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The title compound, [Pd
2(C
12H
10O
3P)
2Cl
2(C
12H
11O
3P)
2], consists of a dinuclear μ-chloro-bridged palladium unit with two diphenoxyphosphinite groups per Pd atom, linked together by a hydrogen bond. The asymmetric unit contains one half of the molecule, with the other half generated by an inversion centre. The geometry around the P atoms may be described as distorted tetrahedral. Adjacent molecules of the complex are linked by weak C—H
O and C—H
Cl hydrogen bonds. The structure is additionally stabilized by π–π stacking interactions between the aryl rings. These interactions form a herring-bone pattern in the crystal structure.
Supporting information
CCDC reference: 625681
PdCl2(cod) (cod is cyclooctadiene) (0.072 g, 0.3 mmol) was dissolved in benzene (1 ml) and then diphenylphosphite (0.12 ml, 0.6 mmol) was added. A white precipitate was formed immediately. The mixture was stirred for 1 h. After that time, the product was filtered off, washed with diethyl ether and dried in vacuo. Finally, the product was recrystallized from chloroform. Analysis, calculated: C 47.32, H 3.47%; found: C 47.18, H 3.29%. Spectroscopic analysis: IR (KBr, ν, cm−1): 1600 (s), 1480 (vs), 1200 (vs), 900 (vs), 750 (m), 700 (m), 500 (m); IR (Nujol, ν, cm−1): 381.7, 338.0 [m(Pd—Cl); 1H NMR (CDCl3, δ, p.p.m.): 7.15 (m, Ph), 10.0 (br, OH); 31P NMR (CDCl3, δ, p.p.m.): 65.5.
Carbon-bound H atoms were positioned geometrically and refined using a riding model, with aromatic C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). The position of H3 was obtained from a difference Fourier map and refined, with Uiso(H) = 1.5Ueq(O). The highest residual peak and the deepest hole in the final difference map are located 2.17 Å from Cl and 0.72 Å from Pd, respectively.
Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
di-µ-chloro-bis[(diphenoxyphosphinite-
κP)(diphenoxyphosphinito-
κP)palladium(II)]
top
Crystal data top
[Pd2(C12H10O3P)2Cl2(C12H11O3P)2] | F(000) = 1224 |
Mr = 1218.40 | Dx = 1.676 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 28302 reflections |
a = 12.268 (3) Å | θ = 4.5–37.5° |
b = 10.514 (2) Å | µ = 1.05 mm−1 |
c = 19.549 (4) Å | T = 110 K |
β = 106.78 (3)° | Plate, colourless |
V = 2414.2 (10) Å3 | 0.20 × 0.13 × 0.06 mm |
Z = 2 | |
Data collection top
Kuma KM-4 CCD area-detector diffractometer | 12649 independent reflections |
Radiation source: fine-focus sealed tube | 8606 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ϕ and ω scans | θmax = 37.5°, θmin = 4.5° |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2003) | h = −20→20 |
Tmin = 0.837, Tmax = 0.933 | k = −17→18 |
57621 measured reflections | l = −33→31 |
Refinement top
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0362P)2 + 0.8428P] where P = (Fo2 + 2Fc2)/3 |
12649 reflections | (Δ/σ)max = 0.001 |
310 parameters | Δρmax = 1.04 e Å−3 |
0 restraints | Δρmin = −0.75 e Å−3 |
Crystal data top
[Pd2(C12H10O3P)2Cl2(C12H11O3P)2] | V = 2414.2 (10) Å3 |
Mr = 1218.40 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.268 (3) Å | µ = 1.05 mm−1 |
b = 10.514 (2) Å | T = 110 K |
c = 19.549 (4) Å | 0.20 × 0.13 × 0.06 mm |
β = 106.78 (3)° | |
Data collection top
Kuma KM-4 CCD area-detector diffractometer | 12649 independent reflections |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2003) | 8606 reflections with I > 2σ(I) |
Tmin = 0.837, Tmax = 0.933 | Rint = 0.053 |
57621 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | Δρmax = 1.04 e Å−3 |
12649 reflections | Δρmin = −0.75 e Å−3 |
310 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pd | 0.36101 (2) | 0.51004 (2) | 0.50536 (1) | 0.01297 (5) | |
Cl | 0.53346 (5) | 0.40069 (6) | 0.56905 (3) | 0.01974 (12) | |
P1 | 0.20802 (5) | 0.61886 (6) | 0.44481 (3) | 0.01690 (12) | |
P2 | 0.27013 (5) | 0.42196 (6) | 0.57661 (3) | 0.01622 (12) | |
O1 | 0.18286 (15) | 0.60351 (17) | 0.36057 (9) | 0.0211 (4) | |
C11 | 0.1461 (2) | 0.4904 (2) | 0.32201 (12) | 0.0186 (5) | |
C12 | 0.2026 (2) | 0.4578 (3) | 0.27290 (13) | 0.0246 (5) | |
H12 | 0.2659 | 0.5063 | 0.2690 | 0.030* | |
C13 | 0.1654 (3) | 0.3524 (3) | 0.22916 (14) | 0.0295 (6) | |
H13 | 0.2030 | 0.3289 | 0.1949 | 0.035* | |
C14 | 0.0738 (3) | 0.2823 (3) | 0.23568 (15) | 0.0312 (6) | |
H14 | 0.0483 | 0.2108 | 0.2056 | 0.037* | |
C15 | 0.0187 (3) | 0.3156 (3) | 0.28578 (14) | 0.0282 (6) | |
H15 | −0.0439 | 0.2662 | 0.2900 | 0.034* | |
C16 | 0.0544 (2) | 0.4210 (3) | 0.33014 (13) | 0.0232 (5) | |
H16 | 0.0172 | 0.4443 | 0.3647 | 0.028* | |
O2 | 0.23974 (16) | 0.76624 (17) | 0.44511 (9) | 0.0224 (4) | |
C21 | 0.2879 (2) | 0.8261 (2) | 0.51191 (14) | 0.0239 (5) | |
C22 | 0.3934 (3) | 0.8793 (3) | 0.52435 (17) | 0.0352 (7) | |
H22 | 0.4345 | 0.8727 | 0.4901 | 0.042* | |
C23 | 0.4391 (3) | 0.9434 (3) | 0.58876 (18) | 0.0416 (8) | |
H23 | 0.5120 | 0.9820 | 0.5981 | 0.050* | |
C24 | 0.3812 (3) | 0.9517 (3) | 0.63853 (16) | 0.0393 (8) | |
H24 | 0.4137 | 0.9949 | 0.6824 | 0.047* | |
C25 | 0.2753 (4) | 0.8970 (4) | 0.62459 (19) | 0.0512 (10) | |
H25 | 0.2344 | 0.9026 | 0.6590 | 0.061* | |
C26 | 0.2277 (3) | 0.8340 (3) | 0.56106 (17) | 0.0418 (8) | |
H26 | 0.1544 | 0.7965 | 0.5515 | 0.050* | |
O3 | 0.09909 (15) | 0.60156 (19) | 0.46543 (9) | 0.0248 (4) | |
H3 | 0.1181 (16) | 0.5258 (18) | 0.5040 (12) | 0.037* | |
O4 | 0.34453 (15) | 0.42536 (16) | 0.65826 (8) | 0.0193 (3) | |
C41 | 0.3641 (2) | 0.5369 (2) | 0.69983 (12) | 0.0181 (5) | |
C42 | 0.4644 (2) | 0.6021 (2) | 0.70876 (13) | 0.0222 (5) | |
H42 | 0.5160 | 0.5781 | 0.6830 | 0.027* | |
C43 | 0.4890 (2) | 0.7041 (3) | 0.75632 (15) | 0.0290 (6) | |
H43 | 0.5579 | 0.7502 | 0.7631 | 0.035* | |
C44 | 0.4135 (3) | 0.7384 (3) | 0.79359 (15) | 0.0308 (6) | |
H44 | 0.4315 | 0.8064 | 0.8270 | 0.037* | |
C45 | 0.3113 (3) | 0.6736 (3) | 0.78221 (15) | 0.0326 (7) | |
H45 | 0.2587 | 0.6985 | 0.8071 | 0.039* | |
C46 | 0.2856 (2) | 0.5723 (3) | 0.73453 (14) | 0.0265 (6) | |
H46 | 0.2153 | 0.5283 | 0.7260 | 0.032* | |
O5 | 0.27312 (16) | 0.27112 (16) | 0.57155 (9) | 0.0229 (4) | |
C51 | 0.2216 (2) | 0.2066 (2) | 0.50654 (13) | 0.0241 (5) | |
C52 | 0.2834 (3) | 0.1883 (3) | 0.45890 (14) | 0.0302 (6) | |
H52 | 0.3575 | 0.2235 | 0.4676 | 0.036* | |
C53 | 0.2349 (3) | 0.1171 (3) | 0.39751 (16) | 0.0407 (8) | |
H53 | 0.2756 | 0.1051 | 0.3634 | 0.049* | |
C54 | 0.1292 (3) | 0.0644 (3) | 0.38610 (16) | 0.0403 (8) | |
H54 | 0.0976 | 0.0137 | 0.3449 | 0.048* | |
C55 | 0.0685 (3) | 0.0851 (3) | 0.43460 (17) | 0.0465 (9) | |
H55 | −0.0052 | 0.0492 | 0.4262 | 0.056* | |
C56 | 0.1143 (3) | 0.1579 (3) | 0.49557 (16) | 0.0396 (8) | |
H56 | 0.0724 | 0.1733 | 0.5287 | 0.048* | |
O6 | 0.15064 (15) | 0.46728 (19) | 0.57140 (10) | 0.0259 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pd | 0.01199 (8) | 0.01610 (9) | 0.01137 (7) | 0.00122 (6) | 0.00426 (5) | 0.00195 (6) |
Cl | 0.0171 (3) | 0.0259 (3) | 0.0183 (3) | 0.0067 (2) | 0.0084 (2) | 0.0115 (2) |
P1 | 0.0145 (3) | 0.0206 (3) | 0.0135 (3) | 0.0040 (2) | 0.0005 (2) | −0.0025 (2) |
P2 | 0.0176 (3) | 0.0191 (3) | 0.0133 (3) | −0.0052 (2) | 0.0067 (2) | −0.0025 (2) |
O1 | 0.0241 (9) | 0.0228 (9) | 0.0130 (7) | 0.0022 (7) | 0.0000 (7) | −0.0027 (7) |
C11 | 0.0203 (11) | 0.0193 (11) | 0.0124 (9) | 0.0061 (9) | −0.0015 (8) | −0.0013 (8) |
C12 | 0.0239 (13) | 0.0296 (14) | 0.0190 (12) | 0.0047 (11) | 0.0040 (10) | −0.0007 (10) |
C13 | 0.0361 (16) | 0.0316 (15) | 0.0189 (12) | 0.0080 (12) | 0.0051 (12) | −0.0048 (11) |
C14 | 0.0413 (17) | 0.0231 (14) | 0.0230 (13) | 0.0039 (12) | −0.0006 (12) | −0.0049 (10) |
C15 | 0.0309 (15) | 0.0257 (14) | 0.0242 (13) | 0.0001 (11) | 0.0019 (12) | −0.0007 (11) |
C16 | 0.0238 (13) | 0.0266 (13) | 0.0160 (11) | 0.0036 (10) | 0.0009 (10) | −0.0012 (10) |
O2 | 0.0286 (10) | 0.0184 (9) | 0.0156 (8) | 0.0064 (7) | −0.0010 (7) | −0.0027 (7) |
C21 | 0.0297 (14) | 0.0176 (12) | 0.0206 (12) | 0.0073 (10) | 0.0013 (11) | −0.0009 (9) |
C22 | 0.0376 (17) | 0.0316 (16) | 0.0338 (16) | −0.0044 (13) | 0.0065 (13) | −0.0068 (12) |
C23 | 0.0386 (18) | 0.0347 (18) | 0.0428 (19) | −0.0080 (14) | −0.0019 (15) | −0.0080 (14) |
C24 | 0.057 (2) | 0.0294 (16) | 0.0242 (14) | −0.0015 (15) | −0.0003 (15) | −0.0051 (12) |
C25 | 0.070 (3) | 0.051 (2) | 0.0384 (19) | −0.0171 (19) | 0.0239 (19) | −0.0233 (16) |
C26 | 0.0399 (19) | 0.054 (2) | 0.0323 (16) | −0.0114 (16) | 0.0124 (14) | −0.0195 (15) |
O3 | 0.0152 (8) | 0.0365 (11) | 0.0208 (9) | 0.0050 (7) | 0.0023 (7) | −0.0047 (8) |
O4 | 0.0253 (9) | 0.0197 (9) | 0.0139 (8) | −0.0035 (7) | 0.0071 (7) | −0.0011 (6) |
C41 | 0.0218 (12) | 0.0201 (12) | 0.0112 (9) | −0.0021 (9) | 0.0031 (9) | −0.0022 (8) |
C42 | 0.0209 (12) | 0.0228 (13) | 0.0218 (12) | −0.0004 (10) | 0.0044 (10) | 0.0002 (10) |
C43 | 0.0256 (14) | 0.0255 (14) | 0.0308 (14) | −0.0047 (11) | 0.0002 (12) | −0.0052 (11) |
C44 | 0.0411 (17) | 0.0245 (14) | 0.0228 (13) | −0.0009 (12) | 0.0031 (12) | −0.0087 (11) |
C45 | 0.0403 (17) | 0.0372 (17) | 0.0252 (14) | 0.0015 (13) | 0.0172 (13) | −0.0083 (12) |
C46 | 0.0298 (14) | 0.0308 (15) | 0.0214 (12) | −0.0060 (11) | 0.0116 (11) | −0.0068 (11) |
O5 | 0.0354 (11) | 0.0182 (9) | 0.0158 (8) | −0.0108 (7) | 0.0083 (8) | −0.0029 (6) |
C51 | 0.0361 (16) | 0.0167 (12) | 0.0177 (12) | −0.0044 (10) | 0.0051 (11) | −0.0005 (9) |
C52 | 0.0319 (16) | 0.0311 (15) | 0.0245 (13) | 0.0036 (12) | 0.0032 (12) | −0.0102 (11) |
C53 | 0.050 (2) | 0.0432 (19) | 0.0239 (14) | 0.0151 (16) | 0.0033 (14) | −0.0099 (13) |
C54 | 0.062 (2) | 0.0238 (15) | 0.0221 (14) | 0.0034 (14) | −0.0094 (15) | −0.0054 (11) |
C55 | 0.056 (2) | 0.0410 (19) | 0.0332 (17) | −0.0271 (17) | −0.0020 (16) | −0.0025 (14) |
C56 | 0.049 (2) | 0.0430 (19) | 0.0277 (15) | −0.0263 (15) | 0.0125 (15) | −0.0053 (13) |
O6 | 0.0166 (9) | 0.0403 (11) | 0.0238 (9) | −0.0055 (8) | 0.0105 (7) | −0.0020 (8) |
Geometric parameters (Å, º) top
Pd—Cl | 2.4139 (8) | C24—C25 | 1.375 (4) |
Pd—Cli | 2.4002 (8) | C24—H24 | 0.9500 |
Cl—Pdi | 2.4002 (8) | C25—C26 | 1.380 (4) |
Pd—P1 | 2.2248 (8) | C25—H25 | 0.9500 |
Pd—P2 | 2.2220 (8) | C26—H26 | 0.9500 |
P1—O1 | 1.594 (2) | O3—H3 | 1.08 (2) |
P1—O2 | 1.597 (2) | O4—C41 | 1.407 (3) |
P1—O3 | 1.514 (2) | C41—C42 | 1.375 (4) |
P2—O4 | 1.594 (2) | C41—C46 | 1.379 (4) |
P2—O5 | 1.590 (2) | C42—C43 | 1.394 (4) |
P2—O6 | 1.517 (2) | C42—H42 | 0.9500 |
O1—C11 | 1.410 (3) | C43—C44 | 1.382 (4) |
C11—C12 | 1.380 (4) | C43—H43 | 0.9500 |
C11—C16 | 1.389 (4) | C44—C45 | 1.387 (4) |
C12—C13 | 1.393 (4) | C44—H44 | 0.9500 |
C12—H12 | 0.9500 | C45—C46 | 1.390 (4) |
C13—C14 | 1.380 (4) | C45—H45 | 0.9500 |
C13—H13 | 0.9500 | C46—H46 | 0.9500 |
C14—C15 | 1.385 (4) | O5—C51 | 1.418 (3) |
C14—H14 | 0.9500 | C51—C56 | 1.371 (4) |
C15—C16 | 1.397 (4) | C51—C52 | 1.373 (4) |
C15—H15 | 0.9500 | C52—C53 | 1.394 (4) |
C16—H16 | 0.9500 | C52—H52 | 0.9500 |
O2—C21 | 1.416 (3) | C53—C54 | 1.368 (4) |
C21—C22 | 1.366 (4) | C53—H53 | 0.9500 |
C21—C26 | 1.372 (4) | C54—C55 | 1.381 (4) |
C22—C23 | 1.395 (4) | C54—H54 | 0.9500 |
C22—H22 | 0.9500 | C55—C56 | 1.391 (4) |
C23—C24 | 1.363 (4) | C55—H55 | 0.9500 |
C23—H23 | 0.9500 | C56—H56 | 0.9500 |
| | | |
P1—Pd—P2 | 92.81 (3) | C23—C24—C25 | 119.3 (3) |
P1—Pd—Cl | 176.81 (2) | C23—C24—H24 | 120.3 |
P1—Pd—Cli | 89.78 (3) | C25—C24—H24 | 120.3 |
P2—Pd—Cl | 90.10 (3) | C24—C25—C26 | 120.6 (3) |
P2—Pd—Cli | 177.40 (2) | C24—C25—H25 | 119.7 |
Cl—Pd—Cli | 87.31 (3) | C26—C25—H25 | 119.7 |
Pd—Cl—Pdi | 92.69 (3) | C21—C26—C25 | 119.1 (3) |
O1—P1—Pd | 112.32 (7) | C21—C26—H26 | 120.5 |
O2—P1—Pd | 109.25 (7) | C25—C26—H26 | 120.5 |
O3—P1—Pd | 118.06 (8) | P1—O3—H3 | 104.2 (8) |
O1—P1—O2 | 94.38 (9) | P2—O4—C41 | 123.4 (2) |
O1—P1—O3 | 109.9 (1) | C42—C41—C46 | 122.0 (2) |
O2—P1—O3 | 110.4 (1) | C42—C41—O4 | 119.1 (2) |
O4—P2—Pd | 111.87 (7) | C46—C41—O4 | 118.8 (2) |
O5—P2—Pd | 110.60 (7) | C41—C42—C43 | 118.8 (2) |
O6—P2—Pd | 118.50 (8) | C41—C42—H42 | 120.6 |
O4—P2—O5 | 93.89 (9) | C43—C42—H42 | 120.6 |
O4—P2—O6 | 108.9 (1) | C44—C43—C42 | 120.2 (3) |
O5—P2—O6 | 110.4 (1) | C44—C43—H43 | 119.9 |
P1—O1—C11 | 125.1 (2) | C42—C43—H43 | 119.9 |
C12—C11—C16 | 122.4 (2) | C43—C44—C45 | 120.0 (3) |
C12—C11—O1 | 115.7 (2) | C43—C44—H44 | 120.0 |
C16—C11—O1 | 121.8 (2) | C45—C44—H44 | 120.0 |
C11—C12—C13 | 118.9 (3) | C44—C45—C46 | 120.3 (3) |
C11—C12—H12 | 120.6 | C44—C45—H45 | 119.9 |
C13—C12—H12 | 120.6 | C46—C45—H45 | 119.9 |
C14—C13—C12 | 120.0 (3) | C41—C46—C45 | 118.7 (3) |
C14—C13—H13 | 120.0 | C41—C46—H46 | 120.6 |
C12—C13—H13 | 120.0 | C45—C46—H46 | 120.6 |
C13—C14—C15 | 120.4 (3) | P2—O5—C51 | 121.4 (2) |
C13—C14—H14 | 119.8 | C56—C51—C52 | 122.3 (2) |
C15—C14—H14 | 119.8 | C56—C51—O5 | 118.6 (2) |
C14—C15—C16 | 120.6 (3) | C52—C51—O5 | 119.0 (2) |
C14—C15—H15 | 119.7 | C51—C52—C53 | 118.5 (3) |
C16—C15—H15 | 119.7 | C51—C52—H52 | 120.7 |
C11—C16—C15 | 117.7 (2) | C53—C52—H52 | 120.7 |
C11—C16—H16 | 121.2 | C54—C53—C52 | 120.4 (3) |
C15—C16—H16 | 121.2 | C54—C53—H53 | 119.8 |
P1—O2—C21 | 118.1 (2) | C52—C53—H53 | 119.8 |
C22—C21—C26 | 121.6 (2) | C53—C54—C55 | 119.8 (3) |
C22—C21—O2 | 117.9 (2) | C53—C54—H54 | 120.1 |
C26—C21—O2 | 120.4 (2) | C55—C54—H54 | 120.1 |
C21—C22—C23 | 118.1 (3) | C54—C55—C56 | 120.7 (3) |
C21—C22—H22 | 120.9 | C54—C55—H55 | 119.7 |
C23—C22—H22 | 120.9 | C56—C55—H55 | 119.7 |
C24—C23—C22 | 121.2 (3) | C51—C56—C55 | 118.2 (3) |
C24—C23—H23 | 119.4 | C51—C56—H56 | 120.9 |
C22—C23—H23 | 119.4 | C55—C56—H56 | 120.9 |
| | | |
P2—Pd—Cl—Pdi | 179.72 (2) | O2—C21—C26—C25 | −177.6 (3) |
Cli—Pd—Cl—Pdi | 0.0 | C26—C21—C22—C23 | −0.5 (5) |
P2—Pd—P1—O1 | −130.85 (8) | C21—C22—C23—C24 | 0.9 (5) |
Cli—Pd—P1—O1 | 48.93 (8) | C22—C23—C24—C25 | −0.7 (5) |
P2—Pd—P1—O2 | 125.80 (8) | C23—C24—C25—C26 | 0.1 (5) |
Cli—Pd—P1—O2 | −54.42 (8) | C24—C25—C26—C21 | 0.2 (5) |
P2—Pd—P1—O3 | −1.37 (9) | C25—C26—C21—C22 | −0.1 (5) |
Cli—Pd—P1—O3 | 178.41 (9) | Pd—P2—O4—C41 | 73.3 (2) |
P1—Pd—P2—O4 | −134.89 (8) | O5—P2—O4—C41 | −172.7 (2) |
Cl—Pd—P2—O4 | 43.81 (8) | O6—P2—O4—C41 | −59.6 (2) |
P1—Pd—P2—O5 | 121.87 (8) | P2—O4—C41—C42 | −98.2 (2) |
Cl—Pd—P2—O5 | −59.43 (8) | P2—O4—C41—C46 | 86.4 (2) |
P1—Pd—P2—O6 | −7.01 (9) | O4—C41—C42—C43 | −172.9 (2) |
Cl—Pd—P2—O6 | 171.69 (9) | O4—C41—C46—C45 | 172.4 (2) |
Pd—P1—O1—C11 | 68.6 (2) | C46—C41—C42—C43 | 2.4 (4) |
O2—P1—O1—C11 | −178.6 (2) | C41—C42—C43—C44 | 0.0 (4) |
O3—P1—O1—C11 | −65.0 (2) | C42—C43—C44—C45 | −1.8 (4) |
P1—O1—C11—C12 | −133.6 (2) | C43—C44—C45—C46 | 1.4 (5) |
P1—O1—C11—C16 | 50.1 (2) | C44—C45—C46—C41 | 0.9 (4) |
O1—C11—C12—C13 | −175.3 (2) | C45—C46—C45—C44 | −2.8 (4) |
O1—C11—C16—C15 | 175.2 (2) | Pd—P2—O5—C51 | −62.3 (2) |
C16—C11—C12—C13 | 0.9 (4) | O4—P2—O5—C51 | −177.4 (2) |
C11—C12—C13—C14 | −0.4 (4) | O6—P2—O5—C51 | 70.8 (2) |
C12—C13—C14—C15 | −0.3 (4) | P2—O5—C51—C52 | 86.7 (3) |
C13—C14—C15—C16 | 0.5 (4) | P2—O5—C51—C56 | −97.3 (3) |
C14—C15—C16—C11 | 0.1 (4) | O5—C51—C52—C53 | 175.5 (3) |
C15—C16—C11—C12 | −0.8 (4) | O5—C51—C56—C55 | −174.4 (3) |
Pd—P1—O2—C21 | −54.8 (2) | C56—C51—C52—C53 | −0.3 (5) |
O1—P1—O2—C21 | −170.2 (2) | C51—C52—C53—C54 | −1.5 (5) |
O3—P1—O2—C21 | 76.7 (2) | C52—C53—C54—C55 | 2.0 (5) |
P1—O2—C21—C22 | 120.4 (3) | C53—C54—C55—C56 | −0.8 (5) |
P1—O2—C21—C26 | −61.9 (3) | C54—C55—C56—C51 | −0.9 (5) |
O2—C21—C22—C23 | 177.2 (3) | C55—C56—C51—C52 | 1.5 (5) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O6 | 1.08 (2) | 1.40 (2) | 2.435 (2) | 158 (2) |
C14—H14···Clii | 0.95 | 2.87 | 3.692 (3) | 145 |
C43—H43···O1iii | 0.95 | 2.58 | 3.332 (3) | 136 |
C45—H45···O5iv | 0.95 | 2.63 | 3.466 (3) | 147 |
Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+3/2, z+1/2; (iv) −x+1/2, y+1/2, −z+3/2. |
Experimental details
Crystal data |
Chemical formula | [Pd2(C12H10O3P)2Cl2(C12H11O3P)2] |
Mr | 1218.40 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 110 |
a, b, c (Å) | 12.268 (3), 10.514 (2), 19.549 (4) |
β (°) | 106.78 (3) |
V (Å3) | 2414.2 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.05 |
Crystal size (mm) | 0.20 × 0.13 × 0.06 |
|
Data collection |
Diffractometer | Kuma KM-4 CCD area-detector diffractometer |
Absorption correction | Analytical (CrysAlis RED; Oxford Diffraction, 2003) |
Tmin, Tmax | 0.837, 0.933 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 57621, 12649, 8606 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.857 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.111, 1.15 |
No. of reflections | 12649 |
No. of parameters | 310 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.04, −0.75 |
Selected geometric parameters (Å, º) topPd—Cl | 2.4139 (8) | P2—O4 | 1.594 (2) |
Pd—Cli | 2.4002 (8) | P2—O5 | 1.590 (2) |
Pd—P1 | 2.2248 (8) | P2—O6 | 1.517 (2) |
Pd—P2 | 2.2220 (8) | O1—C11 | 1.410 (3) |
P1—O1 | 1.594 (2) | O2—C21 | 1.416 (3) |
P1—O2 | 1.597 (2) | O4—C41 | 1.407 (3) |
P1—O3 | 1.514 (2) | O5—C51 | 1.418 (3) |
| | | |
P1—Pd—P2 | 92.81 (3) | O4—P2—Pd | 111.87 (7) |
P1—Pd—Cli | 89.78 (3) | O5—P2—Pd | 110.60 (7) |
P2—Pd—Cl | 90.10 (3) | O6—P2—Pd | 118.50 (8) |
Cl—Pd—Cli | 87.31 (3) | O4—P2—O5 | 93.89 (9) |
O1—P1—Pd | 112.32 (7) | O4—P2—O6 | 108.9 (1) |
O2—P1—Pd | 109.25 (7) | O5—P2—O6 | 110.4 (1) |
O3—P1—Pd | 118.06 (8) | P1—O1—C11 | 125.1 (2) |
O1—P1—O2 | 94.38 (9) | P1—O2—C21 | 118.1 (2) |
O1—P1—O3 | 109.9 (1) | P2—O4—C41 | 123.4 (2) |
O2—P1—O3 | 110.4 (1) | P2—O5—C51 | 121.4 (2) |
| | | |
Cli—Pd—P1—O1 | 48.93 (8) | Cl—Pd—P2—O6 | 171.69 (9) |
Cli—Pd—P1—O2 | −54.42 (8) | Pd—P1—O1—C11 | 68.6 (2) |
Cli—Pd—P1—O3 | 178.41 (9) | Pd—P1—O2—C21 | −54.8 (2) |
Cl—Pd—P2—O4 | 43.81 (8) | Pd—P2—O4—C41 | 73.3 (2) |
Cl—Pd—P2—O5 | −59.43 (8) | Pd—P2—O5—C51 | −62.3 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O6 | 1.08 (2) | 1.40 (2) | 2.435 (2) | 158 (2) |
C14—H14···Clii | 0.95 | 2.87 | 3.692 (3) | 145 |
C43—H43···O1iii | 0.95 | 2.58 | 3.332 (3) | 136 |
C45—H45···O5iv | 0.95 | 2.63 | 3.466 (3) | 147 |
Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+3/2, z+1/2; (iv) −x+1/2, y+1/2, −z+3/2. |
Comparison of the intramolecular hydrogen-bond geometry (Å, °) in various µ-chloro-bridged dinuclear phosphinitopalladium complexes. Comparative data from the Cambridge Structural Database (CSD, Version 5.27; Allen, 2002). topCSD Refcode | O-H | H···O | O···O | O-H···O | Reference |
This structurea | 1.08 (2) | 1.40 (2) | 2.435 (2) | 158 (2) | This work |
EGEGIGb | 1.14 | 1.27 | 2.404 | 174 | Li (2002) |
| 1.19 | 1.22 | 2.405 | 175 | |
HAZFIYa | 1.14 | 1.30 | 2.399 | 160 | Benito-Garagorri et al. (2005) |
HEBXERc | 1.21 | 1.21 | 2.408 | 169 | Ghaffar et al. (1994) |
| 0.88 | 1.53 | 2.403 | 174 | |
HEBXER01c | 1.16 | 1.26 | 2.402 | 166 | Benito-Garagorri et al. (2005) |
| 1.13 | 1.30 | 2.400 | 165 | |
QADTEVb | 1.20 | 1.23 | 2.394 | 161 | Evans et al. (2002) |
| 1.17 | 1.26 | 2.406 | 165 | |
YAZMIWa | 1.04 | 1.30 | 2.406 | 164 | Pryjomska et al. (2006) |
ZATQEQa | 1.04 | 1.37 | 2.401 | 173 | Gebauer et al. (1995) |
Notes: results are provided for (a) one centrosymmetric molecule, (b) one non-centrosymmetric molecule, and (c) two independent centrosymmetric molecules. |
Intermolecular π–π interactions (Å, °). Cg1 denotes the centroid of ring C21–C26 and Cg2 the centroid of ring C51–C56. Cg···Cg is the distance between ring centroids. The dihedral plane is that between the CgI and CgJ planes. The interplanar distance is the perpendicular distance of CgI from ring J plane. The offset is the lateral displacement of ring I relative to ring J. topCgI | CgJ | Cg···Cg | Dihedral angle | Interplanar distance | Offset |
1 | 2v | 3.750 (3) | 5.1 (2) | 3.671 (3) | 0.766 (3) |
2 | 1vi | 3.750 (3) | 5.1 (2) | 3.612 (3) | 1.008 (3) |
Symmetry codes: (v) x, y + 1, z; (vi) x, y − 1, z. |
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Carbon–carbon bond-forming reactions are important fundamental processes in synthetic chemistry. Among such reactions the most commonly recognized are: carbonylation, which, depending on the conditions, enables the synthesis of carboxylic acids, esters or amides in a one-step process (Mägerlein et al., 2000); olefination of aryl halides, the so-called Heck reaction (Beletskaya & Cheprakov, 2000); and the Suzuki process, which leads to the formation of biphenyl derivatives (Miyaura & Suzuki, 1995). Palladium compounds with phosphine ligands are frequently used as catalyst precursors in the above-mentioned reactions. Phosphinites, however, represent an interesting alternative to phosphines as ligands for metal ions employed as catalysts in organic synthesis. Such complexes have proved to be air-stable and highly active in methoxycarbonylation or the Heck reaction (Pryjomska et al., 2006) and also in Suzuki cross-coupling of aryl halides (Li, 2002). In this paper, we report the synthesis and crystallization of the title dimeric phosphinitopalladium complex, (I), which may be successfully used as an efficient catalyst precursor.
The molecule of the compound (I) (Fig. 1) contains a dimetallocyclic Pd2Cl2 core, with a crystallographic centre of inversion at the mid-point of the Pd···Pdi vector [symmetry code: (i) −x + 1, −y + 1, −z + 1]. The positive charge of each Pd atom is balanced by the O− atoms. There is clearly no Pd—Pd bond in the dimer, the Pd···Pdi distance of 3.4830 (9) Å being too long to consider any metal–metal interaction. The Pd atoms are four-coordinated in a square-planar geometry. The angles between adjacent ligands deviate only slightly from the expected value of 90° (Table 1). As a result of the presence of the inversion centre, the Pd/Cl/Pdi/Cli ring is strictly planar. The Pd—Cl and Pd—Cli bond lengths are quite similar [2.4139 (8) and 2.4002 (8) Å, respectively]. These distances appear to be somewhat large compared with the range reported for typical four-coordinate palladium complexes (2.298–2.354 Å; Orpen et al., 1989). However, such long bond distances are normally observed for analogous dinuclear µ-chloro-bridged palladium compounds and might be justified by the trans effect of the phosphorus ligands.
The geometric parameters around the four-coordinate atoms P1 and P2 indicate a noticeable deformation of the ideal tetrahedron towards a trigonal pyramid. The O3—P1—Pd and O6—P2—Pd angles differ considerably from the ideal value of 109.5° and approach 120°, while the O1—P1—O2 and O4—P2–O5 angles are very close to 90° (Table 1). Such large distortions of these angles might be explained by the steric effects of the different substituents or bond types, and are commonly observed for palladium complexes with diphenylphosphane ligands (Stockland et al., 2004). The bond lengths P1—O1, P1—O2, P2—O4 and P2—O5 are typical (Allen et al., 1987). In contrast, the nearly equal distances P1—O3 and P2—O6 fall between the values expected for single and double P—O bonds. As a result, the OH group on each side of the molecule forms a nearly symmetric intramolecular hydrogen bond with O− (Table 2). The existence of this type of hydrogen-bond interaction was also confirmed by 1H NMR spectroscopy (CDCl3), which revealed a broad signal at 10 p.p.m. This O3—H3···O6 interaction generates an S(6) motif (Bernstein et al., 1995) in the crystal structure.
Several µ-chloro-bridged dinuclear phosphinitopalladium complexes have previously been structurally characterized. The intramolecular hydrogen-bond geometries of such compounds are compared with that of (I) in Table 3. The O3—H3 distance of 1.08 (2) Å may at first appear to be rather large, especially when it is contrasted with the value observed for a typical hydroxy group. However, this bond length is comparable with the O—H distances found in the other characterized structures. Furthermore, there are also numerous complexes with longer O—H bond lengths, and in those cases the hydrogen-bond geometry becomes almost ideally symmetric. Finally, it is worth noting that the O···O distance observed for (I) is slightly longer than in all other palladium complexes described.
The molecules of (I) are linked by a few weak hydrogen-bond interactions of C—H···Cl and C—H···O types (Desiraju & Steiner, 1999). The aryl atoms C14, C43 and C45 act as hydrogen-bond donors (Table 2). As a consequence, a three-dimensional network of hydrogen-bond interactions is formed in the crystal structure (Fig. 2). Even though the H···Cl distance may at first appear to be fairly long compared with the expected value (Aullón et al., 1998), the presence of C—H···Cl hydrogen bonds was confirmed spectroscopically for a complex with H···Cl spacings even greater than 3 Å, where Cl was bonded to Pd (Fábry et al., 2004).
Additionally, the C21–C26 and C51–C56 phenyl rings are engaged in π–π stacking contacts (Fig. 3), which further assist in the stabilization of the crystal structure by assembling chains running parallel to the [010] direction. The observed distance between the centroids and the offset of the aryl rings (Table 4) are standard for energetically favourable non-bonded aromatic interactions (McGaughey et al., 1998). The phenyl rings in neighbouring stacks are arranged perpendicularly, thus forming a herring-bone pattern in the crystal structure.