Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102009642/ln1139sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102009642/ln1139Isup2.hkl |
CCDC reference: 192951
The title complex was prepared according to following method: a stochiometric amount of tetrabutylammonium chloride (molar ratio 1:1) was added to a dichloromethane solution (10 ml) of the precursor [Pd{C4(COOMe)4}]n (0.07 g, 0.18 mmol) (see Scheme). The reaction solution was stirred at room temperature for 30 min, and then the solvent was partially evaporated under reduced pressure. The addition of diethyl ether caused the formation of a pale-yellow solid, which was filtered off, washed with diethyl ether and air dried. Crystals of (I) were obtained by recrystallization from dichloromethane-diethyl ether (yield 84%). Analysis found: C 50.5, H 7.4, N 1.9%; calculated for C56H96N2Cl2O16Pd2: C 50.3, H 7.2, N 2.1%. IR (cm-1): 1712, 1694 (C═O, str); 1H NMR (CDCl3, δ, p.p.m.): 3.57 (s, 6H, COOMe), 3,62 (s, 6H, COOMe), 3.40 (t, 16H, NBu4), 1.74 (m, 16H, NBu4), 1.53 (m, 16H, NBu4), 1.00 (t, 24H, NBu4). The palladacyclopentadiene precursor was prepared by the published method of Moseley & Maitlis (1974). The tetrabutylammonium chloride was purchased from Aldrich and used without further purification. CHN analyses were carried out with a Perkin-Elmer 240 C microanalyser. The IR spectra were recorded on a Perkin-Elmer spectrophotometer 16 F PC FT—IR, using Nujol mulls between polyethylene sheets. The NMR data were recorded on a Bruker AC 200E (1H) spectrometer.
H atoms were placed in calculated positions, with C—H distances of 0.99 and 0.98 Å for methylene and methyl groups, respectively, and were refined as riding, with Uiso(H) = 1.2Ueq(C) for the methylene groups and Uiso(H) = 1.5Ueq(C) for the methyl groups.
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997).
(C16H36N)2[Pd2(C12H12O8)2Cl2] | Z = 1 |
Mr = 1337.05 | F(000) = 700 |
Triclinic, P1 | Dx = 1.381 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.5024 (6) Å | Cell parameters from 61 reflections |
b = 12.6678 (7) Å | θ = 9.8–24.7° |
c = 14.637 (1) Å | µ = 0.71 mm−1 |
α = 95.929 (5)° | T = 173 K |
β = 106.777 (5)° | Block, yellow |
γ = 104.100 (5)° | 0.40 × 0.35 × 0.28 mm |
V = 1607.25 (19) Å3 |
Siemens P4 four-circle diffractometer | Rint = 0.020 |
Graphite monochromator | θmax = 25°, θmin = 3.1° |
ω scans | h = −10→11 |
Absorption correction: ψ scan (North et al., 1968) | k = −14→14 |
Tmin = 0.787, Tmax = 0.821 | l = −17→17 |
11249 measured reflections | 3 standard reflections every 247 reflections |
5644 independent reflections | intensity decay: 4.3% |
5057 reflections with I > 2σ(I) |
Refinement on F2 | Primary atom site location: Patterson |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.055 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0286P)2 + 0.2945P] where P = (Fo2 + 2Fc2)/3 |
5644 reflections | (Δ/σ)max = 0.001 |
352 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
(C16H36N)2[Pd2(C12H12O8)2Cl2] | γ = 104.100 (5)° |
Mr = 1337.05 | V = 1607.25 (19) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.5024 (6) Å | Mo Kα radiation |
b = 12.6678 (7) Å | µ = 0.71 mm−1 |
c = 14.637 (1) Å | T = 173 K |
α = 95.929 (5)° | 0.40 × 0.35 × 0.28 mm |
β = 106.777 (5)° |
Siemens P4 four-circle diffractometer | 5057 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.020 |
Tmin = 0.787, Tmax = 0.821 | 3 standard reflections every 247 reflections |
11249 measured reflections | intensity decay: 4.3% |
5644 independent reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.055 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.36 e Å−3 |
5644 reflections | Δρmin = −0.30 e Å−3 |
352 parameters |
Geometry. Mean-plane data from final SHELXL refinement run:- Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 8.4969 (0.0014) x + 7.0902 (0.0041) y + 6.6545 (0.0049) z = 2.6524 (0.0019) * 0.0612 (0.0004) Pd1 * -0.0014 (0.0007) Cl1 * -0.0556 (0.0007) Cl1_$2 * 0.0237 (0.0013) C1 * -0.0792 (0.0014) C2 * 0.0036 (0.0014) C3 * 0.0477 (0.0014) C4 Rms deviation of fitted atoms = 0.0478 |
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 | ||
Pd1 | 0.341355 (17) | 0.409571 (12) | 0.407262 (10) | 0.02387 (6) | |
Cl1 | 0.47927 (6) | 0.40997 (4) | 0.57353 (3) | 0.03337 (12) | |
C4 | 0.2249 (2) | 0.39908 (16) | 0.26774 (13) | 0.0262 (4) | |
C1 | 0.1965 (2) | 0.25730 (16) | 0.37886 (13) | 0.0263 (4) | |
O4 | −0.04187 (16) | 0.03752 (12) | 0.28919 (11) | 0.0382 (3) | |
O2 | 0.28426 (16) | 0.11963 (12) | 0.46152 (10) | 0.0334 (3) | |
O7 | 0.38614 (17) | 0.49555 (12) | 0.19327 (10) | 0.0370 (3) | |
O6 | −0.13533 (17) | 0.23134 (15) | 0.10813 (12) | 0.0516 (4) | |
O3 | 0.03675 (18) | 0.06776 (12) | 0.16151 (10) | 0.0424 (4) | |
O8 | 0.20414 (19) | 0.56965 (13) | 0.21534 (11) | 0.0466 (4) | |
O5 | 0.04985 (17) | 0.34095 (13) | 0.06528 (10) | 0.0401 (4) | |
N1 | 0.35422 (17) | 0.77880 (13) | 0.66800 (11) | 0.0268 (3) | |
O1 | 0.13103 (18) | 0.20452 (14) | 0.51231 (11) | 0.0444 (4) | |
C15 | 0.6339 (2) | 0.75879 (19) | 0.91192 (15) | 0.0359 (5) | |
H15A | 0.7029 | 0.73 | 0.8834 | 0.043* | |
H15B | 0.6779 | 0.8402 | 0.9319 | 0.043* | |
C8 | 0.2641 (2) | 0.49638 (17) | 0.22220 (13) | 0.0313 (5) | |
C13 | 0.4952 (2) | 0.76333 (17) | 0.74026 (14) | 0.0288 (4) | |
H13A | 0.5797 | 0.8329 | 0.7561 | 0.035* | |
H13B | 0.5269 | 0.7046 | 0.7083 | 0.035* | |
C2 | 0.1042 (2) | 0.21948 (17) | 0.28586 (13) | 0.0274 (4) | |
C25 | 0.3234 (2) | 0.88474 (17) | 0.70531 (15) | 0.0336 (5) | |
H25A | 0.2219 | 0.8865 | 0.6633 | 0.04* | |
H25B | 0.3177 | 0.8823 | 0.7716 | 0.04* | |
C17 | 0.2130 (2) | 0.68430 (16) | 0.65572 (15) | 0.0308 (4) | |
H17A | 0.1228 | 0.6991 | 0.6108 | 0.037* | |
H17B | 0.1965 | 0.6831 | 0.7194 | 0.037* | |
C5 | 0.2101 (2) | 0.18497 (16) | 0.45257 (14) | 0.0275 (4) | |
C6 | 0.0226 (2) | 0.10055 (17) | 0.24800 (14) | 0.0303 (4) | |
C14 | 0.4768 (2) | 0.73279 (17) | 0.83506 (14) | 0.0315 (4) | |
H14A | 0.4144 | 0.7753 | 0.8575 | 0.038* | |
H14B | 0.4228 | 0.6529 | 0.8244 | 0.038* | |
C21 | 0.3865 (2) | 0.78435 (18) | 0.57259 (14) | 0.0314 (4) | |
H21A | 0.4018 | 0.713 | 0.5497 | 0.038* | |
H21B | 0.4839 | 0.8429 | 0.585 | 0.038* | |
C3 | 0.1154 (2) | 0.30316 (16) | 0.22352 (13) | 0.0269 (4) | |
C18 | 0.2208 (3) | 0.57063 (18) | 0.61710 (18) | 0.0426 (5) | |
H18A | 0.3221 | 0.5617 | 0.6517 | 0.051* | |
H18B | 0.2091 | 0.5638 | 0.5471 | 0.051* | |
C16 | 0.6269 (3) | 0.7086 (2) | 1.00071 (16) | 0.0484 (6) | |
H16A | 0.7303 | 0.7278 | 1.0481 | 0.073* | |
H16B | 0.5859 | 0.6278 | 0.9816 | 0.073* | |
H16C | 0.56 | 0.7377 | 1.0299 | 0.073* | |
C22 | 0.2624 (2) | 0.80773 (18) | 0.49135 (15) | 0.0339 (5) | |
H22A | 0.1647 | 0.7486 | 0.476 | 0.041* | |
H22B | 0.2457 | 0.8791 | 0.5125 | 0.041* | |
C28 | 0.5450 (4) | 1.0611 (3) | 0.8907 (2) | 0.0803 (10) | |
H28A | 0.5543 | 1.1213 | 0.9418 | 0.12* | |
H28B | 0.6475 | 1.0574 | 0.8925 | 0.12* | |
H28C | 0.4873 | 0.9907 | 0.9014 | 0.12* | |
C7 | −0.0037 (2) | 0.28567 (18) | 0.12742 (14) | 0.0331 (5) | |
C10 | −0.0446 (3) | −0.0460 (2) | 0.11606 (18) | 0.0578 (7) | |
H10A | −0.0273 | −0.0621 | 0.0539 | 0.087* | |
H10B | −0.1546 | −0.0581 | 0.1047 | 0.087* | |
H10C | −0.0072 | −0.095 | 0.1586 | 0.087* | |
C24 | 0.1999 (3) | 0.8415 (2) | 0.31834 (16) | 0.0420 (5) | |
H24A | 0.2382 | 0.8432 | 0.263 | 0.063* | |
H24B | 0.1891 | 0.9145 | 0.3387 | 0.063* | |
H24C | 0.0998 | 0.7857 | 0.2993 | 0.063* | |
C23 | 0.3119 (3) | 0.8125 (2) | 0.40169 (16) | 0.0487 (6) | |
H23A | 0.4132 | 0.8682 | 0.4193 | 0.058* | |
H23B | 0.3241 | 0.7396 | 0.3799 | 0.058* | |
C26 | 0.4422 (3) | 0.99147 (18) | 0.70878 (18) | 0.0449 (6) | |
H26A | 0.4106 | 1.0176 | 0.6466 | 0.054* | |
H26B | 0.5421 | 0.9765 | 0.7164 | 0.054* | |
C12 | 0.4497 (3) | 0.5932 (2) | 0.1603 (2) | 0.0619 (8) | |
H12A | 0.5374 | 0.5847 | 0.1409 | 0.093* | |
H12B | 0.4839 | 0.6576 | 0.2129 | 0.093* | |
H12C | 0.3715 | 0.6041 | 0.1046 | 0.093* | |
C27 | 0.4613 (3) | 1.08237 (19) | 0.79257 (18) | 0.0523 (6) | |
H27A | 0.5189 | 1.1543 | 0.7828 | 0.063* | |
H27B | 0.3587 | 1.0876 | 0.7918 | 0.063* | |
C11 | −0.0626 (3) | 0.3390 (2) | −0.02681 (17) | 0.0588 (7) | |
H11A | −0.0115 | 0.3816 | −0.0663 | 0.088* | |
H11B | −0.1405 | 0.3718 | −0.0149 | 0.088* | |
H11C | −0.1118 | 0.2622 | −0.0614 | 0.088* | |
C9 | 0.1492 (3) | 0.1469 (3) | 0.59282 (19) | 0.0667 (9) | |
H9A | 0.0881 | 0.1661 | 0.6322 | 0.1* | |
H9B | 0.2576 | 0.1686 | 0.6328 | 0.1* | |
H9C | 0.1142 | 0.0668 | 0.5683 | 0.1* | |
C20 | 0.1277 (3) | 0.4606 (2) | 0.7351 (2) | 0.0731 (9) | |
H20A | 0.0423 | 0.4019 | 0.7395 | 0.11* | |
H20B | 0.1403 | 0.5291 | 0.7784 | 0.11* | |
H20C | 0.2222 | 0.4383 | 0.7545 | 0.11* | |
C19 | 0.0938 (3) | 0.4798 (2) | 0.6315 (2) | 0.0607 (8) | |
H19A | −0.0033 | 0.5002 | 0.6119 | 0.073* | |
H19B | 0.079 | 0.4097 | 0.5882 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.02789 (9) | 0.02605 (9) | 0.01788 (8) | 0.01227 (6) | 0.00402 (6) | 0.00403 (5) |
Cl1 | 0.0420 (3) | 0.0286 (3) | 0.0225 (2) | 0.0111 (2) | 0.0001 (2) | 0.00252 (19) |
C4 | 0.0269 (10) | 0.0319 (11) | 0.0224 (9) | 0.0143 (9) | 0.0066 (8) | 0.0063 (8) |
C1 | 0.0249 (10) | 0.0340 (11) | 0.0258 (10) | 0.0141 (8) | 0.0112 (8) | 0.0077 (8) |
O4 | 0.0283 (7) | 0.0413 (9) | 0.0444 (9) | 0.0034 (7) | 0.0138 (7) | 0.0157 (7) |
O2 | 0.0314 (7) | 0.0350 (8) | 0.0388 (8) | 0.0140 (6) | 0.0123 (6) | 0.0149 (6) |
O7 | 0.0413 (8) | 0.0318 (8) | 0.0380 (8) | 0.0070 (7) | 0.0126 (7) | 0.0157 (6) |
O6 | 0.0281 (9) | 0.0695 (12) | 0.0425 (9) | 0.0031 (8) | −0.0014 (7) | 0.0103 (8) |
O3 | 0.0535 (10) | 0.0333 (8) | 0.0323 (8) | −0.0012 (7) | 0.0153 (7) | 0.0006 (6) |
O8 | 0.0584 (10) | 0.0403 (9) | 0.0440 (9) | 0.0279 (8) | 0.0067 (8) | 0.0160 (7) |
O5 | 0.0401 (8) | 0.0496 (9) | 0.0233 (7) | 0.0110 (7) | −0.0017 (6) | 0.0140 (7) |
N1 | 0.0249 (8) | 0.0283 (9) | 0.0293 (8) | 0.0091 (7) | 0.0113 (7) | 0.0027 (7) |
O1 | 0.0516 (9) | 0.0676 (11) | 0.0381 (8) | 0.0346 (9) | 0.0292 (8) | 0.0292 (8) |
C15 | 0.0360 (11) | 0.0387 (12) | 0.0294 (11) | 0.0070 (10) | 0.0087 (9) | 0.0060 (9) |
C8 | 0.0365 (11) | 0.0299 (11) | 0.0197 (9) | 0.0099 (9) | −0.0024 (8) | 0.0033 (8) |
C13 | 0.0234 (10) | 0.0327 (11) | 0.0286 (10) | 0.0061 (8) | 0.0081 (8) | 0.0036 (8) |
C2 | 0.0231 (9) | 0.0364 (11) | 0.0264 (10) | 0.0112 (8) | 0.0102 (8) | 0.0093 (8) |
C25 | 0.0423 (12) | 0.0293 (11) | 0.0364 (11) | 0.0156 (9) | 0.0197 (10) | 0.0047 (9) |
C17 | 0.0219 (10) | 0.0325 (11) | 0.0365 (11) | 0.0059 (8) | 0.0092 (8) | 0.0055 (9) |
C5 | 0.0221 (9) | 0.0325 (11) | 0.0271 (10) | 0.0053 (8) | 0.0081 (8) | 0.0078 (8) |
C6 | 0.0188 (9) | 0.0387 (12) | 0.0313 (10) | 0.0075 (9) | 0.0041 (8) | 0.0106 (9) |
C14 | 0.0319 (11) | 0.0318 (11) | 0.0322 (11) | 0.0074 (9) | 0.0142 (9) | 0.0059 (9) |
C21 | 0.0307 (11) | 0.0387 (12) | 0.0285 (10) | 0.0125 (9) | 0.0137 (9) | 0.0048 (9) |
C3 | 0.0252 (10) | 0.0345 (11) | 0.0225 (9) | 0.0125 (9) | 0.0063 (8) | 0.0068 (8) |
C18 | 0.0383 (12) | 0.0318 (12) | 0.0486 (13) | 0.0065 (10) | 0.0072 (10) | −0.0034 (10) |
C16 | 0.0615 (16) | 0.0496 (15) | 0.0338 (12) | 0.0164 (12) | 0.0132 (11) | 0.0116 (11) |
C22 | 0.0299 (11) | 0.0393 (12) | 0.0323 (11) | 0.0112 (9) | 0.0089 (9) | 0.0059 (9) |
C28 | 0.110 (3) | 0.0524 (18) | 0.0557 (18) | 0.0230 (18) | −0.0012 (18) | −0.0088 (14) |
C7 | 0.0327 (12) | 0.0371 (12) | 0.0273 (10) | 0.0137 (10) | 0.0035 (9) | 0.0052 (9) |
C10 | 0.0768 (19) | 0.0382 (14) | 0.0392 (13) | −0.0024 (13) | 0.0084 (13) | −0.0002 (11) |
C24 | 0.0437 (13) | 0.0473 (13) | 0.0333 (12) | 0.0140 (11) | 0.0089 (10) | 0.0080 (10) |
C23 | 0.0493 (14) | 0.0732 (18) | 0.0339 (12) | 0.0307 (13) | 0.0158 (11) | 0.0160 (12) |
C26 | 0.0575 (15) | 0.0298 (12) | 0.0492 (14) | 0.0086 (11) | 0.0239 (12) | 0.0058 (10) |
C12 | 0.0603 (17) | 0.0532 (16) | 0.0726 (18) | 0.0067 (13) | 0.0202 (14) | 0.0411 (15) |
C27 | 0.0684 (17) | 0.0298 (12) | 0.0530 (15) | 0.0131 (12) | 0.0143 (13) | 0.0010 (11) |
C11 | 0.0643 (17) | 0.0678 (18) | 0.0306 (12) | 0.0222 (14) | −0.0106 (12) | 0.0173 (12) |
C9 | 0.078 (2) | 0.108 (2) | 0.0519 (16) | 0.0525 (19) | 0.0427 (15) | 0.0542 (17) |
C20 | 0.0536 (17) | 0.0507 (17) | 0.106 (3) | 0.0001 (14) | 0.0194 (17) | 0.0307 (17) |
C19 | 0.0403 (14) | 0.0339 (14) | 0.088 (2) | −0.0007 (11) | 0.0033 (14) | 0.0014 (13) |
Pd1—Cl1 | 2.4070 (5) | C21—H21A | 0.99 |
Pd1—Cl1i | 2.4295 (6) | C21—H21B | 0.99 |
Pd1—C1 | 2.000 (2) | C3—C7 | 1.484 (3) |
Pd1—C4 | 1.9950 (18) | C18—C19 | 1.531 (3) |
Pd1—Pd1i | 3.5119 (4) | C18—H18A | 0.99 |
Pd1—N1i | 4.4650 (15) | C18—H18B | 0.99 |
Pd1—N1 | 5.6764 (16) | C16—H16A | 0.98 |
Pd1—N1ii | 6.1776 (16) | C16—H16B | 0.98 |
C4—C3 | 1.346 (3) | C16—H16C | 0.98 |
C4—C8 | 1.481 (3) | C22—C23 | 1.518 (3) |
C1—C2 | 1.350 (3) | C22—H22A | 0.99 |
C1—C5 | 1.484 (3) | C22—H22B | 0.99 |
O4—C6 | 1.204 (2) | C28—C27 | 1.515 (4) |
O2—C5 | 1.205 (2) | C28—H28A | 0.98 |
O7—C8 | 1.346 (3) | C28—H28B | 0.98 |
O7—C12 | 1.434 (3) | C28—H28C | 0.98 |
O6—C7 | 1.206 (3) | C10—H10A | 0.98 |
O3—C6 | 1.345 (2) | C10—H10B | 0.98 |
O3—C10 | 1.442 (3) | C10—H10C | 0.98 |
O8—C8 | 1.200 (2) | C24—C23 | 1.513 (3) |
O5—C7 | 1.342 (3) | C24—H24A | 0.98 |
O5—C11 | 1.452 (3) | C24—H24B | 0.98 |
N1—C17 | 1.517 (2) | C24—H24C | 0.98 |
N1—C13 | 1.518 (2) | C23—H23A | 0.99 |
N1—C21 | 1.519 (2) | C23—H23B | 0.99 |
N1—C25 | 1.522 (2) | C26—C27 | 1.530 (3) |
O1—C5 | 1.347 (2) | C26—H26A | 0.99 |
O1—C9 | 1.440 (3) | C26—H26B | 0.99 |
C15—C16 | 1.516 (3) | C12—H12A | 0.98 |
C15—C14 | 1.523 (3) | C12—H12B | 0.98 |
C15—H15A | 0.99 | C12—H12C | 0.98 |
C15—H15B | 0.99 | C27—H27A | 0.99 |
C13—C14 | 1.525 (3) | C27—H27B | 0.99 |
C13—H13A | 0.99 | C11—H11A | 0.98 |
C13—H13B | 0.99 | C11—H11B | 0.98 |
C2—C3 | 1.473 (3) | C11—H11C | 0.98 |
C2—C6 | 1.479 (3) | C9—H9A | 0.98 |
C25—C26 | 1.521 (3) | C9—H9B | 0.98 |
C25—H25A | 0.99 | C9—H9C | 0.98 |
C25—H25B | 0.99 | C20—C19 | 1.516 (4) |
C17—C18 | 1.519 (3) | C20—H20A | 0.98 |
C17—H17A | 0.99 | C20—H20B | 0.98 |
C17—H17B | 0.99 | C20—H20C | 0.98 |
C14—H14A | 0.99 | C19—H19A | 0.99 |
C14—H14B | 0.99 | C19—H19B | 0.99 |
C21—C22 | 1.525 (3) | ||
Cl1—Pd1—Cl1i | 86.875 (19) | C15—C16—H16A | 109.5 |
C1—Pd1—C4 | 79.79 (8) | C15—C16—H16B | 109.5 |
C1—Pd1—Cl1 | 97.15 (6) | H16A—C16—H16B | 109.5 |
C1—Pd1—Cl1i | 174.38 (5) | C15—C16—H16C | 109.5 |
C4—Pd1—Cl1 | 176.44 (6) | H16A—C16—H16C | 109.5 |
C4—Pd1—Cl1i | 96.06 (6) | H16B—C16—H16C | 109.5 |
Pd1i—Pd1—N1i | 89.91 (2) | C23—C22—C21 | 109.43 (17) |
Pd1i—Pd1—N1ii | 137.035 (16) | C23—C22—H22A | 109.8 |
Pd1—Cl1—Pd1i | 93.125 (19) | C21—C22—H22A | 109.8 |
C3—C4—C8 | 125.72 (17) | C23—C22—H22B | 109.8 |
C3—C4—Pd1 | 116.27 (14) | C21—C22—H22B | 109.8 |
C8—C4—Pd1 | 118.01 (14) | H22A—C22—H22B | 108.2 |
C2—C1—C5 | 122.46 (18) | C27—C28—H28A | 109.5 |
C2—C1—Pd1 | 116.07 (14) | C27—C28—H28B | 109.5 |
C5—C1—Pd1 | 120.68 (13) | H28A—C28—H28B | 109.5 |
C8—O7—C12 | 115.57 (18) | C27—C28—H28C | 109.5 |
C6—O3—C10 | 115.40 (17) | H28A—C28—H28C | 109.5 |
C7—O5—C11 | 116.28 (18) | H28B—C28—H28C | 109.5 |
C17—N1—C13 | 110.88 (15) | O6—C7—O5 | 123.53 (18) |
C17—N1—C21 | 111.09 (15) | O6—C7—C3 | 124.0 (2) |
C13—N1—C21 | 107.10 (14) | O5—C7—C3 | 112.40 (17) |
C17—N1—C25 | 106.87 (14) | O3—C10—H10A | 109.5 |
C13—N1—C25 | 109.91 (15) | O3—C10—H10B | 109.5 |
C21—N1—C25 | 111.03 (15) | H10A—C10—H10B | 109.5 |
C5—O1—C9 | 115.14 (17) | O3—C10—H10C | 109.5 |
C16—C15—C14 | 112.44 (19) | H10A—C10—H10C | 109.5 |
C16—C15—H15A | 109.1 | H10B—C10—H10C | 109.5 |
C14—C15—H15A | 109.1 | C23—C24—H24A | 109.5 |
C16—C15—H15B | 109.1 | C23—C24—H24B | 109.5 |
C14—C15—H15B | 109.1 | H24A—C24—H24B | 109.5 |
H15A—C15—H15B | 107.8 | C23—C24—H24C | 109.5 |
O8—C8—O7 | 123.3 (2) | H24A—C24—H24C | 109.5 |
O8—C8—C4 | 126.8 (2) | H24B—C24—H24C | 109.5 |
O7—C8—C4 | 109.82 (16) | C24—C23—C22 | 113.49 (19) |
N1—C13—C14 | 115.96 (15) | C24—C23—H23A | 108.9 |
N1—C13—H13A | 108.3 | C22—C23—H23A | 108.9 |
C14—C13—H13A | 108.3 | C24—C23—H23B | 108.9 |
N1—C13—H13B | 108.3 | C22—C23—H23B | 108.9 |
C14—C13—H13B | 108.3 | H23A—C23—H23B | 107.7 |
H13A—C13—H13B | 107.4 | C25—C26—C27 | 111.89 (19) |
C1—C2—C3 | 113.54 (18) | C25—C26—H26A | 109.2 |
C1—C2—C6 | 122.04 (18) | C27—C26—H26A | 109.2 |
C3—C2—C6 | 123.53 (17) | C25—C26—H26B | 109.2 |
C26—C25—N1 | 115.11 (17) | C27—C26—H26B | 109.2 |
C26—C25—H25A | 108.5 | H26A—C26—H26B | 107.9 |
N1—C25—H25A | 108.5 | O7—C12—H12A | 109.5 |
C26—C25—H25B | 108.5 | O7—C12—H12B | 109.5 |
N1—C25—H25B | 108.5 | H12A—C12—H12B | 109.5 |
H25A—C25—H25B | 107.5 | O7—C12—H12C | 109.5 |
N1—C17—C18 | 114.75 (16) | H12A—C12—H12C | 109.5 |
N1—C17—H17A | 108.6 | H12B—C12—H12C | 109.5 |
C18—C17—H17A | 108.6 | C28—C27—C26 | 112.6 (2) |
N1—C17—H17B | 108.6 | C28—C27—H27A | 109.1 |
C18—C17—H17B | 108.6 | C26—C27—H27A | 109.1 |
H17A—C17—H17B | 107.6 | C28—C27—H27B | 109.1 |
O2—C5—O1 | 123.32 (18) | C26—C27—H27B | 109.1 |
O2—C5—C1 | 126.14 (17) | H27A—C27—H27B | 107.8 |
O1—C5—C1 | 110.51 (16) | O5—C11—H11A | 109.5 |
O4—C6—O3 | 122.71 (19) | O5—C11—H11B | 109.5 |
O4—C6—C2 | 126.24 (19) | H11A—C11—H11B | 109.5 |
O3—C6—C2 | 110.94 (17) | O5—C11—H11C | 109.5 |
C15—C14—C13 | 109.72 (16) | H11A—C11—H11C | 109.5 |
C15—C14—H14A | 109.7 | H11B—C11—H11C | 109.5 |
C13—C14—H14A | 109.7 | O1—C9—H9A | 109.5 |
C15—C14—H14B | 109.7 | O1—C9—H9B | 109.5 |
C13—C14—H14B | 109.7 | H9A—C9—H9B | 109.5 |
H14A—C14—H14B | 108.2 | O1—C9—H9C | 109.5 |
N1—C21—C22 | 115.59 (16) | H9A—C9—H9C | 109.5 |
N1—C21—H21A | 108.4 | H9B—C9—H9C | 109.5 |
C22—C21—H21A | 108.4 | C19—C20—H20A | 109.5 |
N1—C21—H21B | 108.4 | C19—C20—H20B | 109.5 |
C22—C21—H21B | 108.4 | H20A—C20—H20B | 109.5 |
H21A—C21—H21B | 107.4 | C19—C20—H20C | 109.5 |
C4—C3—C2 | 114.01 (17) | H20A—C20—H20C | 109.5 |
C4—C3—C7 | 124.83 (18) | H20B—C20—H20C | 109.5 |
C2—C3—C7 | 120.34 (18) | C20—C19—C18 | 113.5 (2) |
C17—C18—C19 | 110.3 (2) | C20—C19—H19A | 108.9 |
C17—C18—H18A | 109.6 | C18—C19—H19A | 108.9 |
C19—C18—H18A | 109.6 | C20—C19—H19B | 108.9 |
C17—C18—H18B | 109.6 | C18—C19—H19B | 108.9 |
C19—C18—H18B | 109.6 | H19A—C19—H19B | 107.7 |
H18A—C18—H18B | 108.1 | ||
C1—Pd1—Cl1—Pd1i | 176.05 (5) | C2—C1—C5—O1 | −103.6 (2) |
Cl1i—Pd1—Cl1—Pd1i | 0.02 (10) | Pd1—C1—C5—O1 | 86.92 (18) |
C1—Pd1—C4—C3 | −0.88 (14) | C10—O3—C6—O4 | 6.4 (3) |
Cl1i—Pd1—C4—C3 | 175.28 (14) | C10—O3—C6—C2 | −177.33 (19) |
C1—Pd1—C4—C8 | 178.46 (16) | C1—C2—C6—O4 | 42.2 (3) |
Cl1i—Pd1—C4—C8 | −5.38 (15) | C4—C3—C7—O6 | −140.9 (2) |
C4—Pd1—C1—C2 | 4.14 (14) | C3—C2—C6—O4 | −149.3 (2) |
Cl1—Pd1—C1—C2 | −174.02 (14) | C1—C2—C6—O3 | −133.95 (19) |
C4—Pd1—C1—C5 | 174.24 (16) | C3—C2—C6—O3 | 34.6 (2) |
Cl1—Pd1—C1—C5 | −3.93 (15) | C16—C15—C14—C13 | −167.83 (18) |
C12—O7—C8—O8 | 4.9 (3) | N1—C13—C14—C15 | −160.52 (16) |
C12—O7—C8—C4 | −171.59 (19) | C17—N1—C21—C22 | 62.8 (2) |
C3—C4—C8—O8 | 86.0 (3) | C13—N1—C21—C22 | −176.00 (17) |
Pd1—C4—C8—O8 | −93.3 (2) | C25—N1—C21—C22 | −56.0 (2) |
C3—C4—C8—O7 | −97.7 (2) | C8—C4—C3—C2 | 178.52 (17) |
Pd1—C1—C5—O2 | −90.9 (2) | Pd1—C4—C3—C2 | −2.2 (2) |
Pd1—C4—C8—O7 | 83.06 (17) | C8—C4—C3—C7 | −11.9 (3) |
C17—N1—C13—C14 | −47.0 (2) | Pd1—C4—C3—C7 | 167.37 (15) |
C21—N1—C13—C14 | −168.32 (16) | C1—C2—C3—C4 | 5.6 (2) |
C25—N1—C13—C14 | 71.0 (2) | C6—C2—C3—C4 | −163.82 (18) |
C5—C1—C2—C3 | −176.29 (16) | C1—C2—C3—C7 | −164.52 (17) |
Pd1—C1—C2—C3 | −6.4 (2) | C6—C2—C3—C7 | 26.1 (3) |
C5—C1—C2—C6 | −6.7 (3) | N1—C17—C18—C19 | 165.76 (18) |
Pd1—C1—C2—C6 | 163.18 (14) | N1—C21—C22—C23 | 179.16 (18) |
C17—N1—C25—C26 | −171.60 (18) | C11—O5—C7—O6 | 4.2 (3) |
C13—N1—C25—C26 | 68.0 (2) | C11—O5—C7—C3 | −173.27 (19) |
C21—N1—C25—C26 | −50.3 (2) | C2—C3—C7—O6 | 28.0 (3) |
C13—N1—C17—C18 | −61.2 (2) | C4—C3—C7—O5 | 36.5 (3) |
C21—N1—C17—C18 | 57.8 (2) | C2—C3—C7—O5 | −154.55 (17) |
C25—N1—C17—C18 | 179.07 (17) | C21—C22—C23—C24 | −176.9 (2) |
C9—O1—C5—O2 | 4.0 (3) | N1—C25—C26—C27 | −147.8 (2) |
C9—O1—C5—C1 | −173.9 (2) | C25—C26—C27—C28 | 72.6 (3) |
C2—C1—C5—O2 | 78.5 (3) | C17—C18—C19—C20 | −76.7 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C16H36N)2[Pd2(C12H12O8)2Cl2] |
Mr | 1337.05 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 9.5024 (6), 12.6678 (7), 14.637 (1) |
α, β, γ (°) | 95.929 (5), 106.777 (5), 104.100 (5) |
V (Å3) | 1607.25 (19) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.71 |
Crystal size (mm) | 0.40 × 0.35 × 0.28 |
Data collection | |
Diffractometer | Siemens P4 four-circle diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.787, 0.821 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11249, 5644, 5057 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.055, 1.03 |
No. of reflections | 5644 |
No. of parameters | 352 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.30 |
Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).
Pd1—Cl1 | 2.4070 (5) | Pd1—C4 | 1.9950 (18) |
Pd1—Cl1i | 2.4295 (6) | Pd1—Pd1i | 3.5119 (4) |
Pd1—C1 | 2.000 (2) | ||
Cl1—Pd1—Cl1i | 86.875 (19) | C1—Pd1—Cl1i | 174.38 (5) |
C1—Pd1—C4 | 79.79 (8) | C4—Pd1—Cl1 | 176.44 (6) |
C1—Pd1—Cl1 | 97.15 (6) | C4—Pd1—Cl1i | 96.06 (6) |
Pd1—C4—C8—O8 | −93.3 (2) | C1—C2—C6—O4 | 42.2 (3) |
Pd1—C1—C5—O2 | −90.9 (2) | C4—C3—C7—O6 | −140.9 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
The chemistry of metallacycles has been of increasing interest during recent years, as a result of their involvement in catalytic processes and their application in organic syntheses (Ojima et al., 1996). The cycloaddition of two unsaturated fragments to a metal unit is one of the most useful methods of metallacycle synthesis, since it gives access to relatively complex structures starting from small unsaturated molecules (Cámpora et al., 1999). In particular, the oxidative cycloaddition of acetylenic esters such as dimethyl acetylenedicarboxylate (dmad) to Ni, Pd and Pt has received much attention, due in part to its involvement in different oligomerization and co-oligomerization catalytic reactions, and also because of the interesting behaviour of the compounds formed as precursors in organometallic chemistry. Thus, the polymer complex, palladacyclopentadiene, [Pd(C4R4)]n (R is COOMe), formed in the reaction of dmad with Pd(dba)2 (dba is dibenzylidene acetone), reacts with a wide range of donor ligands to give discrete soluble molecules (tom Dieck et al., 1990). Other aspects recently studied are the use of these compounds as catalysts in the metathesis of enynes (Trost et al., 1993), dimerization of allenyl ketones (Hashmi, 1995), conversion of alkynes to conjugated dienes (van Belzen et al., 1998, and references therein) and co-cyclotrimerizations of acetylenes with other acetylenes, alkenes and allenes (Munz et al., 1991). With this background, we present here the crystal structure of one such dinuclear metallacycle, the title compound, (I). \sch
In complex (I) (Fig. 1), the coordination around the PdII atoms is approximately planar, the largest deviation from the plane defined by the metallacycle ring and the Cl atoms (r.m.s. deviation 0.0478 Å) being 0.0792 (14) Å for atom C2. The bond angles around the Pd atom deviate from ideal square-planar values (Table 1); the largest deviation is the C1—Pd1—C4 angle of 79.79 (8)°. This value is within the range found for related complexes in the Cambridge Structural Database (CSD; October 2001 release; Allen & Kennard, 1993), where the C—Pd—C angle for the tetraalkyl buta-1,3-diene-1,2,3,4-tetracarboxylate PdII fragment in the CSD (7 hits) ranges from 79.18 to 80.38°. The –CO2 groups of the ester functions bound to the C atoms trans to Cl are nearly perpendicular to the palladacycle ring, as indicated by the Pd1—C1—C5—O2 and Pd1—C4—C8—O8 torsion angles. The angle between the other two carboxylate groups and the palladacycle plane is smaller (Table 1). The Pd—Cl distances are typical for µ-Cl dinuclear complexes of Pd. The Pd—C distances are similar to those found in other complexes containing this ligand (Sánchez et al., 2002).
The molecule of (I) lies on a centre of inversion, so the [Pd2(µ-Cl)2] moiety is strictly planar. The CSD contains 151 entries for dinuclear complexes of PdII bridged by two Cl atoms, in which the [Pd2(µ-Cl)2] moiety is either planar or bent. A statistical analysis of the dihedral angle of the [Pd2(µ-Cl)2] unit along the Cl···Cl axis reveals that the most frequent conformation is planar (Fig. 2): 39.7% of the hits are strictly planar. In the title complex, the Pd1···Pd1i distance [symmetry code: (i) 1 - x, 1 - y, 1 - z] is 3.5119 (4) Å, which is within the most frequently occupied region of the range found in dinuclear complexes containing the [Pd2(µ-Cl)2] core (Fig. 3); 28% of the structures exhibit a distance of between 3.50 and 3.55 Å.
The anionic complex in (I) is sandwiched between two [NBu4]+ cations. The N atoms from the cations lie on the perpendicular to the [Pd2(µ-Cl)2] core, over the PdII atoms [N1—Pd1—Pd1i 89.91 (2)°]. The distances from Pd1 to the two nearest N atoms are 4.4650 (15) and 5.6764 (16) Å. The next nearest N atom to Pd1 is 6.1776 (16) Å away. The structure does not present hydrogen bonds.
The structure of the analogous iodo complex has been reported by Rheingold et al. (1989), the cation being methyltriphenylphosphonium. The iodo complex is also centrosymmetric and the Pd···Pd distance is 3.912 Å, which is larger than that found in the chloro complex, (I), due to the larger radius of the bridging I atom. The geometrical features of the palladacycle fragment are similar in both compounds. The mean Pd—C distance is 2.017 (3) Å in the iodo complex, which is larger than that found in (I) (Table 1), due to a stronger trans influence from I- than from Cl-. The –CO2 groups of the ester functions nearest to the Pd atom are approximately perpendicular to the palladacycle ring (Pd—C—C═O torsion angles of 100.3° and 82.3°), as in (I) (Table 1). The tilt of the other carboxylate groups from the palladacycle plane is also smaller (torsion angles of -163.7° and 56.2°). The anionic iodo complex is sandwiched between two [PMe(Ph)3]+ cations and the P atoms in the cations are placed on the perpendicular to the Pd···Pd axis (P—Pd—Pd 106.4°), with the shortest P—Pd distance being 5.064 Å.
The conformation found for the methoxycarbonyl groups in the above complexes suggests that, as the methoxycarbonyl groups at the α position relative to Pd become more perpendicular to the palladacycle ring, the adjacent methoxycarbonyl groups at the β position become more parallel to the ring. This is confirmed by the scatter plot of these angles for the tetramethyl buta-1,3-diene-1,2,3,4-tetracarboxylate PdII fragments in the CSD (Fig. 4), the angle between the planes defined by two adjacent methoxycarbonyl groups ranging from 42.4 to 74.7°.