | 0.001 (4) | −0.007 (3) | 0.004 (4) |
C14 | 0.040 (4) | 0.056 (5) | 0.040 (4) | −0.012 (3) | 0.006 (3) | 0.014 (4) |
C15 | 0.032 (3) | 0.066 (5) | 0.046 (4) | 0.004 (3) | 0.001 (3) | 0.009 (4) |
C16 | 0.078 (6) | 0.047 (5) | 0.056 (5) | 0.013 (4) | −0.007 (5) | −0.006 (4) |
C17 | 0.101 (7) | 0.054 (5) | 0.058 (6) | −0.003 (5) | −0.003 (5) | 0.013 (4) |
C18 | 0.049 (3) | 0.048 (3) | 0.020 (5) | 0.001 (3) | −0.001 (3) | 0.007 (3) |
C19 | 0.046 (3) | 0.058 (3) | 0.030 (4) | −0.002 (3) | 0.007 (4) | 0.000 (5) |
C20 | 0.038 (3) | 0.040 (4) | 0.039 (4) | 0.004 (3) | 0.002 (3) | 0.001 (4) |
C21 | 0.030 (3) | 0.037 (3) | 0.034 (4) | −0.005 (3) | −0.007 (3) | −0.006 (3) |
C22 | 0.039 (4) | 0.049 (4) | 0.029 (4) | −0.004 (3) | 0.003 (3) | −0.001 (3) |
C23 | 0.041 (4) | 0.045 (4) | 0.041 (4) | 0.006 (3) | −0.006 (3) | −0.003 (3) |
C24 | 0.040 (3) | 0.031 (3) | 0.034 (3) | 0.007 (3) | −0.005 (3) | −0.008 (3) |
C25 | 0.035 (3) | 0.040 (3) | 0.030 (4) | −0.003 (3) | −0.007 (2) | −0.004 (3) |
C26 | 0.037 (3) | 0.037 (3) | 0.036 (4) | −0.007 (2) | 0.002 (5) | −0.004 (5) |
C27 | 0.055 (4) | 0.033 (4) | 0.039 (4) | 0.001 (3) | −0.013 (3) | −0.003 (3) |
C28 | 0.058 (4) | 0.038 (3) | 0.041 (4) | −0.016 (4) | −0.006 (3) | 0.002 (4) |
C29 | 0.037 (3) | 0.062 (5) | 0.045 (5) | −0.010 (3) | 0.006 (3) | 0.007 (4) |
C30 | 0.035 (3) | 0.050 (3) | 0.048 (5) | 0.000 (3) | −0.003 (4) | 0.009 (5) |
Pd1—C7 | 2.014 (6) | C10—C15 | 1.389 (9) |
Pd1—N2 | 2.037 (5) | C11—C12 | 1.384 (9) |
Pd1—N3 | 2.055 (5) | C11—H11 | 0.9300 |
Pd1—O3 | 2.062 (4) | C12—C13 | 1.407 (10) |
N1—C3 | 1.366 (8) | C12—H12 | 0.9300 |
N1—C1 | 1.423 (8) | C13—C14 | 1.383 (10) |
N1—C2 | 1.453 (8) | C14—C15 | 1.371 (9) |
N2—C9 | 1.291 (8) | C14—H14 | 0.9300 |
N2—C10 | 1.417 (8) | C15—H15 | 0.9300 |
N3—C24 | 1.306 (8) | C16—H16A | 0.9600 |
N3—C21 | 1.431 (8) | C16—H16B | 0.9600 |
N4—O5 | 1.200 (8) | C16—H16C | 0.9600 |
N4—O4 | 1.202 (9) | C17—H17A | 0.9600 |
N4—C28 | 1.489 (9) | C17—H17B | 0.9600 |
O1—C13 | 1.362 (8) | C17—H17C | 0.9600 |
O1—C16 | 1.393 (9) | C18—C23 | 1.372 (9) |
O2—C18 | 1.362 (8) | C18—C19 | 1.377 (8) |
O2—C17 | 1.399 (9) | C19—C20 | 1.362 (10) |
O3—C26 | 1.298 (6) | C19—H19 | 0.9300 |
C1—H1A | 0.9600 | C20—C21 | 1.379 (8) |
C1—H1B | 0.9600 | C20—H20 | 0.9300 |
C1—H1C | 0.9600 | C21—C22 | 1.376 (8) |
C2—H2A | 0.9600 | C22—C23 | 1.407 (9) |
C2—H2B | 0.9600 | C22—H22 | 0.9300 |
C2—H2C | 0.9600 | C23—H23 | 0.9300 |
C3—C4 | 1.396 (9) | C24—C25 | 1.447 (8) |
C3—C8 | 1.400 (8) | C24—H24 | 0.9300 |
C4—C5 | 1.348 (9) | C25—C30 | 1.392 (8) |
C4—H4 | 0.9300 | C25—C26 | 1.416 (8) |
C5—C6 | 1.393 (9) | C26—C27 | 1.421 (9) |
C5—H5 | 0.9300 | C27—C28 | 1.342 (9) |
C6—C9 | 1.411 (9) | C27—H27 | 0.9300 |
C6—C7 | 1.424 (8) | C28—C29 | 1.388 (9) |
C7—C8 | 1.392 (8) | C29—C30 | 1.346 (9) |
C8—H8 | 0.9300 | C29—H29 | 0.9300 |
C9—H9 | 0.9300 | C30—H30 | 0.9300 |
C10—C11 | 1.386 (9) | ||
C7—Pd1—N2 | 81.3 (2) | C13—C12—H12 | 120.6 |
C7—Pd1—N3 | 100.3 (2) | O1—C13—C14 | 115.6 (6) |
N2—Pd1—N3 | 177.8 (2) | O1—C13—C12 | 124.7 (7) |
C7—Pd1—O3 | 173.0 (2) | C14—C13—C12 | 119.7 (7) |
N2—Pd1—O3 | 92.2 (2) | C15—C14—C13 | 120.1 (6) |
N3—Pd1—O3 | 86.2 (2) | C15—C14—H14 | 120.0 |
C3—N1—C1 | 122.4 (6) | C13—C14—H14 | 120.0 |
C3—N1—C2 | 120.4 (6) | C14—C15—C10 | 121.6 (6) |
C1—N1—C2 | 116.8 (6) | C14—C15—H15 | 119.2 |
C9—N2—C10 | 119.0 (6) | C10—C15—H15 | 119.2 |
C9—N2—Pd1 | 113.7 (5) | O1—C16—H16A | 109.5 |
C10—N2—Pd1 | 127.3 (4) | O1—C16—H16B | 109.5 |
C24—N3—C21 | 117.4 (5) | H16A—C16—H16B | 109.5 |
C24—N3—Pd1 | 120.7 (4) | O1—C16—H16C | 109.5 |
C21—N3—Pd1 | 121.9 (4) | H16A—C16—H16C | 109.5 |
O5—N4—O4 | 124.9 (7) | H16B—C16—H16C | 109.5 |
O5—N4—C28 | 117.7 (7) | O2—C17—H17A | 109.5 |
O4—N4—C28 | 117.4 (7) | O2—C17—H17B | 109.5 |
C13—O1—C16 | 120.0 (6) | H17A—C17—H17B | 109.5 |
C18—O2—C17 | 118.6 (6) | O2—C17—H17C | 109.5 |
C26—O3—Pd1 | 120.5 (4) | H17A—C17—H17C | 109.5 |
N1—C1—H1A | 109.5 | H17B—C17—H17C | 109.5 |
N1—C1—H1B | 109.5 | O2—C18—C23 | 124.3 (6) |
H1A—C1—H1B | 109.5 | O2—C18—C19 | 115.6 (7) |
N1—C1—H1C | 109.5 | C23—C18—C19 | 120.0 (7) |
H1A—C1—H1C | 109.5 | C20—C19—C18 | 120.0 (8) |
H1B—C1—H1C | 109.5 | C20—C19—H19 | 120.0 |
N1—C2—H2A | 109.5 | C18—C19—H19 | 120.0 |
N1—C2—H2B | 109.5 | C19—C20—C21 | 121.0 (6) |
H2A—C2—H2B | 109.5 | C19—C20—H20 | 119.5 |
N1—C2—H2C | 109.5 | C21—C20—H20 | 119.5 |
H2A—C2—H2C | 109.5 | C22—C21—C20 | 119.9 (6) |
H2B—C2—H2C | 109.5 | C22—C21—N3 | 121.5 (6) |
N1—C3—C4 | 120.4 (6) | C20—C21—N3 | 118.5 (6) |
N1—C3—C8 | 121.4 (6) | C21—C22—C23 | 119.0 (6) |
C4—C3—C8 | 118.2 (6) | C21—C22—H22 | 120.5 |
C5—C4—C3 | 121.0 (6) | C23—C22—H22 | 120.5 |
C5—C4—H4 | 119.5 | C18—C23—C22 | 120.0 (6) |
C3—C4—H4 | 119.5 | C18—C23—H23 | 120.0 |
C4—C5—C6 | 121.3 (6) | C22—C23—H23 | 120.0 |
C4—C5—H5 | 119.3 | N3—C24—C25 | 126.8 (6) |
C6—C5—H5 | 119.3 | N3—C24—H24 | 116.6 |
C5—C6—C9 | 124.7 (6) | C25—C24—H24 | 116.6 |
C5—C6—C7 | 120.0 (6) | C30—C25—C26 | 120.4 (6) |
C9—C6—C7 | 115.2 (6) | C30—C25—C24 | 118.1 (6) |
C8—C7—C6 | 117.0 (6) | C26—C25—C24 | 120.9 (6) |
C8—C7—Pd1 | 131.8 (4) | O3—C26—C25 | 124.1 (6) |
C6—C7—Pd1 | 111.1 (5) | O3—C26—C27 | 120.1 (6) |
C7—C8—C3 | 122.4 (6) | C25—C26—C27 | 115.8 (5) |
C7—C8—H8 | 118.8 | C28—C27—C26 | 121.0 (6) |
C3—C8—H8 | 118.8 | C28—C27—H27 | 119.5 |
N2—C9—C6 | 118.6 (6) | C26—C27—H27 | 119.5 |
N2—C9—H9 | 120.7 | C27—C28—C29 | 123.0 (6) |
C6—C9—H9 | 120.7 | C27—C28—N4 | 118.6 (7) |
C11—C10—C15 | 117.8 (7) | C29—C28—N4 | 118.4 (6) |
C11—C10—N2 | 121.7 (6) | C30—C29—C28 | 117.4 (6) |
C15—C10—N2 | 120.5 (6) | C30—C29—H29 | 121.3 |
C12—C11—C10 | 121.9 (6) | C28—C29—H29 | 121.3 |
C12—C11—H11 | 119.0 | C29—C30—C25 | 122.3 (6) |
C10—C11—H11 | 119.0 | C29—C30—H30 | 118.8 |
C11—C12—C13 | 118.7 (6) | C25—C30—H30 | 118.8 |
C11—C12—H12 | 120.6 | ||
C20—C21—N3—C24 | 133.4 (6) | C24—C25—C26—O3 | −9.6 (13) |
C21—N3—C24—C25 | −171.5 (6) | C25—C26—O3—Pd1 | −31.7 (13) |
N3—C24—C25—C30 | −166.9 (7) | C26—O3—Pd1—N2 | −135.2 (7) |
C5—C6—C9—N2 | −176.7 (7) | O3—Pd1—N2—C9 | −179.8 (5) |
C6—C9—N2—C10 | 178.5 (6) | Pd1—N2—C9—C6 | −2.8 (8) |
C9—N2—C10—C15 | −131.3 (7) | N2—C9—C6—C7 | 0.7 (9) |
N3—C24—C25—C26 | 22.1 (10) | C1—N1—C3—C4 | −179.2 (7) |
[Pd(C14H11N2O3)(C18H21N2O2)]·0.5CH2Cl2 | F(000) = 2872 |
Mr = 701.48 | Dx = 1.516 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
a = 31.582 (10) Å | Cell parameters from 24 reflections |
b = 7.5847 (10) Å | θ = 8.5–11.8° |
c = 26.557 (6) Å | µ = 0.74 mm−1 |
β = 104.96 (3)° | T = 293 K |
V = 6146 (3) Å3 | Prism, dark orange |
Z = 8 | 0.5 × 0.1 × 0.06 mm |
Enraf-Nonius MACH3 diffractometer | 3705 reflections with I > 2σ(I) |
Radiation source: Enraf Nonius FR590 | Rint = 0.060 |
Graphite monochromator | θmax = 28.0°, θmin = 1.3° |
ω/θ scans | h = −41→40 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→10 |
Tmin = 0.952, Tmax = 1.000 | l = 0→34 |
7552 measured reflections | 1 standard reflections every 120 min |
7388 independent reflections | intensity decay: 1% |
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0525P)2] where P = (Fo2 + 2Fc2)/3 |
7388 reflections | (Δ/σ)max < 0.001 |
393 parameters | Δρmax = 0.66 e Å−3 |
0 restraints | Δρmin = −0.75 e Å−3 |
[Pd(C14H11N2O3)(C18H21N2O2)]·0.5CH2Cl2 | V = 6146 (3) Å3 |
Mr = 701.48 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 31.582 (10) Å | µ = 0.74 mm−1 |
b = 7.5847 (10) Å | T = 293 K |
c = 26.557 (6) Å | 0.5 × 0.1 × 0.06 mm |
β = 104.96 (3)° |
Enraf-Nonius MACH3 diffractometer | 3705 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.060 |
Tmin = 0.952, Tmax = 1.000 | 1 standard reflections every 120 min |
7552 measured reflections | intensity decay: 1% |
7388 independent reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.66 e Å−3 |
7388 reflections | Δρmin = −0.75 e Å−3 |
393 parameters |
Experimental. Pd content in (1) and (2) was determined by thermogravimetric analysis (Mettler TG 50, scanning rate 20 C/min, air atmosphere). NMR analysis of (1) and (2), as well as of synthetic precursors, was performed on a Varian Gemini XL 200 Mhz spectrometer. UV-VIS spectra were recorded at ambient temperature with a Perkin Elmer Lambda 7 spectrometer. Transition temperatures were determined by DSC analysis (Perkin Elmer DSC-7 apparatus). |
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. All H atoms were stereochemically positioned. For all H atoms refinement was by the riding model, with Uiso equal to Ueq of the carrier atom. |
x | y | z | Uiso*/Ueq | ||
Pd1 | 0.192569 (16) | 0.58907 (6) | 0.151034 (17) | 0.03280 (13) | |
N1 | 0.22485 (17) | 0.6935 (7) | 0.22168 (19) | 0.0367 (12) | |
N2 | 0.02152 (19) | 0.6326 (10) | 0.1624 (3) | 0.0604 (19) | |
N3 | 0.32671 (18) | 0.0010 (7) | 0.0894 (2) | 0.0490 (15) | |
N4 | 0.15873 (16) | 0.5164 (7) | 0.07874 (18) | 0.0356 (12) | |
O1 | 0.40472 (16) | 0.7259 (7) | 0.3076 (2) | 0.0608 (14) | |
O2 | −0.00407 (18) | 0.6699 (12) | 0.1875 (2) | 0.112 (3) | |
O3 | 0.01069 (17) | 0.5570 (9) | 0.1214 (2) | 0.0786 (18) | |
O4 | 0.24843 (13) | 0.4736 (5) | 0.13842 (16) | 0.0385 (10) | |
O5 | 0.01872 (17) | 0.8930 (8) | −0.0465 (2) | 0.0714 (15) | |
C1 | 0.4236 (3) | 0.6686 (12) | 0.3592 (3) | 0.074 (3) | |
H1A | 0.4549 | 0.6815 | 0.3671 | 0.074* | |
H1B | 0.4164 | 0.5469 | 0.3625 | 0.074* | |
H1C | 0.4124 | 0.7383 | 0.3830 | 0.074* | |
C2 | 0.3606 (2) | 0.7153 (9) | 0.2899 (3) | 0.0432 (16) | |
C3 | 0.3325 (2) | 0.6591 (9) | 0.3186 (3) | 0.0448 (17) | |
H3 | 0.3433 | 0.6263 | 0.3533 | 0.045* | |
C4 | 0.2880 (2) | 0.6521 (9) | 0.2952 (3) | 0.0424 (16) | |
H4 | 0.2690 | 0.6149 | 0.3146 | 0.042* | |
C5 | 0.2713 (2) | 0.6983 (8) | 0.2443 (2) | 0.0356 (14) | |
C6 | 0.2993 (2) | 0.7528 (9) | 0.2151 (3) | 0.0452 (16) | |
H6 | 0.2882 | 0.7815 | 0.1801 | 0.045* | |
C7 | 0.3437 (2) | 0.7645 (9) | 0.2380 (3) | 0.0484 (17) | |
H7 | 0.3624 | 0.8053 | 0.2187 | 0.048* | |
C8 | 0.2001 (2) | 0.7662 (8) | 0.2476 (2) | 0.0382 (15) | |
H8 | 0.2114 | 0.8248 | 0.2789 | 0.038* | |
C9 | 0.1536 (2) | 0.7503 (7) | 0.2244 (2) | 0.0332 (14) | |
C10 | 0.1230 (2) | 0.8063 (9) | 0.2512 (2) | 0.0430 (16) | |
H10 | 0.1322 | 0.8663 | 0.2827 | 0.043* | |
C11 | 0.0791 (2) | 0.7715 (10) | 0.2303 (3) | 0.0487 (18) | |
H11 | 0.0581 | 0.8075 | 0.2470 | 0.049* | |
C12 | 0.0678 (2) | 0.6819 (9) | 0.1841 (3) | 0.0420 (16) | |
C13 | 0.0973 (2) | 0.6329 (8) | 0.1556 (2) | 0.0404 (16) | |
H13 | 0.0874 | 0.5780 | 0.1234 | 0.040* | |
C14 | 0.1414 (2) | 0.6669 (8) | 0.1757 (2) | 0.0335 (14) | |
C15 | 0.3214 (3) | −0.3229 (10) | 0.0817 (3) | 0.085 (3) | |
H15A | 0.3243 | −0.4188 | 0.0593 | 0.085* | |
H15B | 0.2920 | −0.3199 | 0.0855 | 0.085* | |
H15C | 0.3415 | −0.3389 | 0.1153 | 0.085* | |
C16 | 0.3313 (2) | −0.1527 (9) | 0.0584 (3) | 0.0518 (19) | |
H16A | 0.3610 | −0.1569 | 0.0547 | 0.052* | |
H16B | 0.3117 | −0.1401 | 0.0239 | 0.052* | |
C17 | 0.3663 (2) | 0.0518 (9) | 0.1276 (3) | 0.0513 (19) | |
H17A | 0.3853 | −0.0502 | 0.1362 | 0.051* | |
H17B | 0.3587 | 0.0891 | 0.1591 | 0.051* | |
C18 | 0.3911 (2) | 0.1990 (12) | 0.1094 (3) | 0.071 (2) | |
H18A | 0.4169 | 0.2266 | 0.1363 | 0.071* | |
H18B | 0.3727 | 0.3016 | 0.1016 | 0.071* | |
H18C | 0.3993 | 0.1622 | 0.0786 | 0.071* | |
C19 | 0.2887 (2) | 0.0929 (9) | 0.0832 (2) | 0.0386 (13) | |
C20 | 0.2864 (2) | 0.2413 (8) | 0.1132 (2) | 0.0362 (15) | |
H20 | 0.3116 | 0.2782 | 0.1376 | 0.036* | |
C21 | 0.2475 (2) | 0.3378 (8) | 0.1083 (2) | 0.0348 (14) | |
C22 | 0.2098 (2) | 0.2863 (8) | 0.0695 (2) | 0.0374 (14) | |
C23 | 0.2131 (2) | 0.1352 (8) | 0.0391 (3) | 0.0456 (17) | |
H23 | 0.1886 | 0.1007 | 0.0133 | 0.046* | |
C24 | 0.2501 (2) | 0.0394 (9) | 0.0459 (3) | 0.0490 (18) | |
H24 | 0.2504 | −0.0615 | 0.0261 | 0.049* | |
C25 | 0.1713 (2) | 0.3859 (9) | 0.0544 (2) | 0.0386 (15) | |
H25 | 0.1521 | 0.3544 | 0.0228 | 0.039* | |
C26 | 0.1217 (2) | 0.6140 (9) | 0.0489 (2) | 0.0379 (15) | |
C27 | 0.0839 (2) | 0.5348 (10) | 0.0198 (2) | 0.0470 (17) | |
H27 | 0.0813 | 0.4129 | 0.0213 | 0.047* | |
C28 | 0.0504 (2) | 0.6286 (10) | −0.0108 (3) | 0.0522 (19) | |
H28 | 0.0252 | 0.5716 | −0.0294 | 0.052* | |
C29 | 0.0541 (2) | 0.8095 (11) | −0.0141 (3) | 0.0541 (19) | |
C30 | 0.0907 (2) | 0.8925 (10) | 0.0160 (3) | 0.0498 (17) | |
H30 | 0.0927 | 1.0148 | 0.0153 | 0.050* | |
C31 | 0.1246 (2) | 0.7958 (9) | 0.0474 (2) | 0.0432 (16) | |
H31 | 0.1492 | 0.8530 | 0.0674 | 0.043* | |
C32 | 0.0226 (3) | 1.0715 (13) | −0.0566 (4) | 0.096 (3) | |
H32A | −0.0041 | 1.1129 | −0.0796 | 0.096* | |
H32B | 0.0464 | 1.0884 | −0.0725 | 0.096* | |
H32C | 0.0284 | 1.1363 | −0.0245 | 0.096* | |
Cl1 | 0.0312 (3) | 0.1473 (10) | 0.3017 (3) | 0.273 (3) | |
C33 | 0.0000 | 0.269 (3) | 0.2500 | 0.260 (19) | |
H33B | 0.0196 | 0.3445 | 0.2369 | 0.260* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0413 (2) | 0.0292 (2) | 0.0299 (2) | 0.0002 (3) | 0.01264 (16) | −0.0033 (3) |
N1 | 0.045 (3) | 0.027 (3) | 0.040 (3) | 0.002 (2) | 0.015 (2) | −0.001 (2) |
N2 | 0.044 (4) | 0.086 (6) | 0.054 (4) | 0.007 (3) | 0.018 (3) | 0.011 (4) |
N3 | 0.049 (4) | 0.034 (3) | 0.066 (4) | −0.002 (3) | 0.019 (3) | −0.023 (3) |
N4 | 0.042 (3) | 0.036 (3) | 0.030 (3) | 0.005 (2) | 0.013 (2) | −0.001 (2) |
O1 | 0.045 (3) | 0.064 (4) | 0.068 (4) | −0.001 (3) | 0.005 (3) | −0.007 (3) |
O2 | 0.048 (3) | 0.214 (9) | 0.079 (4) | 0.000 (5) | 0.021 (3) | −0.029 (5) |
O3 | 0.058 (3) | 0.103 (5) | 0.073 (4) | −0.005 (3) | 0.014 (3) | −0.016 (4) |
O4 | 0.042 (2) | 0.034 (2) | 0.041 (2) | −0.001 (2) | 0.014 (2) | −0.012 (2) |
O5 | 0.064 (3) | 0.068 (4) | 0.074 (4) | 0.010 (3) | 0.002 (3) | 0.022 (3) |
C1 | 0.060 (5) | 0.063 (6) | 0.087 (6) | −0.008 (5) | −0.003 (5) | −0.011 (5) |
C2 | 0.045 (4) | 0.035 (4) | 0.048 (4) | 0.001 (3) | 0.010 (3) | −0.009 (3) |
C3 | 0.060 (5) | 0.038 (4) | 0.037 (4) | 0.012 (3) | 0.013 (3) | −0.005 (3) |
C4 | 0.054 (4) | 0.037 (4) | 0.044 (4) | −0.001 (3) | 0.025 (3) | −0.002 (3) |
C5 | 0.046 (4) | 0.027 (3) | 0.036 (3) | −0.001 (3) | 0.014 (3) | −0.006 (3) |
C6 | 0.058 (4) | 0.041 (4) | 0.037 (3) | 0.000 (3) | 0.015 (3) | 0.000 (3) |
C7 | 0.055 (4) | 0.042 (4) | 0.051 (4) | −0.008 (4) | 0.019 (3) | 0.001 (3) |
C8 | 0.055 (4) | 0.028 (3) | 0.030 (3) | −0.004 (3) | 0.009 (3) | −0.005 (3) |
C9 | 0.050 (4) | 0.020 (3) | 0.033 (3) | 0.002 (3) | 0.016 (3) | 0.002 (2) |
C10 | 0.053 (4) | 0.044 (4) | 0.033 (3) | 0.011 (3) | 0.012 (3) | −0.001 (3) |
C11 | 0.058 (5) | 0.050 (4) | 0.045 (4) | 0.023 (4) | 0.028 (3) | 0.011 (3) |
C12 | 0.044 (4) | 0.040 (4) | 0.042 (4) | 0.006 (3) | 0.012 (3) | 0.013 (3) |
C13 | 0.048 (4) | 0.035 (4) | 0.042 (3) | −0.002 (3) | 0.019 (3) | 0.002 (3) |
C14 | 0.040 (4) | 0.025 (3) | 0.038 (3) | 0.004 (3) | 0.016 (3) | 0.004 (3) |
C15 | 0.163 (10) | 0.035 (5) | 0.068 (6) | −0.010 (6) | 0.050 (6) | −0.012 (4) |
C16 | 0.067 (5) | 0.045 (4) | 0.054 (4) | 0.001 (4) | 0.036 (4) | −0.007 (3) |
C17 | 0.051 (4) | 0.045 (5) | 0.060 (4) | 0.021 (3) | 0.018 (3) | 0.006 (3) |
C18 | 0.048 (5) | 0.081 (6) | 0.081 (6) | −0.004 (5) | 0.011 (4) | −0.008 (5) |
C19 | 0.046 (3) | 0.027 (3) | 0.048 (3) | 0.002 (3) | 0.023 (3) | 0.000 (3) |
C20 | 0.041 (4) | 0.028 (3) | 0.044 (4) | −0.006 (3) | 0.018 (3) | −0.010 (3) |
C21 | 0.043 (4) | 0.032 (3) | 0.036 (3) | −0.007 (3) | 0.021 (3) | −0.002 (3) |
C22 | 0.043 (4) | 0.028 (3) | 0.044 (4) | −0.002 (3) | 0.017 (3) | −0.006 (3) |
C23 | 0.046 (4) | 0.038 (4) | 0.050 (4) | −0.004 (3) | 0.007 (3) | −0.020 (3) |
C24 | 0.058 (4) | 0.032 (4) | 0.058 (4) | −0.003 (3) | 0.018 (4) | −0.018 (3) |
C25 | 0.044 (3) | 0.044 (4) | 0.027 (3) | −0.005 (3) | 0.008 (3) | −0.001 (3) |
C26 | 0.044 (4) | 0.041 (4) | 0.032 (3) | 0.008 (3) | 0.018 (3) | −0.001 (3) |
C27 | 0.046 (4) | 0.047 (4) | 0.045 (4) | 0.001 (3) | 0.007 (3) | −0.002 (3) |
C28 | 0.044 (4) | 0.059 (5) | 0.050 (4) | −0.004 (4) | 0.005 (3) | −0.003 (4) |
C29 | 0.044 (4) | 0.061 (5) | 0.052 (4) | 0.002 (4) | 0.004 (3) | 0.001 (4) |
C30 | 0.062 (4) | 0.033 (4) | 0.055 (4) | 0.004 (4) | 0.017 (3) | 0.007 (4) |
C31 | 0.041 (4) | 0.042 (4) | 0.045 (4) | 0.000 (3) | 0.009 (3) | −0.002 (3) |
C32 | 0.069 (6) | 0.089 (8) | 0.122 (8) | 0.001 (6) | 0.011 (5) | 0.040 (7) |
Cl1 | 0.363 (9) | 0.213 (6) | 0.314 (8) | 0.011 (6) | 0.214 (7) | 0.000 (6) |
C33 | 0.58 (6) | 0.074 (15) | 0.16 (2) | 0.000 | 0.16 (3) | 0.000 |
Pd1—C14 | 1.984 (6) | C13—C14 | 1.382 (8) |
Pd1—N4 | 2.018 (5) | C13—H13 | 0.9300 |
Pd1—N1 | 2.049 (5) | C15—C16 | 1.499 (10) |
Pd1—O4 | 2.073 (4) | C15—H15A | 0.9600 |
N1—C8 | 1.291 (7) | C15—H15B | 0.9600 |
N1—C5 | 1.434 (8) | C15—H15C | 0.9600 |
N2—O3 | 1.201 (8) | C16—H16A | 0.9700 |
N2—O2 | 1.205 (8) | C16—H16B | 0.9700 |
N2—C12 | 1.474 (9) | C17—C18 | 1.513 (10) |
N3—C19 | 1.362 (8) | C17—H17A | 0.9700 |
N3—C17 | 1.443 (8) | C17—H17B | 0.9700 |
N3—C16 | 1.456 (8) | C18—H18A | 0.9600 |
N4—C25 | 1.298 (7) | C18—H18B | 0.9600 |
N4—C26 | 1.436 (8) | C18—H18C | 0.9600 |
O1—C2 | 1.352 (8) | C19—C20 | 1.392 (8) |
O1—C1 | 1.414 (9) | C19—C24 | 1.416 (9) |
O4—C21 | 1.300 (7) | C20—C21 | 1.407 (8) |
O5—C29 | 1.377 (8) | C20—H20 | 0.9300 |
O5—C32 | 1.392 (10) | C21—C22 | 1.414 (8) |
C1—H1A | 0.9600 | C22—C25 | 1.399 (8) |
C1—H1B | 0.9600 | C22—C23 | 1.421 (8) |
C1—H1C | 0.9600 | C23—C24 | 1.349 (9) |
C2—C3 | 1.380 (9) | C23—H23 | 0.9300 |
C2—C7 | 1.395 (9) | C24—H24 | 0.9300 |
C3—C4 | 1.383 (9) | C25—H25 | 0.9300 |
C3—H3 | 0.9300 | C26—C27 | 1.381 (9) |
C4—C5 | 1.362 (8) | C26—C31 | 1.383 (9) |
C4—H4 | 0.9300 | C27—C28 | 1.357 (9) |
C5—C6 | 1.382 (8) | C27—H27 | 0.9300 |
C6—C7 | 1.380 (9) | C28—C29 | 1.381 (11) |
C6—H6 | 0.9300 | C28—H28 | 0.9300 |
C7—H7 | 0.9300 | C29—C30 | 1.375 (10) |
C8—C9 | 1.441 (8) | C30—C31 | 1.385 (9) |
C8—H8 | 0.9300 | C30—H30 | 0.9300 |
C9—C14 | 1.401 (8) | C31—H31 | 0.9300 |
C9—C10 | 1.406 (8) | C32—H32A | 0.9600 |
C10—C11 | 1.378 (9) | C32—H32B | 0.9600 |
C10—H10 | 0.9300 | C32—H32C | 0.9600 |
C11—C12 | 1.368 (9) | Cl1—C33 | 1.736 (13) |
C11—H11 | 0.9300 | C33—Cl1i | 1.736 (12) |
C12—C13 | 1.395 (9) | C33—H33B | 0.9701 |
C14—Pd1—N4 | 96.9 (2) | C16—C15—H15C | 109.5 |
C14—Pd1—N1 | 80.6 (2) | H15A—C15—H15C | 109.5 |
N4—Pd1—N1 | 173.1 (2) | H15B—C15—H15C | 109.5 |
C14—Pd1—O4 | 168.2 (2) | N3—C16—C15 | 113.2 (6) |
N4—Pd1—O4 | 89.70 (18) | N3—C16—H16A | 108.9 |
N1—Pd1—O4 | 93.91 (18) | C15—C16—H16A | 108.9 |
C8—N1—C5 | 117.4 (5) | N3—C16—H16B | 108.9 |
C8—N1—Pd1 | 115.2 (4) | C15—C16—H16B | 108.9 |
C5—N1—Pd1 | 127.4 (4) | H16A—C16—H16B | 107.8 |
O3—N2—O2 | 122.6 (7) | N3—C17—C18 | 113.5 (6) |
O3—N2—C12 | 119.8 (6) | N3—C17—H17A | 108.9 |
O2—N2—C12 | 117.6 (7) | C18—C17—H17A | 108.9 |
C19—N3—C17 | 121.7 (5) | N3—C17—H17B | 108.9 |
C19—N3—C16 | 123.7 (6) | C18—C17—H17B | 108.9 |
C17—N3—C16 | 114.6 (6) | H17A—C17—H17B | 107.7 |
C25—N4—C26 | 115.3 (5) | C17—C18—H18A | 109.5 |
C25—N4—Pd1 | 121.8 (4) | C17—C18—H18B | 109.5 |
C26—N4—Pd1 | 122.7 (4) | H18A—C18—H18B | 109.5 |
C2—O1—C1 | 117.2 (6) | C17—C18—H18C | 109.5 |
C21—O4—Pd1 | 123.3 (4) | H18A—C18—H18C | 109.5 |
C29—O5—C32 | 118.0 (7) | H18B—C18—H18C | 109.5 |
O1—C1—H1A | 109.5 | N3—C19—C20 | 121.3 (6) |
O1—C1—H1B | 109.5 | N3—C19—C24 | 120.7 (6) |
H1A—C1—H1B | 109.5 | C20—C19—C24 | 118.0 (6) |
O1—C1—H1C | 109.5 | C19—C20—C21 | 122.8 (6) |
H1A—C1—H1C | 109.5 | C19—C20—H20 | 118.6 |
H1B—C1—H1C | 109.5 | C21—C20—H20 | 118.6 |
O1—C2—C3 | 125.4 (6) | O4—C21—C20 | 118.3 (6) |
O1—C2—C7 | 115.2 (6) | O4—C21—C22 | 123.3 (6) |
C3—C2—C7 | 119.4 (6) | C20—C21—C22 | 118.3 (6) |
C2—C3—C4 | 119.3 (6) | C25—C22—C21 | 124.4 (6) |
C2—C3—H3 | 120.4 | C25—C22—C23 | 117.3 (6) |
C4—C3—H3 | 120.4 | C21—C22—C23 | 117.7 (6) |
C5—C4—C3 | 121.6 (6) | C24—C23—C22 | 123.2 (6) |
C5—C4—H4 | 119.2 | C24—C23—H23 | 118.4 |
C3—C4—H4 | 119.2 | C22—C23—H23 | 118.4 |
C4—C5—C6 | 119.6 (6) | C23—C24—C19 | 119.9 (6) |
C4—C5—N1 | 120.1 (6) | C23—C24—H24 | 120.1 |
C6—C5—N1 | 120.3 (6) | C19—C24—H24 | 120.1 |
C7—C6—C5 | 119.8 (6) | N4—C25—C22 | 128.6 (6) |
C7—C6—H6 | 120.1 | N4—C25—H25 | 115.7 |
C5—C6—H6 | 120.1 | C22—C25—H25 | 115.7 |
C6—C7—C2 | 120.3 (6) | C27—C26—C31 | 118.1 (6) |
C6—C7—H7 | 119.8 | C27—C26—N4 | 123.2 (6) |
C2—C7—H7 | 119.8 | C31—C26—N4 | 118.7 (6) |
N1—C8—C9 | 115.3 (5) | C28—C27—C26 | 122.3 (7) |
N1—C8—H8 | 122.4 | C28—C27—H27 | 118.9 |
C9—C8—H8 | 122.4 | C26—C27—H27 | 118.9 |
C14—C9—C10 | 122.8 (6) | C27—C28—C29 | 119.5 (7) |
C14—C9—C8 | 116.0 (5) | C27—C28—H28 | 120.2 |
C10—C9—C8 | 121.1 (5) | C29—C28—H28 | 120.2 |
C11—C10—C9 | 119.4 (6) | C30—C29—O5 | 125.2 (7) |
C11—C10—H10 | 120.3 | C30—C29—C28 | 119.4 (7) |
C9—C10—H10 | 120.3 | O5—C29—C28 | 115.4 (7) |
C12—C11—C10 | 117.3 (6) | C29—C30—C31 | 120.6 (7) |
C12—C11—H11 | 121.4 | C29—C30—H30 | 119.7 |
C10—C11—H11 | 121.4 | C31—C30—H30 | 119.7 |
C11—C12—C13 | 124.3 (6) | C26—C31—C30 | 120.0 (7) |
C11—C12—N2 | 118.6 (6) | C26—C31—H31 | 120.0 |
C13—C12—N2 | 117.1 (6) | C30—C31—H31 | 120.0 |
C14—C13—C12 | 119.2 (6) | O5—C32—H32A | 109.5 |
C14—C13—H13 | 120.4 | O5—C32—H32B | 109.5 |
C12—C13—H13 | 120.4 | H32A—C32—H32B | 109.5 |
C13—C14—C9 | 116.9 (5) | O5—C32—H32C | 109.5 |
C13—C14—Pd1 | 129.9 (5) | H32A—C32—H32C | 109.5 |
C9—C14—Pd1 | 112.7 (4) | H32B—C32—H32C | 109.5 |
C16—C15—H15A | 109.5 | Cl1—C33—Cl1i | 115.6 (14) |
C16—C15—H15B | 109.5 | Cl1—C33—H33B | 108.3 |
H15A—C15—H15B | 109.5 | Cl1i—C33—H33B | 108.3 |
C16—N3—C19—C20 | −178.6 (6) | N1—C8—C9—C10 | 172.9 (6) |
C23—C22—C25—N4 | 172.1 (6) | O4—C21—C22—C25 | 8.5 (9) |
C22—C25—N4—C26 | 168.5 (6) | C21—C22—C25—N4 | −16.6 (10) |
C25—N4—C26—C31 | −130.0 (6) | C22—C25—N4—Pd1 | −6.2 (9) |
C6—C5—N1—C8 | −131.0 (6) | N1—C8—C9—C14 | −3.3 (8) |
C5—N1—C8—C9 | −177.0 (5) | C8—C9—C14—Pd1 | 0.4 (7) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C30H28N4O5Pd | [Pd(C14H11N2O3)(C18H21N2O2)]·0.5CH2Cl2 |
Mr | 630.96 | 701.48 |
Crystal system, space group | Orthorhombic, Pca21 | Monoclinic, C2/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 24.41 (2), 14.479 (6), 7.630 (4) | 31.582 (10), 7.5847 (10), 26.557 (6) |
α, β, γ (°) | 90, 90, 90 | 90, 104.96 (3), 90 |
V (Å3) | 2697 (3) | 6146 (3) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.74 | 0.74 |
Crystal size (mm) | 0.5 × 0.1 × 0.04 | 0.5 × 0.1 × 0.06 |
Data collection | ||
Diffractometer | Enraf Nonius MACH 3 diffractometer | Enraf-Nonius MACH3 diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.939, 1.000 | 0.952, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8378, 7823, 4033 | 7552, 7388, 3705 |
Rint | 0.054 | 0.060 |
(sin θ/λ)max (Å−1) | 0.703 | 0.660 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.124, 0.96 | 0.061, 0.151, 0.98 |
No. of reflections | 7823 | 7388 |
No. of parameters | 361 | 393 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.51 | 0.66, −0.75 |
Absolute structure | Flack (1983) | ? |
Absolute structure parameter | 0.11 (5) | ? |
Computer programs: MACH3 Software (Nonius, 1996), CELLDIM (Nonius, 1996), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1999).
Pd1—C7 | 2.014 (6) | C3—C8 | 1.400 (8) |
Pd1—N2 | 2.037 (5) | C4—C5 | 1.348 (9) |
Pd1—N3 | 2.055 (5) | C5—C6 | 1.393 (9) |
Pd1—O3 | 2.062 (4) | C6—C7 | 1.424 (8) |
N1—C3 | 1.366 (8) | C7—C8 | 1.392 (8) |
C3—C4 | 1.396 (9) | ||
C7—Pd1—N2 | 81.3 (2) | C10—N2—Pd1 | 127.3 (4) |
C7—Pd1—N3 | 100.3 (2) | C21—N3—Pd1 | 121.9 (4) |
N2—Pd1—N3 | 177.8 (2) | C26—O3—Pd1 | 120.5 (4) |
C7—Pd1—O3 | 173.0 (2) | C8—C7—C6 | 117.0 (6) |
N2—Pd1—O3 | 92.2 (2) | C8—C7—Pd1 | 131.8 (4) |
N3—Pd1—O3 | 86.2 (2) | C6—C7—Pd1 | 111.1 (5) |
C20—C21—N3—C24 | 133.4 (6) | C24—C25—C26—O3 | −9.6 (13) |
C21—N3—C24—C25 | −171.5 (6) | C25—C26—O3—Pd1 | −31.7 (13) |
N3—C24—C25—C30 | −166.9 (7) | C26—O3—Pd1—N2 | −135.2 (7) |
C5—C6—C9—N2 | −176.7 (7) | O3—Pd1—N2—C9 | −179.8 (5) |
C6—C9—N2—C10 | 178.5 (6) | Pd1—N2—C9—C6 | −2.8 (8) |
C9—N2—C10—C15 | −131.3 (7) | N2—C9—C6—C7 | 0.7 (9) |
N3—C24—C25—C26 | 22.1 (10) |
Pd1—C14 | 1.984 (6) | C19—C24 | 1.416 (9) |
Pd1—N4 | 2.018 (5) | C20—C21 | 1.407 (8) |
Pd1—N1 | 2.049 (5) | C21—C22 | 1.414 (8) |
Pd1—O4 | 2.073 (4) | C22—C23 | 1.421 (8) |
N3—C19 | 1.362 (8) | C23—C24 | 1.349 (9) |
C19—C20 | 1.392 (8) | ||
C14—Pd1—N4 | 96.9 (2) | C5—N1—Pd1 | 127.4 (4) |
C14—Pd1—N1 | 80.6 (2) | C26—N4—Pd1 | 122.7 (4) |
N4—Pd1—N1 | 173.1 (2) | C21—O4—Pd1 | 123.3 (4) |
C14—Pd1—O4 | 168.2 (2) | C13—C14—Pd1 | 129.9 (5) |
N4—Pd1—O4 | 89.70 (18) | C9—C14—Pd1 | 112.7 (4) |
N1—Pd1—O4 | 93.91 (18) | ||
C23—C22—C25—N4 | 172.1 (6) | O4—C21—C22—C25 | 8.5 (9) |
C22—C25—N4—C26 | 168.5 (6) | C21—C22—C25—N4 | −16.6 (10) |
C25—N4—C26—C31 | −130.0 (6) | C22—C25—N4—Pd1 | −6.2 (9) |
C6—C5—N1—C8 | −131.0 (6) | N1—C8—C9—C14 | −3.3 (8) |
C5—N1—C8—C9 | −177.0 (5) | C8—C9—C14—Pd1 | 0.4 (7) |
N1—C8—C9—C10 | 172.9 (6) |
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Organometallic complexes containing metallic centres bonded to organic π-electron conjugated systems are materials under investigation for applications in second-order non-linear optics (NLO). In comparison with all organic compounds, they show additional chemical variables (the nature of the metal, its oxidation state, coordination geometry etc.) that may lead, in principle, to enhanced NLO properties. Some interesting results have been reported for organometallic fragments attached at the end of organic conjugated systems and acting as electron donor or acceptor groups (Whittall et al., 1998).
A less investigated possibility is the use of metallic centres acting as conjugation bridges along push–pull systems (Buey et al., 1998). In this case, conjugation should involve π interactions between the metal and the organic ligands. This obviously poses some limitations on the nature of the metal, since its coordination geometry should allow, in the optimal case, a coplanar arrangement of the metal coordination sphere and of the organic conjugated ligands. Cyclometallated compounds (e.g. cyclometallated Schiff bases) seem a suitable choice since, in these compounds, a coplanar arrangement of metallated and ortho-aromatic rings must occur (Dehand & Pfeffer, 1976; Churchill et al., 1980); furthermore, aromatic imines may be easily functionalized with electron donor or acceptor groups, resulting in fairly highly NLO active compounds (Morley, 1995).
We have recently started a systematic investigation on the synthesis and structure of orthopalladated aromatic imines as precursors of fragments to be incorporated in polymers, and in the two complexes reported here, (I) and (II), a Pd atom is coordinated to two aromatic Schiff bases.
In both title compounds, the imines are functionalized with strong electron donor–acceptor groups. In particular, one imine is of the push–pull type and contains methoxy donor and nitro acceptor groups, while the second coordinated imine is of the electron-rich type as it contains only electron-donor groups (i.e. methoxy and dialkylamino). The two complexes substantially differ in the nature of the cyclometallated imine which is the push–pull group in the case of (I) and the electron-rich group in the case of (II). Furthermore, in both (I) and (II), the strongest electron-donor group (i.e. dialkylamino) and the nitro acceptor group are placed in opposite directions with respect to the Pd atom, so as to favour a charge transfer possibly involving the metal.
Both compounds show a strong absorption band in the UV-vis region which should correspond to the HOMO–LUMO transition (HOMO is highest occupied molecular orbital and LUMO is lowest unoccupied molecular orbital). A positive solvatochromic effect is observed for this band (see Experimental), as generally found in second-order NLO active compounds. The effect, though rather small, is comparable with values reported in the literature for other organometallic compounds (Di Bella et al., 1994). The NLO activity of the compounds has been tested by EFISH measurements in chloroform solution at λ = 1907 nm (Levine & Bethea, 1975). The values obtained, i.e. µβ = 120 × 10 -48 e.s.u. for (I) and µβ = 75 × 10 -48 e.s.u. for (II), indicate a moderate activity (Dalton et al., 1999) (esu = ?).
The coordination around the Pd atom is substantially square planar in both complexes, showing standard values for the distances from metal to coordinated atoms (O'Keefe & Steel, 2000). Of the two rings to which the metal atom belongs, the cyclopalladated (five-membered) ring is substantially planar, while the salicylaldiminate (six-membered) ring is not, mainly as a result of metal atom being out of the mean plane defined by the remaining five atoms. A planar-trigonal geometry is observed around the N atom of the amino group [N1 in (I) and N3 in (II)]. The sp2 hybridization of this atom should favour electron donation to the adjacent phenyl ring. This is consistent with the observed shortening of N1—C3 for (I) and N3—C19 for (II) (Allen et al., 1987) and with some distortions of bond lenghts observed in the phenyl ring attached to the dialkylamino group.
Deviations from coplanarity of the phenyl rings are observed in coordinated imines of both compounds through torsions around the bonds not constrained by coordination [i.e. N2—C10 and N3—C21 in (I), and N4—C26 and N1—C5 in (II)]. These deviations seem to be due to internal steric repulsions [C9···C11 2.95 (1) Å and C22···C24 2.916 (9) Å for (I); C4···C8 2.871 (9) Å and C25···C27 2.902 (9) Å for (II)], but also to short contacts involving atoms of different ligands [C8···C20 3.44 (1) Å, C8···C21 3.237 (9) Å and O3···C15 2.929 (9) Å for (I); C13···C26 3.12 (1) Å and C13···C31 3.44 (1) Å for (II)]. These contacts, in particular those involving atoms of different ligands, probably also play a role in determining the non-planar conformation of the six-membered ring containing the Pd atom.
In the case of (II), solvent molecules (dichloromethane) in special positions (binary axis) are also present in the crystals. Although the C and Cl atoms of the solvent molecule have high anisotropic displacement parameters, no evidence of static disorder was found.