Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100011768/de1153sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100011768/de1153IIsup2.hkl |
CCDC reference: 156151
Complex (II) was prepared as previously described (De Geest et al., 1999). Crystals were obtained by slow evaporation of an acetonitrile solution. Not CHCl3?
Crystal decay was monitored by the measurement of duplicate reflections. The chloroform and water solvate molecules were disordered over three and two sites, respectively. The chloroform molecules were restrained to have the same geometry and their site occupancies refined to sum to 1.0. The H atoms of the water solvate molecules were not included in the refinement; other H atoms were treated as riding?
Data collection: SMART (Siemens 1999); cell refinement: SAINT (Siemens 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.
Fig. 1. A perspective view and of (II) with the atom-labelling scheme. H atoms and solvate molecules are omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. |
[Pd4(C16H10N2O2)2(C2H3O2)4]·2CHCl3·2H2O | F(000) = 1432 |
Mr = 1461.06 | Dx = 1.861 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.225 (5) Å | Cell parameters from 6111 reflections |
b = 15.052 (5) Å | θ = 2.2–26.4° |
c = 14.135 (5) Å | µ = 1.74 mm−1 |
β = 91.797 (5)° | T = 168 K |
V = 2599.7 (16) Å3 | Plate, yellow |
Z = 2 | 0.38 × 0.35 × 0.04 mm |
Siemens SMART CCD diffractometer | 5261 independent reflections |
Radiation source: fine-focus sealed tube | 3476 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.089 |
Detector resolution: 8.19 pixels mm-1 | θmax = 26.4°, θmin = 2.2° |
Exposures over 0.5° ϕ or ω rotation scans | h = −15→15 |
Absorption correction: multi-scan (SADABS; Siemens, 1999) | k = −18→13 |
Tmin = 0.559, Tmax = 0.934 | l = −17→17 |
26967 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)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.134 | w = 1/[σ2(Fo2) + (0.0748P)2 + 0.2065P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.027 |
5261 reflections | Δρmax = 0.96 e Å−3 |
404 parameters | Δρmin = −0.95 e Å−3 |
145 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: 0.0010 (3) |
[Pd4(C16H10N2O2)2(C2H3O2)4]·2CHCl3·2H2O | V = 2599.7 (16) Å3 |
Mr = 1461.06 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.225 (5) Å | µ = 1.74 mm−1 |
b = 15.052 (5) Å | T = 168 K |
c = 14.135 (5) Å | 0.38 × 0.35 × 0.04 mm |
β = 91.797 (5)° |
Siemens SMART CCD diffractometer | 5261 independent reflections |
Absorption correction: multi-scan (SADABS; Siemens, 1999) | 3476 reflections with I > 2σ(I) |
Tmin = 0.559, Tmax = 0.934 | Rint = 0.089 |
26967 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 145 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.96 e Å−3 |
5261 reflections | Δρmin = −0.95 e Å−3 |
404 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pd1 | 0.31144 (4) | 0.54255 (3) | 0.19048 (4) | 0.02685 (17) | |
Pd2 | 0.80465 (4) | 0.49483 (3) | −0.01135 (4) | 0.02634 (17) | |
C1 | 0.5411 (6) | 0.5935 (4) | 0.1517 (5) | 0.0289 (15) | |
C2 | 0.4638 (5) | 0.5269 (4) | 0.1499 (5) | 0.0262 (15) | |
C3 | 0.4986 (6) | 0.4466 (4) | 0.1102 (4) | 0.0285 (15) | |
H3 | 0.4501 | 0.3973 | 0.1079 | 0.034* | |
C4 | 0.6020 (6) | 0.4377 (4) | 0.0746 (4) | 0.0248 (15) | |
C5 | 0.6764 (6) | 0.5074 (4) | 0.0677 (5) | 0.0282 (15) | |
C6 | 0.6432 (5) | 0.5865 (5) | 0.1103 (4) | 0.0285 (15) | |
H6 | 0.6909 | 0.6363 | 0.1111 | 0.034* | |
O1 | 0.5244 (4) | 0.6767 (3) | 0.1959 (4) | 0.0400 (13) | |
N11 | 0.3325 (5) | 0.6772 (4) | 0.1852 (4) | 0.0317 (14) | |
C12 | 0.4276 (6) | 0.7198 (4) | 0.1953 (5) | 0.0335 (17) | |
C13 | 0.4343 (7) | 0.8120 (5) | 0.2058 (6) | 0.043 (2) | |
H13 | 0.5033 | 0.8402 | 0.2153 | 0.052* | |
C14 | 0.3410 (7) | 0.8603 (5) | 0.2024 (6) | 0.050 (2) | |
H14 | 0.3436 | 0.9229 | 0.2105 | 0.060* | |
C15 | 0.2414 (8) | 0.8177 (5) | 0.1868 (6) | 0.051 (2) | |
H15 | 0.1753 | 0.8507 | 0.1808 | 0.061* | |
C16 | 0.2405 (6) | 0.7285 (5) | 0.1805 (5) | 0.0401 (19) | |
H16 | 0.1718 | 0.6995 | 0.1722 | 0.048* | |
O4 | 0.6256 (4) | 0.3517 (3) | 0.0401 (3) | 0.0317 (11) | |
N41 | 0.8167 (4) | 0.3706 (4) | 0.0396 (4) | 0.0281 (13) | |
C42 | 0.7275 (6) | 0.3184 (4) | 0.0505 (4) | 0.0273 (15) | |
C43 | 0.7377 (7) | 0.2288 (5) | 0.0704 (5) | 0.0369 (17) | |
H43 | 0.6741 | 0.1933 | 0.0761 | 0.044* | |
C44 | 0.8405 (7) | 0.1908 (5) | 0.0821 (5) | 0.0422 (19) | |
H44 | 0.8483 | 0.1293 | 0.0960 | 0.051* | |
C45 | 0.9317 (7) | 0.2445 (5) | 0.0731 (6) | 0.045 (2) | |
H45 | 1.0030 | 0.2201 | 0.0818 | 0.054* | |
C46 | 0.9191 (6) | 0.3336 (5) | 0.0513 (5) | 0.0383 (18) | |
H46 | 0.9820 | 0.3697 | 0.0444 | 0.046* | |
O1A | 0.2912 (4) | 0.4079 (3) | 0.2043 (3) | 0.0308 (11) | |
C1A | 0.2491 (5) | 0.3557 (5) | 0.1423 (5) | 0.0299 (16) | |
C2A | 0.2488 (8) | 0.2582 (5) | 0.1683 (7) | 0.059 (3) | |
H2A1 | 0.2193 | 0.2509 | 0.2315 | 0.089* | |
H2A2 | 0.3238 | 0.2351 | 0.1681 | 0.089* | |
H2A3 | 0.2031 | 0.2254 | 0.1220 | 0.089* | |
O2A | 0.2103 (4) | 0.3768 (3) | 0.0619 (3) | 0.0319 (11) | |
O1B | 0.1448 (4) | 0.5543 (3) | 0.2377 (3) | 0.0375 (12) | |
C1B | 0.0596 (6) | 0.5397 (5) | 0.1865 (5) | 0.0319 (16) | |
C2B | −0.0502 (7) | 0.5541 (7) | 0.2334 (6) | 0.063 (3) | |
H2B1 | −0.0727 | 0.6162 | 0.2256 | 0.094* | |
H2B2 | −0.0425 | 0.5401 | 0.3009 | 0.094* | |
H2B3 | −0.1056 | 0.5152 | 0.2036 | 0.094* | |
O2B | 0.0568 (4) | 0.5231 (3) | 0.1003 (3) | 0.0368 (12) | |
C70 | 0.8801 (19) | 0.8743 (11) | 0.1312 (12) | 0.056 (8) | 0.365 (3) |
H70 | 0.8167 | 0.9071 | 0.1576 | 0.067* | 0.365 (3) |
Cl71 | 0.9690 (4) | 0.8403 (4) | 0.2261 (4) | 0.0492 (16) | 0.365 (3) |
Cl72 | 0.8314 (6) | 0.7779 (5) | 0.0740 (5) | 0.062 (2) | 0.365 (3) |
Cl73 | 0.9463 (7) | 0.9439 (4) | 0.0506 (5) | 0.069 (2) | 0.365 (3) |
C80 | 0.7814 (14) | 0.5897 (10) | 0.5848 (12) | 0.115 (6) | 0.416 (7) |
H80 | 0.7607 | 0.5495 | 0.6377 | 0.138* | 0.416 (7) |
Cl81 | 0.6787 (9) | 0.6717 (5) | 0.5660 (6) | 0.105 (4) | 0.416 (7) |
Cl82 | 0.7915 (16) | 0.5281 (7) | 0.4797 (7) | 0.246 (10) | 0.416 (7) |
Cl83 | 0.9089 (11) | 0.6404 (11) | 0.6123 (13) | 0.233 (8) | 0.416 (7) |
C90 | 0.665 (2) | 0.6198 (14) | 0.560 (3) | 0.134 (11) | 0.219 (7) |
H90 | 0.6386 | 0.6087 | 0.6251 | 0.160* | 0.219 (7) |
Cl91 | 0.5664 (17) | 0.6846 (10) | 0.5001 (12) | 0.131 (7) | 0.219 (7) |
Cl92 | 0.684 (3) | 0.5162 (10) | 0.5068 (15) | 0.181 (13) | 0.219 (7) |
Cl93 | 0.789 (2) | 0.6790 (17) | 0.573 (2) | 0.204 (13) | 0.219 (7) |
O70A | 0.5919 (19) | 0.5102 (14) | 0.5751 (14) | 0.032 (7) | 0.26 (2) |
O70B | 0.5147 (11) | 0.4590 (7) | 0.5992 (5) | 0.080 (6) | 0.74 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0298 (3) | 0.0248 (3) | 0.0261 (3) | −0.0027 (2) | 0.0015 (2) | −0.0019 (2) |
Pd2 | 0.0293 (3) | 0.0236 (3) | 0.0261 (3) | −0.0025 (2) | 0.0013 (2) | 0.0020 (2) |
C1 | 0.039 (4) | 0.020 (3) | 0.027 (4) | −0.003 (3) | −0.004 (3) | −0.006 (3) |
C2 | 0.028 (4) | 0.026 (4) | 0.024 (3) | −0.003 (3) | −0.002 (3) | 0.002 (3) |
C3 | 0.037 (4) | 0.022 (3) | 0.026 (3) | −0.006 (3) | −0.005 (3) | 0.003 (3) |
C4 | 0.033 (4) | 0.015 (3) | 0.026 (3) | −0.002 (3) | −0.003 (3) | 0.003 (3) |
C5 | 0.036 (4) | 0.024 (3) | 0.024 (3) | −0.006 (3) | −0.007 (3) | 0.000 (3) |
C6 | 0.029 (4) | 0.030 (4) | 0.027 (3) | −0.008 (3) | 0.002 (3) | −0.006 (3) |
O1 | 0.033 (3) | 0.030 (3) | 0.056 (3) | −0.005 (2) | 0.002 (2) | −0.019 (2) |
N11 | 0.036 (4) | 0.030 (3) | 0.030 (3) | −0.002 (3) | 0.003 (3) | −0.001 (3) |
C12 | 0.044 (5) | 0.028 (4) | 0.028 (4) | −0.005 (3) | 0.002 (3) | −0.007 (3) |
C13 | 0.054 (5) | 0.027 (4) | 0.049 (5) | −0.007 (4) | −0.004 (4) | −0.010 (4) |
C14 | 0.075 (7) | 0.029 (4) | 0.045 (5) | 0.005 (4) | −0.003 (4) | −0.005 (4) |
C15 | 0.068 (6) | 0.037 (5) | 0.047 (5) | 0.012 (4) | −0.012 (4) | −0.003 (4) |
C16 | 0.041 (5) | 0.038 (4) | 0.041 (4) | 0.003 (4) | −0.006 (4) | −0.004 (4) |
O4 | 0.041 (3) | 0.018 (2) | 0.037 (3) | −0.001 (2) | 0.001 (2) | −0.001 (2) |
N41 | 0.032 (3) | 0.027 (3) | 0.026 (3) | 0.002 (3) | 0.002 (2) | −0.001 (2) |
C42 | 0.034 (4) | 0.026 (4) | 0.022 (3) | −0.002 (3) | 0.000 (3) | 0.004 (3) |
C43 | 0.047 (5) | 0.025 (4) | 0.039 (4) | −0.002 (3) | 0.004 (4) | 0.000 (3) |
C44 | 0.062 (6) | 0.027 (4) | 0.038 (4) | 0.007 (4) | 0.007 (4) | 0.004 (3) |
C45 | 0.050 (5) | 0.040 (5) | 0.045 (5) | 0.016 (4) | −0.005 (4) | 0.004 (4) |
C46 | 0.035 (4) | 0.040 (4) | 0.039 (4) | 0.006 (3) | −0.004 (3) | 0.000 (3) |
O1A | 0.034 (3) | 0.028 (3) | 0.031 (3) | −0.005 (2) | 0.001 (2) | 0.001 (2) |
C1A | 0.023 (4) | 0.029 (4) | 0.037 (4) | −0.004 (3) | −0.001 (3) | 0.003 (3) |
C2A | 0.078 (7) | 0.030 (4) | 0.069 (6) | −0.012 (4) | −0.025 (5) | 0.014 (4) |
O2A | 0.038 (3) | 0.024 (2) | 0.033 (3) | −0.004 (2) | −0.002 (2) | 0.001 (2) |
O1B | 0.035 (3) | 0.041 (3) | 0.037 (3) | −0.001 (2) | 0.004 (2) | −0.009 (2) |
C1B | 0.031 (4) | 0.043 (4) | 0.021 (3) | 0.002 (3) | 0.007 (3) | 0.001 (3) |
C2B | 0.034 (5) | 0.094 (8) | 0.061 (6) | 0.000 (5) | 0.015 (4) | −0.022 (5) |
O2B | 0.031 (3) | 0.041 (3) | 0.038 (3) | −0.002 (2) | 0.004 (2) | 0.003 (2) |
C70 | 0.052 (18) | 0.015 (10) | 0.102 (18) | −0.017 (11) | −0.005 (12) | 0.016 (10) |
Cl71 | 0.031 (3) | 0.051 (3) | 0.065 (4) | 0.003 (2) | 0.001 (3) | −0.011 (3) |
Cl72 | 0.087 (5) | 0.059 (4) | 0.039 (3) | −0.031 (4) | 0.009 (3) | 0.002 (3) |
Cl73 | 0.114 (6) | 0.035 (3) | 0.061 (4) | −0.027 (3) | 0.052 (4) | −0.021 (3) |
C80 | 0.218 (15) | 0.041 (13) | 0.092 (14) | 0.054 (10) | 0.101 (16) | 0.052 (8) |
Cl81 | 0.183 (9) | 0.055 (4) | 0.081 (5) | 0.047 (5) | 0.053 (6) | 0.016 (4) |
Cl82 | 0.54 (3) | 0.097 (7) | 0.109 (7) | 0.178 (11) | 0.180 (12) | 0.045 (5) |
Cl83 | 0.137 (9) | 0.234 (16) | 0.334 (19) | 0.038 (10) | 0.116 (11) | 0.161 (12) |
C90 | 0.22 (3) | 0.08 (2) | 0.11 (3) | 0.002 (19) | 0.09 (3) | 0.024 (19) |
Cl91 | 0.216 (19) | 0.078 (10) | 0.103 (13) | −0.014 (10) | 0.069 (12) | 0.011 (9) |
Cl92 | 0.36 (4) | 0.083 (11) | 0.091 (14) | 0.029 (14) | −0.11 (2) | −0.009 (10) |
Cl93 | 0.28 (2) | 0.18 (2) | 0.15 (2) | −0.07 (2) | 0.01 (2) | −0.01 (2) |
O70A | 0.039 (10) | 0.035 (9) | 0.021 (9) | 0.021 (6) | −0.008 (6) | 0.010 (6) |
O70B | 0.144 (12) | 0.069 (8) | 0.028 (4) | 0.076 (8) | 0.004 (5) | −0.004 (4) |
Pd1—C2 | 1.980 (7) | O4—C42 | 1.346 (8) |
Pd1—N11 | 2.044 (6) | N41—C42 | 1.356 (8) |
Pd1—O1A | 2.052 (5) | N41—C46 | 1.375 (9) |
Pd1—O1B | 2.171 (5) | C42—C43 | 1.383 (9) |
Pd1—Pd2i | 2.9182 (11) | C43—C44 | 1.386 (10) |
Pd2—C5 | 1.962 (7) | C44—C45 | 1.387 (11) |
Pd2—N41 | 2.007 (5) | C45—C46 | 1.383 (10) |
Pd2—O2Ai | 2.067 (4) | O1A—C1A | 1.273 (8) |
Pd2—O2Bi | 2.158 (5) | C1A—O2A | 1.258 (8) |
Pd2—Pd1i | 2.9182 (11) | C1A—C2A | 1.514 (9) |
C1—C2 | 1.378 (9) | O2A—Pd2i | 2.067 (4) |
C1—C6 | 1.399 (9) | O1B—C1B | 1.269 (8) |
C1—O1 | 1.417 (8) | C1B—O2B | 1.243 (8) |
C2—C3 | 1.403 (9) | C1B—C2B | 1.531 (10) |
C3—C4 | 1.381 (10) | O2B—Pd2i | 2.158 (5) |
C4—C5 | 1.395 (9) | C70—Cl72 | 1.756 (14) |
C4—O4 | 1.417 (7) | C70—Cl73 | 1.763 (15) |
C5—C6 | 1.400 (9) | C70—Cl71 | 1.775 (14) |
O1—C12 | 1.350 (9) | C80—Cl82 | 1.759 (13) |
N11—C12 | 1.332 (9) | C80—Cl83 | 1.767 (14) |
N11—C16 | 1.364 (9) | C80—Cl81 | 1.774 (13) |
C12—C13 | 1.398 (9) | C90—Cl92 | 1.749 (16) |
C13—C14 | 1.352 (11) | C90—Cl91 | 1.752 (16) |
C14—C15 | 1.388 (11) | C90—Cl93 | 1.763 (16) |
C15—C16 | 1.346 (10) | ||
C2—Pd1—N11 | 89.3 (2) | N11—C12—O1 | 122.2 (6) |
C2—Pd1—O1A | 91.6 (2) | N11—C12—C13 | 122.6 (7) |
N11—Pd1—O1A | 176.6 (2) | O1—C12—C13 | 115.3 (7) |
C2—Pd1—O1B | 177.6 (2) | C14—C13—C12 | 118.9 (8) |
N11—Pd1—O1B | 92.9 (2) | C13—C14—C15 | 119.5 (7) |
O1A—Pd1—O1B | 86.22 (18) | C16—C15—C14 | 118.5 (8) |
C2—Pd1—Pd2i | 99.30 (18) | C15—C16—N11 | 123.8 (8) |
N11—Pd1—Pd2i | 102.59 (16) | C42—O4—C4 | 120.0 (5) |
O1A—Pd1—Pd2i | 80.51 (12) | C42—N41—C46 | 118.9 (6) |
O1B—Pd1—Pd2i | 81.20 (13) | C42—N41—Pd2 | 122.0 (4) |
C5—Pd2—N41 | 86.4 (2) | C46—N41—Pd2 | 118.5 (5) |
C5—Pd2—O2Ai | 92.5 (2) | O4—C42—N41 | 121.1 (6) |
N41—Pd2—O2Ai | 178.8 (2) | O4—C42—C43 | 117.5 (6) |
C5—Pd2—O2Bi | 178.1 (2) | N41—C42—C43 | 121.3 (6) |
N41—Pd2—O2Bi | 92.5 (2) | C42—C43—C44 | 120.2 (7) |
O2Ai—Pd2—O2Bi | 88.71 (18) | C43—C44—C45 | 118.4 (7) |
C5—Pd2—Pd1i | 97.88 (19) | C46—C45—C44 | 120.1 (7) |
N41—Pd2—Pd1i | 99.20 (15) | N41—C46—C45 | 121.0 (7) |
O2Ai—Pd2—Pd1i | 81.09 (12) | C1A—O1A—Pd1 | 126.2 (4) |
O2Bi—Pd2—Pd1i | 80.77 (13) | O2A—C1A—O1A | 126.8 (6) |
C2—C1—C6 | 123.9 (6) | O2A—C1A—C2A | 117.3 (6) |
C2—C1—O1 | 122.9 (6) | O1A—C1A—C2A | 115.8 (6) |
C6—C1—O1 | 113.2 (6) | C1A—O2A—Pd2i | 125.0 (4) |
C1—C2—C3 | 114.7 (6) | C1B—O1B—Pd1 | 124.9 (4) |
C1—C2—Pd1 | 124.0 (5) | O2B—C1B—O1B | 126.2 (6) |
C3—C2—Pd1 | 121.2 (5) | O2B—C1B—C2B | 117.1 (7) |
C4—C3—C2 | 121.4 (6) | O1B—C1B—C2B | 116.3 (6) |
C3—C4—C5 | 124.0 (6) | C1B—O2B—Pd2i | 126.7 (5) |
C3—C4—O4 | 114.4 (5) | Cl72—C70—Cl73 | 110.4 (11) |
C5—C4—O4 | 121.5 (6) | Cl72—C70—Cl71 | 107.4 (9) |
C4—C5—C6 | 114.2 (6) | Cl73—C70—Cl71 | 112.1 (11) |
C4—C5—Pd2 | 120.2 (5) | Cl82—C80—Cl83 | 109.2 (10) |
C6—C5—Pd2 | 125.1 (5) | Cl82—C80—Cl81 | 107.9 (9) |
C1—C6—C5 | 121.3 (6) | Cl83—C80—Cl81 | 110.4 (9) |
C12—O1—C1 | 124.0 (5) | Cl92—C90—Cl91 | 112.5 (14) |
C12—N11—C16 | 116.6 (6) | Cl92—C90—Cl93 | 112.0 (14) |
C12—N11—Pd1 | 125.7 (5) | Cl91—C90—Cl93 | 110.3 (14) |
C16—N11—Pd1 | 117.3 (5) | ||
C6—C1—C2—C3 | 5.6 (10) | O1—C12—C13—C14 | 177.6 (7) |
O1—C1—C2—C3 | −174.6 (6) | C12—C13—C14—C15 | −1.1 (12) |
C6—C1—C2—Pd1 | −170.1 (5) | C13—C14—C15—C16 | 3.4 (12) |
O1—C1—C2—Pd1 | 9.6 (9) | C14—C15—C16—N11 | −2.3 (12) |
N11—Pd1—C2—C1 | 15.1 (6) | C12—N11—C16—C15 | −1.1 (11) |
O1A—Pd1—C2—C1 | −161.6 (6) | Pd1—N11—C16—C15 | 172.6 (6) |
Pd2i—Pd1—C2—C1 | 117.8 (5) | C3—C4—O4—C42 | −144.7 (6) |
N11—Pd1—C2—C3 | −160.4 (5) | C5—C4—O4—C42 | 38.5 (8) |
O1A—Pd1—C2—C3 | 22.9 (5) | C5—Pd2—N41—C42 | 41.5 (5) |
Pd2i—Pd1—C2—C3 | −57.7 (5) | O2Bi—Pd2—N41—C42 | −137.0 (5) |
C1—C2—C3—C4 | −1.3 (9) | Pd1i—Pd2—N41—C42 | −55.9 (5) |
Pd1—C2—C3—C4 | 174.6 (5) | C5—Pd2—N41—C46 | −147.6 (5) |
C2—C3—C4—C5 | −5.3 (10) | O2Bi—Pd2—N41—C46 | 33.9 (5) |
C2—C3—C4—O4 | 178.0 (5) | Pd1i—Pd2—N41—C46 | 115.0 (5) |
C3—C4—C5—C6 | 7.2 (9) | C4—O4—C42—N41 | −39.1 (8) |
O4—C4—C5—C6 | −176.3 (5) | C4—O4—C42—C43 | 142.4 (6) |
C3—C4—C5—Pd2 | −164.9 (5) | C46—N41—C42—O4 | 179.7 (6) |
O4—C4—C5—Pd2 | 11.6 (8) | Pd2—N41—C42—O4 | −9.4 (8) |
N41—Pd2—C5—C4 | −40.8 (5) | C46—N41—C42—C43 | −1.8 (9) |
O2Ai—Pd2—C5—C4 | 139.4 (5) | Pd2—N41—C42—C43 | 169.1 (5) |
Pd1i—Pd2—C5—C4 | 58.1 (5) | O4—C42—C43—C44 | −179.8 (6) |
N41—Pd2—C5—C6 | 148.0 (6) | N41—C42—C43—C44 | 1.6 (10) |
O2Ai—Pd2—C5—C6 | −31.8 (6) | C42—C43—C44—C45 | −0.2 (11) |
Pd1i—Pd2—C5—C6 | −113.2 (6) | C43—C44—C45—C46 | −1.0 (11) |
C2—C1—C6—C5 | −3.6 (10) | C42—N41—C46—C45 | 0.6 (10) |
O1—C1—C6—C5 | 176.6 (6) | Pd2—N41—C46—C45 | −170.6 (5) |
C4—C5—C6—C1 | −2.8 (9) | C44—C45—C46—N41 | 0.9 (11) |
Pd2—C5—C6—C1 | 168.8 (5) | C2—Pd1—O1A—C1A | −95.3 (6) |
C2—C1—O1—C12 | −36.9 (10) | N11—Pd1—O1A—C1A | 161 (3) |
C6—C1—O1—C12 | 142.8 (7) | O1B—Pd1—O1A—C1A | 85.6 (5) |
C2—Pd1—N11—C12 | −25.9 (6) | Pd2i—Pd1—O1A—C1A | 3.9 (5) |
O1B—Pd1—N11—C12 | 153.1 (6) | Pd1—O1A—C1A—O2A | −1.5 (10) |
Pd2i—Pd1—N11—C12 | −125.2 (5) | Pd1—O1A—C1A—C2A | 177.1 (5) |
C2—Pd1—N11—C16 | 161.1 (5) | O1A—C1A—O2A—Pd2i | −4.1 (10) |
O1B—Pd1—N11—C16 | −19.9 (5) | C2A—C1A—O2A—Pd2i | 177.4 (5) |
Pd2i—Pd1—N11—C16 | 61.7 (5) | N11—Pd1—O1B—C1B | 105.9 (6) |
C16—N11—C12—O1 | −176.5 (6) | O1A—Pd1—O1B—C1B | −77.4 (6) |
Pd1—N11—C12—O1 | 10.4 (10) | Pd2i—Pd1—O1B—C1B | 3.6 (5) |
C16—N11—C12—C13 | 3.5 (10) | Pd1—O1B—C1B—O2B | −5.8 (10) |
Pd1—N11—C12—C13 | −169.6 (5) | Pd1—O1B—C1B—C2B | −178.6 (5) |
C1—O1—C12—N11 | 25.5 (10) | O1B—C1B—O2B—Pd2i | 4.3 (11) |
C1—O1—C12—C13 | −154.5 (6) | C2B—C1B—O2B—Pd2i | 177.0 (5) |
N11—C12—C13—C14 | −2.4 (11) |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Pd4(C16H10N2O2)2(C2H3O2)4]·2CHCl3·2H2O |
Mr | 1461.06 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 168 |
a, b, c (Å) | 12.225 (5), 15.052 (5), 14.135 (5) |
β (°) | 91.797 (5) |
V (Å3) | 2599.7 (16) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.74 |
Crystal size (mm) | 0.38 × 0.35 × 0.04 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Siemens, 1999) |
Tmin, Tmax | 0.559, 0.934 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26967, 5261, 3476 |
Rint | 0.089 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.134, 1.03 |
No. of reflections | 5261 |
No. of parameters | 404 |
No. of restraints | 145 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.96, −0.95 |
Computer programs: SMART (Siemens 1999), SAINT (Siemens 1999), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97.
Pd1—C2 | 1.980 (7) | C2—C3 | 1.403 (9) |
Pd1—N11 | 2.044 (6) | C3—C4 | 1.381 (10) |
Pd1—O1A | 2.052 (5) | C4—C5 | 1.395 (9) |
Pd1—O1B | 2.171 (5) | C4—O4 | 1.417 (7) |
Pd2—C5 | 1.962 (7) | C5—C6 | 1.400 (9) |
Pd2—N41 | 2.007 (5) | O1A—C1A | 1.273 (8) |
Pd2—O2Ai | 2.067 (4) | C1A—O2A | 1.258 (8) |
Pd2—O2Bi | 2.158 (5) | C1A—C2A | 1.514 (9) |
C1—C2 | 1.378 (9) | O1B—C1B | 1.269 (8) |
C1—C6 | 1.399 (9) | C1B—O2B | 1.243 (8) |
C1—O1 | 1.417 (8) | C1B—C2B | 1.531 (10) |
C2—Pd1—N11 | 89.3 (2) | C3—C4—C5 | 124.0 (6) |
C2—Pd1—O1A | 91.6 (2) | C3—C4—O4 | 114.4 (5) |
N11—Pd1—O1A | 176.6 (2) | C5—C4—O4 | 121.5 (6) |
C2—Pd1—O1B | 177.6 (2) | C4—C5—C6 | 114.2 (6) |
N11—Pd1—O1B | 92.9 (2) | C4—C5—Pd2 | 120.2 (5) |
O1A—Pd1—O1B | 86.22 (18) | C6—C5—Pd2 | 125.1 (5) |
C5—Pd2—N41 | 86.4 (2) | C1—C6—C5 | 121.3 (6) |
C5—Pd2—O2Ai | 92.5 (2) | C12—O1—C1 | 124.0 (5) |
N41—Pd2—O2Ai | 178.8 (2) | C42—O4—C4 | 120.0 (5) |
C5—Pd2—O2Bi | 178.1 (2) | C1A—O1A—Pd1 | 126.2 (4) |
N41—Pd2—O2Bi | 92.5 (2) | O2A—C1A—O1A | 126.8 (6) |
O2Ai—Pd2—O2Bi | 88.71 (18) | O2A—C1A—C2A | 117.3 (6) |
C2—C1—C6 | 123.9 (6) | O1A—C1A—C2A | 115.8 (6) |
C2—C1—O1 | 122.9 (6) | C1A—O2A—Pd2i | 125.0 (4) |
C6—C1—O1 | 113.2 (6) | C1B—O1B—Pd1 | 124.9 (4) |
C1—C2—C3 | 114.7 (6) | O2B—C1B—O1B | 126.2 (6) |
C1—C2—Pd1 | 124.0 (5) | O2B—C1B—C2B | 117.1 (7) |
C3—C2—Pd1 | 121.2 (5) | O1B—C1B—C2B | 116.3 (6) |
C4—C3—C2 | 121.4 (6) | C1B—O2B—Pd2i | 126.7 (5) |
Symmetry code: (i) −x+1, −y+1, −z. |
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For some time we have been interested in the preparation of doubly cyclopalladated compounds (O'Keefe & Steel, 1999), particularly examples involving the double cyclopalladation of a single benzene ring (Caygill & Steel, 1990; Phillips & Steel, 1991; Hartshorn & Steel, 1998). Recently, we reported the cyclopalladation chemistry of all three isomers of bis(2-pyridyloxy)benzene (De Geest et al., 1999). We described therein the preparation of the dinuclear complex, (III), which, due to its insolubilty in common NMR solvents, we were only able to characterize by elemental analysis and mass spectrometry. This complex was prepared (see Scheme) by reaction of 1,4-bis(2-pyridyloxy)benzene, (I), with palladium acetate to give an intermediate, (II), which was converted to the corresponding chloride by metathesis and thereafter to the acetylacetonate complex, (III). The nature of the initially formed product, (II), was a subject of doubt. Related acetate-bridged species have generally been considered to be polymeric in nature (Lydon & Rourke, 1997; Vicente et al., 1997), but we proposed that (II) is a tetranuclear species, based on our previous determination of the structure of the product of the reaction of palladium acetate with 1,4-bis(benzothiazol-2-yl)benzene (O'Keefe & Steel, 1998). To resolve this ambiguity, we now report the X-ray crystal structure of (II), which we have since managed to crystallize by slow evaporation from a chloroform solution. \sch
Complex (II) crystallizes in the monoclinic space group P21/c, the asymmetric unit containing one doubly-palladated molecule of (I), two Pd atoms, two acetates, a molecule of chloroform disordered over three sites and a molecule of water disordered over two sites. The two cyclopalladated units are positioned about a centre of inversion with four acetates bridging the four Pd atoms, so that the molecular structure has the shape of a counter-hinged molecular box (Fig. 1).
The ligand acts as a doubly chelating C,N-donor bridging two Pd atoms through six-membered chelate rings. The benzene ring is dipalladated in a para arrangement, and thus the ligand adopts an anti conformation of the two pyridine rings with respect to the benzene ring. Unlike the situation in a structurally related tetranuclear complex (O'Keefe & Steel, 1998), the cyclopalladated ligand is far from planar. The planes of the pyridine rings are inclined to the benzene ring at angles of 30.1 (5) and 37.7 (5)°, for the pyridines containing N11 and N41, respectively, with one ring being inclined above the plane of the benzene ring and the other below. This lack of planarity is due to flexibility provided by the O atom spacer and the formation of six-membered chelate rings, rather than the five-membered rings of our earlier complex. The six-membered chelate rings have shallow boat conformations, with the Pd and O atoms lying out of the planes of the C and N atoms [Pd1 0.410 (6) and O1 0.288 (8) Å, Pd2 0.821 (6) and O4 0.372 (8) Å].
All Pd-donor bond lengths are normal and show the usual lengthening of the bond trans to the C-donor (Churchill et al., 1980; Navarro-Ranninger et al., 1996). The geometry at each Pd is square-planar and the Pd1—Pd2A separation is 2.918 (1) Å, which is considered non-bonding (Churchill et al., 1980). The two central benzene rings, being related by a centre of inversion, are necessarily parallel and are separated by 3.21 (1) Å. These two rings are offset such that a bond of one ring sits over the centroid of the other ring and a significant π-π interaction is indicated.
This structure determination confirms our earlier proposal (De Geest et al., 1999) that (II) exists as a tetranuclear, rather than a polymeric, species, and suggests that other related compounds may also be so. It represents the first reported example of a crystal structure of a compound containing a doubly-cyclopalladated benzene ring with six-membered N,C-chelate rings.