Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112032192/fa3283sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112032192/fa3283Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112032192/fa3283IIsup3.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112032192/fa3283Isup4.cml |
CCDC references: 908118; 908119
For related literature, see: Abel et al. (1982); Allain et al. (1980); Boyd et al. (2004); Dräger et al. (1973); Grant (1990); James et al. (1980); Johnson et al. (1981); Lewis et al. (1976); Maezaki et al. (2000); Pettinari et al. (1999); Preston & du Preez (2002); Schwarze et al. (2012); Traeger, König, Städtke & Holdt (2012); Traeger, Klamroth, Kelling, Lubahn, Cleve, Mickler, Heydenreich, Müller & Holdt (2012).
The synthesis of ligand (I) has already been described (Traeger, König et al., 2012). Complex (II) was prepared following the procedure reported earlier (Traeger, Klamroth et al., 2012). Ligand (I) (30.18 mg, 0.11 mmol) was dissolved in MeOH (5 ml) and a solution of Na2PdCl4 (29.42 mg, 0.1 mmol) in MeOH (15 ml) was added. This solution was allowed to stand at 278 K for 48 h. The orange precipitate which formed was collected by filtration and washed with MeOH (yield: 0.38 mg, 0.08 mmol, 84%; m.p. 444.9–445.9 K).
H atoms were placed at calculated positions (aromatic C—H = 0.93 Å, methylene C—H = 0.97 Å and methyl C—H = 0.96 Å) and refined as riding atoms, with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2UUeq(C) otherwise. In (II), the methoxymethyl group at C7 is disordered over two sites of approximately equal occupancies. Similarity restraints were used for equivalent distances in the two disorder components. The H atoms were calculated in their expected positions and refined with a riding model.
For both compounds, data collection: X-AREA (Stoe & Cie, 2011); cell refinement: X-AREA (Stoe & Cie, 2011); data reduction: X-RED (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) based on ORTEPIII (Burnett & Johnson, 1996) for (I); ORTEP-3 for Windows (Farrugia, 1997), based on ORTEPIII (Burnett & Johnson, 1996) for (II). For both compounds, software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C12H18O3S2 | Dx = 1.309 Mg m−3 |
Mr = 274.38 | Melting point = 313–314 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.6089 (9) Å | Cell parameters from 18173 reflections |
b = 6.7055 (2) Å | θ = 1.7–29.6° |
c = 14.2492 (8) Å | µ = 0.38 mm−1 |
β = 111.044 (4)° | T = 210 K |
V = 1391.93 (12) Å3 | Block, colourless |
Z = 4 | 0.50 × 0.33 × 0.20 mm |
F(000) = 584 |
Stoe IPDS 2 diffractometer | 2444 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 2154 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.021 |
Detector resolution: 6.67 pixels mm-1 | θmax = 25.0°, θmin = 2.8° |
ω scan, Δω = 1° | h = −18→18 |
Absorption correction: integration (X-SHAPE; Stoe & Cie, 2011) | k = −7→7 |
Tmin = 0.859, Tmax = 0.984 | l = −16→16 |
10341 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)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.068 | w = 1/[σ2(Fo2) + (0.0349P)2 + 0.3882P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2444 reflections | Δρmax = 0.22 e Å−3 |
155 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0029 (8) |
C12H18O3S2 | V = 1391.93 (12) Å3 |
Mr = 274.38 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.6089 (9) Å | µ = 0.38 mm−1 |
b = 6.7055 (2) Å | T = 210 K |
c = 14.2492 (8) Å | 0.50 × 0.33 × 0.20 mm |
β = 111.044 (4)° |
Stoe IPDS 2 diffractometer | 2444 independent reflections |
Absorption correction: integration (X-SHAPE; Stoe & Cie, 2011) | 2154 reflections with I > 2σ(I) |
Tmin = 0.859, Tmax = 0.984 | Rint = 0.021 |
10341 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.22 e Å−3 |
2444 reflections | Δρmin = −0.19 e Å−3 |
155 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.68937 (9) | 0.71705 (19) | 0.83999 (9) | 0.0272 (3) | |
C2 | 0.78244 (9) | 0.7206 (2) | 0.85505 (10) | 0.0303 (3) | |
C3 | 0.81156 (11) | 0.8366 (2) | 0.79106 (12) | 0.0406 (4) | |
H3 | 0.8735 | 0.8416 | 0.8000 | 0.049* | |
C4 | 0.74867 (12) | 0.9441 (2) | 0.71439 (12) | 0.0433 (4) | |
H4 | 0.7688 | 1.0220 | 0.6724 | 0.052* | |
C5 | 0.65681 (11) | 0.9374 (2) | 0.69937 (11) | 0.0389 (4) | |
H5 | 0.6148 | 1.0083 | 0.6467 | 0.047* | |
C6 | 0.62721 (10) | 0.8250 (2) | 0.76275 (10) | 0.0327 (3) | |
H6 | 0.5651 | 0.8217 | 0.7535 | 0.039* | |
C7 | 0.64129 (10) | 0.3427 (2) | 0.87859 (10) | 0.0341 (3) | |
H7A | 0.6021 | 0.3404 | 0.8082 | 0.041* | |
H7B | 0.7020 | 0.2975 | 0.8841 | 0.041* | |
C8 | 0.60265 (10) | 0.2066 (2) | 0.93804 (11) | 0.0349 (3) | |
H8A | 0.5479 | 0.2649 | 0.9439 | 0.042* | |
H8B | 0.5865 | 0.0785 | 0.9047 | 0.042* | |
C9 | 0.64138 (12) | 0.0546 (2) | 1.09608 (12) | 0.0454 (4) | |
H9A | 0.5877 | 0.1101 | 1.1041 | 0.068* | |
H9B | 0.6893 | 0.0417 | 1.1608 | 0.068* | |
H9C | 0.6270 | −0.0744 | 1.0651 | 0.068* | |
C10 | 0.93694 (10) | 0.7610 (3) | 1.02782 (12) | 0.0414 (4) | |
H10A | 0.9871 | 0.6965 | 1.0804 | 0.050* | |
H10B | 0.9628 | 0.8368 | 0.9864 | 0.050* | |
C11 | 0.88897 (10) | 0.9008 (2) | 1.07479 (11) | 0.0402 (4) | |
H11A | 0.8403 | 0.9709 | 1.0229 | 0.048* | |
H11B | 0.8620 | 0.8267 | 1.1157 | 0.048* | |
C12 | 0.91348 (13) | 1.1842 (3) | 1.17715 (14) | 0.0570 (5) | |
H12A | 0.8684 | 1.2570 | 1.1242 | 0.086* | |
H12B | 0.9598 | 1.2744 | 1.2176 | 0.086* | |
H12C | 0.8845 | 1.1204 | 1.2183 | 0.086* | |
O1 | 0.55041 (8) | 0.65819 (17) | 0.90010 (10) | 0.0509 (3) | |
O2 | 0.67121 (7) | 0.18233 (16) | 1.03438 (8) | 0.0408 (3) | |
O3 | 0.95426 (7) | 1.03838 (18) | 1.13509 (8) | 0.0444 (3) | |
S1 | 0.64788 (3) | 0.59443 (5) | 0.92771 (3) | 0.03315 (12) | |
S2 | 0.86032 (3) | 0.57247 (6) | 0.95139 (3) | 0.04182 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0308 (7) | 0.0237 (6) | 0.0275 (6) | −0.0023 (5) | 0.0108 (5) | −0.0030 (5) |
C2 | 0.0305 (7) | 0.0289 (7) | 0.0298 (7) | −0.0005 (6) | 0.0086 (6) | −0.0022 (5) |
C3 | 0.0352 (8) | 0.0468 (9) | 0.0430 (8) | −0.0086 (7) | 0.0177 (7) | −0.0021 (7) |
C4 | 0.0556 (10) | 0.0386 (9) | 0.0372 (8) | −0.0107 (7) | 0.0186 (7) | 0.0043 (7) |
C5 | 0.0507 (9) | 0.0290 (7) | 0.0310 (7) | 0.0026 (7) | 0.0073 (6) | 0.0024 (6) |
C6 | 0.0310 (7) | 0.0308 (7) | 0.0325 (7) | 0.0013 (6) | 0.0066 (6) | −0.0033 (6) |
C7 | 0.0417 (8) | 0.0289 (7) | 0.0322 (7) | −0.0027 (6) | 0.0139 (6) | −0.0040 (6) |
C8 | 0.0382 (8) | 0.0290 (7) | 0.0362 (7) | −0.0043 (6) | 0.0119 (6) | −0.0009 (6) |
C9 | 0.0604 (11) | 0.0363 (8) | 0.0450 (9) | 0.0005 (7) | 0.0257 (8) | 0.0091 (7) |
C10 | 0.0272 (7) | 0.0506 (9) | 0.0406 (8) | 0.0037 (7) | 0.0052 (6) | −0.0030 (7) |
C11 | 0.0293 (7) | 0.0514 (9) | 0.0386 (8) | −0.0012 (7) | 0.0105 (6) | −0.0037 (7) |
C12 | 0.0532 (11) | 0.0614 (12) | 0.0514 (10) | 0.0058 (9) | 0.0127 (8) | −0.0145 (9) |
O1 | 0.0455 (7) | 0.0418 (6) | 0.0802 (9) | 0.0011 (5) | 0.0407 (6) | −0.0007 (6) |
O2 | 0.0384 (6) | 0.0430 (6) | 0.0397 (6) | −0.0033 (5) | 0.0122 (5) | 0.0116 (5) |
O3 | 0.0329 (6) | 0.0525 (7) | 0.0432 (6) | −0.0002 (5) | 0.0082 (5) | −0.0097 (5) |
S1 | 0.0415 (2) | 0.02861 (19) | 0.0348 (2) | −0.00416 (15) | 0.02035 (16) | −0.00373 (14) |
S2 | 0.0355 (2) | 0.0362 (2) | 0.0445 (2) | 0.00653 (16) | 0.00304 (16) | 0.00224 (16) |
C1—C6 | 1.3819 (19) | C8—H8B | 0.9700 |
C1—C2 | 1.3905 (19) | C9—O2 | 1.4204 (18) |
C1—S1 | 1.7997 (13) | C9—H9A | 0.9600 |
C2—C3 | 1.393 (2) | C9—H9B | 0.9600 |
C2—S2 | 1.7748 (14) | C9—H9C | 0.9600 |
C3—C4 | 1.381 (2) | C10—C11 | 1.499 (2) |
C3—H3 | 0.9300 | C10—S2 | 1.8110 (16) |
C4—C5 | 1.372 (2) | C10—H10A | 0.9700 |
C4—H4 | 0.9300 | C10—H10B | 0.9700 |
C5—C6 | 1.377 (2) | C11—O3 | 1.4140 (19) |
C5—H5 | 0.9300 | C11—H11A | 0.9700 |
C6—H6 | 0.9300 | C11—H11B | 0.9700 |
C7—C8 | 1.5102 (19) | C12—O3 | 1.412 (2) |
C7—S1 | 1.8163 (14) | C12—H12A | 0.9600 |
C7—H7A | 0.9700 | C12—H12B | 0.9600 |
C7—H7B | 0.9700 | C12—H12C | 0.9600 |
C8—O2 | 1.4146 (18) | O1—S1 | 1.4907 (12) |
C8—H8A | 0.9700 | ||
C6—C1—C2 | 120.65 (12) | O2—C9—H9A | 109.5 |
C6—C1—S1 | 117.88 (10) | O2—C9—H9B | 109.5 |
C2—C1—S1 | 121.14 (10) | H9A—C9—H9B | 109.5 |
C1—C2—C3 | 118.48 (13) | O2—C9—H9C | 109.5 |
C1—C2—S2 | 119.82 (10) | H9A—C9—H9C | 109.5 |
C3—C2—S2 | 121.66 (11) | H9B—C9—H9C | 109.5 |
C4—C3—C2 | 120.20 (14) | C11—C10—S2 | 112.15 (11) |
C4—C3—H3 | 119.9 | C11—C10—H10A | 109.2 |
C2—C3—H3 | 119.9 | S2—C10—H10A | 109.2 |
C5—C4—C3 | 120.83 (14) | C11—C10—H10B | 109.2 |
C5—C4—H4 | 119.6 | S2—C10—H10B | 109.2 |
C3—C4—H4 | 119.6 | H10A—C10—H10B | 107.9 |
C4—C5—C6 | 119.57 (14) | O3—C11—C10 | 108.22 (12) |
C4—C5—H5 | 120.2 | O3—C11—H11A | 110.1 |
C6—C5—H5 | 120.2 | C10—C11—H11A | 110.1 |
C5—C6—C1 | 120.26 (14) | O3—C11—H11B | 110.1 |
C5—C6—H6 | 119.9 | C10—C11—H11B | 110.1 |
C1—C6—H6 | 119.9 | H11A—C11—H11B | 108.4 |
C8—C7—S1 | 108.91 (10) | O3—C12—H12A | 109.5 |
C8—C7—H7A | 109.9 | O3—C12—H12B | 109.5 |
S1—C7—H7A | 109.9 | H12A—C12—H12B | 109.5 |
C8—C7—H7B | 109.9 | O3—C12—H12C | 109.5 |
S1—C7—H7B | 109.9 | H12A—C12—H12C | 109.5 |
H7A—C7—H7B | 108.3 | H12B—C12—H12C | 109.5 |
O2—C8—C7 | 107.37 (11) | C8—O2—C9 | 111.60 (12) |
O2—C8—H8A | 110.2 | C12—O3—C11 | 111.92 (13) |
C7—C8—H8A | 110.2 | O1—S1—C1 | 105.86 (7) |
O2—C8—H8B | 110.2 | O1—S1—C7 | 104.70 (7) |
C7—C8—H8B | 110.2 | C1—S1—C7 | 98.15 (6) |
H8A—C8—H8B | 108.5 | C2—S2—C10 | 101.27 (7) |
C6—C1—C2—C3 | 0.5 (2) | S2—C10—C11—O3 | 178.29 (10) |
S1—C1—C2—C3 | −172.81 (11) | C7—C8—O2—C9 | −179.56 (12) |
C6—C1—C2—S2 | −177.34 (10) | C10—C11—O3—C12 | 176.14 (14) |
S1—C1—C2—S2 | 9.33 (16) | C6—C1—S1—O1 | −5.52 (12) |
C1—C2—C3—C4 | −0.3 (2) | C2—C1—S1—O1 | 167.98 (11) |
S2—C2—C3—C4 | 177.49 (12) | C6—C1—S1—C7 | 102.36 (11) |
C2—C3—C4—C5 | −0.6 (2) | C2—C1—S1—C7 | −84.13 (12) |
C3—C4—C5—C6 | 1.2 (2) | C8—C7—S1—O1 | −68.44 (11) |
C4—C5—C6—C1 | −1.0 (2) | C8—C7—S1—C1 | −177.28 (10) |
C2—C1—C6—C5 | 0.2 (2) | C1—C2—S2—C10 | −120.77 (12) |
S1—C1—C6—C5 | 173.71 (11) | C3—C2—S2—C10 | 61.45 (13) |
S1—C7—C8—O2 | −71.79 (13) | C11—C10—S2—C2 | 64.48 (13) |
[PdCl2(C12H18O3S2)] | Dx = 1.776 Mg m−3 |
Mr = 451.68 | Melting point = 455–456 K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.6595 (5) Å | Cell parameters from 10870 reflections |
b = 12.9818 (7) Å | θ = 1.6–29.7° |
c = 12.2828 (8) Å | µ = 1.66 mm−1 |
β = 96.416 (4)° | T = 210 K |
V = 1689.04 (15) Å3 | Block, yellow |
Z = 4 | 0.20 × 0.13 × 0.10 mm |
F(000) = 904 |
Stoe IPDS 2 diffractometer | 2973 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 2571 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.025 |
Detector resolution: 6.67 pixels mm-1 | θmax = 25.0°, θmin = 2.3° |
ω scan, Δω = 1° | h = −12→12 |
Absorption correction: integration (X-SHAPE; Stoe & Cie, 2011) | k = −15→15 |
Tmin = 0.820, Tmax = 0.897 | l = −14→14 |
10614 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)] = 0.021 | H-atom parameters constrained |
wR(F2) = 0.054 | w = 1/[σ2(Fo2) + (0.0375P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.002 |
2973 reflections | Δρmax = 0.63 e Å−3 |
213 parameters | Δρmin = −0.39 e Å−3 |
3 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0052 (3) |
[PdCl2(C12H18O3S2)] | V = 1689.04 (15) Å3 |
Mr = 451.68 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.6595 (5) Å | µ = 1.66 mm−1 |
b = 12.9818 (7) Å | T = 210 K |
c = 12.2828 (8) Å | 0.20 × 0.13 × 0.10 mm |
β = 96.416 (4)° |
Stoe IPDS 2 diffractometer | 2973 independent reflections |
Absorption correction: integration (X-SHAPE; Stoe & Cie, 2011) | 2571 reflections with I > 2σ(I) |
Tmin = 0.820, Tmax = 0.897 | Rint = 0.025 |
10614 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 3 restraints |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.63 e Å−3 |
2973 reflections | Δρmin = −0.39 e Å−3 |
213 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.6020 (2) | 0.65338 (19) | 0.7083 (2) | 0.0339 (5) | |
C2 | 0.6188 (2) | 0.70384 (18) | 0.8082 (2) | 0.0349 (6) | |
C3 | 0.7396 (3) | 0.7301 (2) | 0.8545 (3) | 0.0485 (7) | |
H3 | 0.7517 | 0.7630 | 0.9221 | 0.058* | |
C4 | 0.8409 (3) | 0.7066 (3) | 0.7988 (3) | 0.0605 (9) | |
H4 | 0.9222 | 0.7229 | 0.8297 | 0.073* | |
C5 | 0.8234 (3) | 0.6593 (3) | 0.6983 (3) | 0.0626 (10) | |
H5 | 0.8929 | 0.6461 | 0.6609 | 0.075* | |
C6 | 0.7036 (3) | 0.6309 (2) | 0.6514 (3) | 0.0484 (7) | |
H6 | 0.6921 | 0.5977 | 0.5839 | 0.058* | |
C7 | 0.4431 (3) | 0.48078 (19) | 0.6701 (2) | 0.0411 (6) | |
H7A | 0.3587 | 0.4568 | 0.6448 | 0.049* | 0.51 |
H7B | 0.5003 | 0.4499 | 0.6233 | 0.049* | 0.51 |
H7C | 0.5199 | 0.4508 | 0.6484 | 0.049* | 0.49 |
H7D | 0.3724 | 0.4526 | 0.6229 | 0.049* | 0.49 |
C10 | 0.4874 (3) | 0.8756 (2) | 0.8654 (2) | 0.0484 (7) | |
H10A | 0.4121 | 0.9025 | 0.8930 | 0.058* | |
H10B | 0.5597 | 0.9024 | 0.9117 | 0.058* | |
C11 | 0.4920 (4) | 0.9150 (2) | 0.7532 (3) | 0.0598 (9) | |
H11A | 0.4950 | 0.9897 | 0.7545 | 0.072* | |
H11B | 0.5677 | 0.8901 | 0.7248 | 0.072* | |
C12 | 0.3852 (9) | 0.9213 (4) | 0.5798 (4) | 0.157 (3) | |
H12A | 0.3922 | 0.9950 | 0.5820 | 0.235* | |
H12B | 0.3070 | 0.9021 | 0.5382 | 0.235* | |
H12C | 0.4544 | 0.8929 | 0.5460 | 0.235* | |
Cl1 | 0.15133 (6) | 0.63419 (6) | 0.63733 (5) | 0.04489 (17) | |
Cl2 | 0.19145 (7) | 0.74338 (5) | 0.88979 (5) | 0.04498 (17) | |
O1 | 0.43262 (19) | 0.63931 (17) | 0.53435 (14) | 0.0466 (5) | |
O3 | 0.3879 (3) | 0.88304 (18) | 0.6868 (2) | 0.0899 (10) | |
Pd1 | 0.318552 (16) | 0.685109 (12) | 0.761851 (14) | 0.02647 (8) | |
S1 | 0.44711 (6) | 0.61825 (4) | 0.65221 (4) | 0.03019 (14) | |
S2 | 0.48669 (6) | 0.73508 (5) | 0.87884 (5) | 0.03579 (15) | |
C8 | 0.4772 (10) | 0.4422 (12) | 0.7840 (8) | 0.050 (3) | 0.504 (7) |
H8A | 0.4377 | 0.4838 | 0.8362 | 0.060* | 0.504 (7) |
H8B | 0.4509 | 0.3712 | 0.7906 | 0.060* | 0.504 (7) |
O2 | 0.6097 (5) | 0.4506 (4) | 0.8020 (4) | 0.0500 (15) | 0.504 (7) |
C9 | 0.648 (2) | 0.4126 (10) | 0.9068 (13) | 0.066 (4) | 0.504 (7) |
H9A | 0.6259 | 0.3412 | 0.9104 | 0.099* | 0.504 (7) |
H9B | 0.6077 | 0.4509 | 0.9598 | 0.099* | 0.504 (7) |
H9C | 0.7383 | 0.4198 | 0.9222 | 0.099* | 0.504 (7) |
C81 | 0.4313 (13) | 0.4511 (11) | 0.7870 (9) | 0.054 (3) | 0.496 (7) |
H81A | 0.3495 | 0.4743 | 0.8045 | 0.065* | 0.496 (7) |
H81B | 0.4313 | 0.3765 | 0.7910 | 0.065* | 0.496 (7) |
O21 | 0.5236 (5) | 0.4879 (3) | 0.8698 (3) | 0.0533 (17) | 0.496 (7) |
C91 | 0.6399 (16) | 0.4369 (13) | 0.8777 (17) | 0.084 (6) | 0.496 (7) |
H91A | 0.6695 | 0.4340 | 0.8068 | 0.127* | 0.496 (7) |
H91B | 0.6301 | 0.3683 | 0.9045 | 0.127* | 0.496 (7) |
H91C | 0.7001 | 0.4736 | 0.9274 | 0.127* | 0.496 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0216 (12) | 0.0386 (12) | 0.0413 (13) | 0.0020 (10) | 0.0020 (10) | 0.0108 (11) |
C2 | 0.0256 (13) | 0.0313 (12) | 0.0462 (14) | 0.0001 (10) | −0.0028 (11) | 0.0068 (10) |
C3 | 0.0285 (15) | 0.0435 (15) | 0.0695 (19) | −0.0039 (12) | −0.0126 (14) | 0.0106 (14) |
C4 | 0.0289 (16) | 0.0553 (18) | 0.093 (3) | −0.0060 (13) | −0.0107 (16) | 0.0303 (18) |
C5 | 0.0291 (16) | 0.069 (2) | 0.093 (3) | 0.0121 (15) | 0.0214 (16) | 0.042 (2) |
C6 | 0.0353 (16) | 0.0575 (17) | 0.0546 (17) | 0.0114 (13) | 0.0146 (13) | 0.0172 (14) |
C7 | 0.0462 (16) | 0.0316 (12) | 0.0454 (14) | 0.0030 (12) | 0.0046 (12) | −0.0106 (11) |
C10 | 0.0514 (18) | 0.0342 (13) | 0.0563 (17) | 0.0004 (12) | −0.0093 (14) | −0.0150 (12) |
C11 | 0.075 (2) | 0.0315 (14) | 0.073 (2) | −0.0070 (14) | 0.0108 (18) | −0.0040 (14) |
C12 | 0.323 (10) | 0.065 (3) | 0.068 (3) | −0.026 (4) | −0.042 (4) | 0.023 (2) |
Cl1 | 0.0272 (3) | 0.0601 (4) | 0.0454 (4) | −0.0093 (3) | −0.0046 (3) | −0.0006 (3) |
Cl2 | 0.0402 (4) | 0.0531 (4) | 0.0433 (4) | 0.0162 (3) | 0.0118 (3) | −0.0015 (3) |
O1 | 0.0422 (11) | 0.0699 (13) | 0.0279 (9) | 0.0104 (10) | 0.0047 (8) | 0.0031 (8) |
O3 | 0.146 (3) | 0.0509 (13) | 0.0625 (15) | −0.0321 (15) | −0.0319 (17) | 0.0170 (12) |
Pd1 | 0.02235 (11) | 0.02810 (11) | 0.02865 (11) | 0.00241 (7) | 0.00151 (7) | −0.00010 (7) |
S1 | 0.0271 (3) | 0.0360 (3) | 0.0272 (3) | 0.0034 (2) | 0.0020 (2) | −0.0014 (2) |
S2 | 0.0344 (3) | 0.0376 (3) | 0.0335 (3) | 0.0012 (3) | −0.0047 (3) | −0.0052 (2) |
C8 | 0.073 (9) | 0.029 (4) | 0.043 (4) | 0.022 (6) | −0.014 (4) | 0.001 (3) |
O2 | 0.059 (3) | 0.049 (3) | 0.040 (3) | 0.003 (2) | −0.002 (2) | 0.020 (2) |
C9 | 0.105 (8) | 0.042 (7) | 0.049 (5) | 0.008 (6) | −0.004 (4) | 0.003 (5) |
C81 | 0.066 (8) | 0.025 (5) | 0.067 (6) | 0.008 (6) | −0.018 (5) | 0.002 (3) |
O21 | 0.077 (4) | 0.036 (2) | 0.044 (3) | 0.002 (2) | −0.006 (2) | −0.0043 (17) |
C91 | 0.075 (8) | 0.040 (7) | 0.14 (2) | 0.009 (5) | 0.004 (11) | 0.016 (9) |
C1—C6 | 1.384 (4) | C11—H11B | 0.9700 |
C1—C2 | 1.384 (4) | C12—O3 | 1.402 (5) |
C1—S1 | 1.777 (2) | C12—H12A | 0.9600 |
C2—C3 | 1.391 (4) | C12—H12B | 0.9600 |
C2—S2 | 1.781 (3) | C12—H12C | 0.9600 |
C3—C4 | 1.375 (5) | Cl1—Pd1 | 2.3117 (6) |
C3—H3 | 0.9300 | Cl2—Pd1 | 2.3137 (7) |
C4—C5 | 1.373 (6) | O1—S1 | 1.4644 (18) |
C4—H4 | 0.9300 | Pd1—S1 | 2.2040 (6) |
C5—C6 | 1.391 (5) | Pd1—S2 | 2.2632 (6) |
C5—H5 | 0.9300 | C8—O2 | 1.409 (11) |
C6—H6 | 0.9300 | C8—H8A | 0.9700 |
C7—C8 | 1.492 (10) | C8—H8B | 0.9700 |
C7—C81 | 1.505 (11) | O2—C9 | 1.397 (12) |
C7—S1 | 1.799 (3) | C9—H9A | 0.9600 |
C7—H7A | 0.9700 | C9—H9B | 0.9600 |
C7—H7B | 0.9700 | C9—H9C | 0.9600 |
C7—H7C | 0.9700 | C81—O21 | 1.416 (13) |
C7—H7D | 0.9700 | C81—H81A | 0.9700 |
C10—C11 | 1.476 (4) | C81—H81B | 0.9700 |
C10—S2 | 1.832 (3) | O21—C91 | 1.400 (15) |
C10—H10A | 0.9700 | C91—H91A | 0.9600 |
C10—H10B | 0.9700 | C91—H91B | 0.9600 |
C11—O3 | 1.367 (4) | C91—H91C | 0.9600 |
C11—H11A | 0.9700 | ||
C6—C1—C2 | 121.1 (2) | C10—C11—H11A | 109.7 |
C6—C1—S1 | 119.7 (2) | O3—C11—H11B | 109.7 |
C2—C1—S1 | 119.17 (19) | C10—C11—H11B | 109.7 |
C1—C2—C3 | 120.0 (3) | H11A—C11—H11B | 108.2 |
C1—C2—S2 | 120.59 (19) | O3—C12—H12A | 109.5 |
C3—C2—S2 | 119.4 (2) | O3—C12—H12B | 109.5 |
C4—C3—C2 | 119.0 (3) | H12A—C12—H12B | 109.5 |
C4—C3—H3 | 120.5 | O3—C12—H12C | 109.5 |
C2—C3—H3 | 120.5 | H12A—C12—H12C | 109.5 |
C5—C4—C3 | 120.7 (3) | H12B—C12—H12C | 109.5 |
C5—C4—H4 | 119.6 | C11—O3—C12 | 112.5 (4) |
C3—C4—H4 | 119.6 | S1—Pd1—S2 | 89.91 (2) |
C4—C5—C6 | 121.2 (3) | S1—Pd1—Cl1 | 88.24 (2) |
C4—C5—H5 | 119.4 | S2—Pd1—Cl1 | 177.96 (3) |
C6—C5—H5 | 119.4 | S1—Pd1—Cl2 | 174.30 (2) |
C1—C6—C5 | 117.9 (3) | S2—Pd1—Cl2 | 87.55 (3) |
C1—C6—H6 | 121.0 | Cl1—Pd1—Cl2 | 94.37 (3) |
C5—C6—H6 | 121.0 | O1—S1—C1 | 109.05 (12) |
C8—C7—C81 | 19.5 (7) | O1—S1—C7 | 107.73 (12) |
C8—C7—S1 | 116.2 (6) | C1—S1—C7 | 103.94 (13) |
C81—C7—S1 | 112.1 (6) | O1—S1—Pd1 | 121.76 (8) |
C8—C7—H7A | 108.2 | C1—S1—Pd1 | 106.04 (9) |
C81—C7—H7A | 92.9 | C7—S1—Pd1 | 106.93 (10) |
S1—C7—H7A | 108.2 | C2—S2—C10 | 99.88 (14) |
C8—C7—H7B | 108.2 | C2—S2—Pd1 | 103.79 (9) |
C81—C7—H7B | 125.7 | C10—S2—Pd1 | 103.85 (9) |
S1—C7—H7B | 108.2 | O2—C8—C7 | 104.8 (8) |
H7A—C7—H7B | 107.4 | O2—C8—H8A | 110.8 |
C8—C7—H7C | 89.9 | C7—C8—H8A | 110.8 |
C81—C7—H7C | 108.8 | O2—C8—H8B | 110.8 |
S1—C7—H7C | 109.4 | C7—C8—H8B | 110.8 |
H7A—C7—H7C | 124.3 | H8A—C8—H8B | 108.9 |
H7B—C7—H7C | 20.9 | C9—O2—C8 | 107.8 (11) |
C8—C7—H7D | 121.7 | O21—C81—C7 | 118.2 (10) |
C81—C7—H7D | 109.4 | O21—C81—H81A | 107.7 |
S1—C7—H7D | 109.2 | C7—C81—H81A | 107.7 |
H7A—C7—H7D | 19.2 | O21—C81—H81B | 107.7 |
H7B—C7—H7D | 89.3 | C7—C81—H81B | 107.7 |
H7C—C7—H7D | 107.9 | H81A—C81—H81B | 107.1 |
C11—C10—S2 | 115.5 (2) | C91—O21—C81 | 115.4 (11) |
C11—C10—H10A | 108.4 | O21—C91—H91A | 109.5 |
S2—C10—H10A | 108.4 | O21—C91—H91B | 109.5 |
C11—C10—H10B | 108.4 | H91A—C91—H91B | 109.5 |
S2—C10—H10B | 108.4 | O21—C91—H91C | 109.5 |
H10A—C10—H10B | 107.5 | H91A—C91—H91C | 109.5 |
O3—C11—C10 | 110.0 (3) | H91B—C91—H91C | 109.5 |
O3—C11—H11A | 109.7 | ||
C6—C1—C2—C3 | −1.9 (4) | Cl1—Pd1—S1—O1 | 47.62 (11) |
S1—C1—C2—C3 | 178.68 (19) | Cl2—Pd1—S1—O1 | 164.9 (3) |
C6—C1—C2—S2 | 178.4 (2) | S2—Pd1—S1—C1 | −6.23 (8) |
S1—C1—C2—S2 | −1.0 (3) | Cl1—Pd1—S1—C1 | 172.90 (9) |
C1—C2—C3—C4 | 1.0 (4) | Cl2—Pd1—S1—C1 | −69.8 (3) |
S2—C2—C3—C4 | −179.4 (2) | S2—Pd1—S1—C7 | 104.23 (10) |
C2—C3—C4—C5 | 1.0 (4) | Cl1—Pd1—S1—C7 | −76.64 (10) |
C3—C4—C5—C6 | −2.1 (5) | Cl2—Pd1—S1—C7 | 40.6 (3) |
C2—C1—C6—C5 | 0.8 (4) | C1—C2—S2—C10 | −111.1 (2) |
S1—C1—C6—C5 | −179.8 (2) | C3—C2—S2—C10 | 69.2 (2) |
C4—C5—C6—C1 | 1.2 (4) | C1—C2—S2—Pd1 | −4.1 (2) |
S2—C10—C11—O3 | 61.3 (4) | C3—C2—S2—Pd1 | 176.26 (19) |
C10—C11—O3—C12 | 177.9 (4) | C11—C10—S2—C2 | 50.9 (3) |
C6—C1—S1—O1 | −41.0 (2) | C11—C10—S2—Pd1 | −56.0 (3) |
C2—C1—S1—O1 | 138.4 (2) | S1—Pd1—S2—C2 | 5.75 (8) |
C6—C1—S1—C7 | 73.7 (2) | Cl1—Pd1—S2—C2 | −19.4 (7) |
C2—C1—S1—C7 | −106.9 (2) | Cl2—Pd1—S2—C2 | −179.36 (8) |
C6—C1—S1—Pd1 | −173.74 (19) | S1—Pd1—S2—C10 | 109.79 (11) |
C2—C1—S1—Pd1 | 5.7 (2) | Cl1—Pd1—S2—C10 | 84.6 (7) |
C8—C7—S1—O1 | 170.4 (5) | Cl2—Pd1—S2—C10 | −75.32 (11) |
C81—C7—S1—O1 | −168.7 (6) | C81—C7—C8—O2 | −159 (4) |
C8—C7—S1—C1 | 54.8 (5) | S1—C7—C8—O2 | −76.2 (10) |
C81—C7—S1—C1 | 75.7 (6) | C7—C8—O2—C9 | −178.3 (9) |
C8—C7—S1—Pd1 | −57.1 (5) | C8—C7—C81—O21 | 50 (3) |
C81—C7—S1—Pd1 | −36.2 (6) | S1—C7—C81—O21 | −56.6 (11) |
S2—Pd1—S1—O1 | −131.51 (11) | C7—C81—O21—C91 | −76.7 (14) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C12H18O3S2 | [PdCl2(C12H18O3S2)] |
Mr | 274.38 | 451.68 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 210 | 210 |
a, b, c (Å) | 15.6089 (9), 6.7055 (2), 14.2492 (8) | 10.6595 (5), 12.9818 (7), 12.2828 (8) |
β (°) | 111.044 (4) | 96.416 (4) |
V (Å3) | 1391.93 (12) | 1689.04 (15) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.38 | 1.66 |
Crystal size (mm) | 0.50 × 0.33 × 0.20 | 0.20 × 0.13 × 0.10 |
Data collection | ||
Diffractometer | Stoe IPDS 2 diffractometer | Stoe IPDS 2 diffractometer |
Absorption correction | Integration (X-SHAPE; Stoe & Cie, 2011) | Integration (X-SHAPE; Stoe & Cie, 2011) |
Tmin, Tmax | 0.859, 0.984 | 0.820, 0.897 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10341, 2444, 2154 | 10614, 2973, 2571 |
Rint | 0.021 | 0.025 |
(sin θ/λ)max (Å−1) | 0.595 | 0.594 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.068, 1.05 | 0.021, 0.054, 1.01 |
No. of reflections | 2444 | 2973 |
No. of parameters | 155 | 213 |
No. of restraints | 0 | 3 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.19 | 0.63, −0.39 |
Computer programs: X-AREA (Stoe & Cie, 2011), X-RED (Stoe & Cie, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) based on ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997), based on ORTEPIII (Burnett & Johnson, 1996).
C1—C2 | 1.3905 (19) | C8—O2 | 1.4146 (18) |
C1—S1 | 1.7997 (13) | C11—O3 | 1.4140 (19) |
C2—S2 | 1.7748 (14) | O1—S1 | 1.4907 (12) |
C7—S1 | 1.8163 (14) | ||
C6—C1—C2 | 120.65 (12) | C3—C2—S2 | 121.66 (11) |
C6—C1—S1 | 117.88 (10) | O1—S1—C1 | 105.86 (7) |
C2—C1—S1 | 121.14 (10) | O1—S1—C7 | 104.70 (7) |
C1—C2—C3 | 118.48 (13) | C1—S1—C7 | 98.15 (6) |
C1—C2—S2 | 119.82 (10) | C2—S2—C10 | 101.27 (7) |
S1—C1—C2—S2 | 9.33 (16) | C6—C1—S1—O1 | −5.52 (12) |
S2—C2—C3—C4 | 177.49 (12) | C6—C1—S1—C7 | 102.36 (11) |
S1—C1—C6—C5 | 173.71 (11) | C1—C2—S2—C10 | −120.77 (12) |
C1—C2 | 1.384 (4) | Cl1—Pd1 | 2.3117 (6) |
C1—S1 | 1.777 (2) | Cl2—Pd1 | 2.3137 (7) |
C2—S2 | 1.781 (3) | Pd1—S1 | 2.2040 (6) |
C11—O3 | 1.367 (4) | Pd1—S2 | 2.2632 (6) |
C6—C1—C2 | 121.1 (2) | Cl1—Pd1—Cl2 | 94.37 (3) |
C6—C1—S1 | 119.7 (2) | O1—S1—C1 | 109.05 (12) |
C2—C1—S1 | 119.17 (19) | O1—S1—C7 | 107.73 (12) |
C1—C2—C3 | 120.0 (3) | C1—S1—C7 | 103.94 (13) |
C1—C2—S2 | 120.59 (19) | O1—S1—Pd1 | 121.76 (8) |
S1—Pd1—S2 | 89.91 (2) | C1—S1—Pd1 | 106.04 (9) |
S1—Pd1—Cl1 | 88.24 (2) | C7—S1—Pd1 | 106.93 (10) |
S2—Pd1—Cl1 | 177.96 (3) | C2—S2—C10 | 99.88 (14) |
S1—Pd1—Cl2 | 174.30 (2) | C2—S2—Pd1 | 103.79 (9) |
S2—Pd1—Cl2 | 87.55 (3) | C10—S2—Pd1 | 103.85 (9) |
S1—C1—C2—S2 | −1.0 (3) | C6—C1—S1—C7 | 73.7 (2) |
S2—C2—C3—C4 | −179.4 (2) | C8—C7—S1—O1 | 170.4 (5) |
S1—C1—C6—C5 | −179.8 (2) | C1—C2—S2—C10 | −111.1 (2) |
C2—C1—S1—O1 | 138.4 (2) |
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The chelating dithioether 1,2-bis[(2-methoxyethyl)sulfanyl]benzene is a novel, highly selective solvent extractant for the recovery of palladium from spent automotive catalysts (Traeger, Klamroth et al., 2012). In oxidizing hydrochloric acid media, traces of the mono-oxidized derivative, a thioether sulfoxide, occur (Traeger, König et al., 2012). This compound, 1-[(2-methoxyethyl)sulfanyl]-2-[(2-methoxyethyl)sulfinyl]benzene, (I) (Fig. 1), has been found to affect the extraction behaviour considerably in highly acidic media, probably via the formation of protonated species and subsequent ion pairing with [PdCl4]2-. It is assumed (Grant, 1990) that in extraction processes rhodium(III) and dialkyl sulfoxides form species similar to the complex [H(R2SO)2][RhCl4(R2SO)2], that was found by James et al. (1980). Regarding palladium(II), Preston & du Preez (2002) have suggested that, depending on the hydrochloric acid concentration, either the coordination complex [PdCl2L2] or an outer sphere complex [L2.H3O]+[PdCl3L]-, which contains an oxonium ion solvated by dialkyl sulfoxides, predominates (L = dialkyl sulfoxide). On the other hand, Lewis et al. (1976) postulated the formation of the neutral species [PdCl2L2] (L = di-n-heptyl sulfoxide) even under strongly acidic conditions. The crystal structure of the square-planar tetrakis(dimethyl sulfoxide)palladium(II) bis(tetrafluoroborate) dimethyl sulfoxide solvate reported by Johnson et al. (1981) shows that, in principle, sulfoxides can bind PdII via the S and the O atoms. In the deprotonated form, the chelating thioether sulfoxide (I) can coordinate PdII similarly to the dithioether via the two S atoms in square-planar complexes. The molecular structure of the dithioether PdII complex was recently characterized by Traeger, Klamroth et al. (2012). We describe here the crystal structure of the thioether sulfoxide, (I), and the corresponding coordination compound dichlorido{1-[(2-methoxyethyl)sulfanyl]-2-[(2-methoxyethyl)sulfinyl]benzene-κ2S,S'}palladium(II), (II), which is, to the best of our knowledge, the first PdCl2 complex coordinated by a thioether and a sulfoxide functional group ever reported. The structure of (II) is shown in Fig. 2.
Unlike the analogous open-chain dithioethers, which are based on a vicinal dithioether unit with electron-withdrawing backbones and containing 2-hydroxyethyl or 2-methoxyethyl arms (Traeger, Klamroth et al., 2012), thioether sulfoxide (I) is chiral and gives a racemate. For this reason the two H atoms in both of the methylene groups C7/H7A/H7B and C8/H8A/H8B near the S1O1 sulfinyl group are diastereotopic and each of the H atoms gives a single 1H NMR signal (Traeger, König et al., 2012). The three substituents and the free electron pair of atom S1 form a distorted tetrahedron. The bond angles at S1 are all found to be smaller than the ideal tetrahedral value (Table 1). Molecular structures of thioether sulfoxide compounds with similar structural fragments have been published by Boyd et al. (2004) and Maezaki et al. (2000). The vicinal S atoms are also connected via a benzene ring, yet in those cases the S atoms themselves are part of a seven-membered ring. However, all bond lengths and angles involving the S atoms in the previously reported structures are comparable to those observed in (I). The short S1···S2 distance [3.2137 (7) Å], which is less than the sum of van der Waals radii (3.6 Å), is typical for compounds containing sulfur atoms that are connected via an aromatic bond or double bond. Dräger et al. (1973) interpreted this phenomenon as a contact of gaps between sp3-hybridized orbitals, which means that the close proximity is caused by a steric effect but not by an overlapping of orbitals. Another structural characteristic of unsaturated dithioethers with electron-withdrawing backbones – the relatively short S—C bonds, which can be considered as partial double bonds (Dräger et al., 1973) or described with a mesomeric effect (Schwarze et al., 2012) – is eased when one of the S atoms becomes oxidized. The pushing of electron density from the sulfur to the electron-withdrawing benzene ring is suppressed. As a result, interestingly, both the C1—S1 [1.7997 (13) Å] and the C2—S2 [1.7748 (14) Å] bonds in (I) are longer than those in the comparable dithioether 1,2-bis[(2-hydroxyethyl)sulfanyl]benzene [1.766 (2) and 1.762 (2) Å; Traeger, Klamroth et al., 2012]. Moreover, in (I), the aromatic C1≐C2 bond [1.3905 (19) Å] bridging the two S atoms does not differ significantly from the other bonds in the aromatic ring. By contrast, in 1,2-bis[(2-hydroxyethyl)sulfanyl]benzene, this bond is longer [1.414 (3) Å], which is also assumed to be caused by the partial mesomeric effect mentioned above.
In PdII complex (II), the square-planar-coordinated central atom forms a five-membered chelate ring with ligand (I). This is similar to the known PdII complexes of the unsaturated open-chain dithioethers (Traeger, Klamroth et al., 2012). The maximum deviation from the best plane formed by S1/S2/Cl1/Cl2 is 0.0602 (3) Å (for S1). The central atom is located 0.0422 (4) Å from that plane. The torsion angle S1—C1—C2—S2 is reduced to -1.0 (3)° in comparison to that in the pure ligand [9.33 (16)°]. Owing to the binding to the PdII atom, atom S2 also becomes a centre of chirality. We obtained racemic crystals with the two 2-methoxyethyl arms in an anti conformation. The analogous dithioether complex dichlorido{1,2-bis[(2-methoxyethyl)sulfanyl]benzene}palladium(II) was also obtained as a racemic mixture, but for dichlorido{1,2-bis[(2-hydroxyethyl)sulfanyl]benzene}palladium(II), both the racemate and the meso form were obtained. However, according to Abel et al. (1982) the anti conformation of the arms is more stable. Paralleling the racemic dithioether PdII complexes, in thioether sulfoxide complex (II) there is an O atom situated above the central Pd atom at a Pd1···O3 distance [2.854 (3) Å] which is shorter than the sum of the van der Waals radii (3.1 Å). This indicates a weak interaction of the O atom with a d orbital of the PdII atom. Another remarkable aspect is the unusually short C11—O3 bond (Table 2) which is ca 0.05 Å shorter than in (I), probably in order to accommodate the Pd1···O3 interaction. The Pd1—S1 [2.2039 (6) Å] and Pd1—S2 [2.2633 (6) Å] bond lengths differ more from each other in (II) than do those in the analogous dithioether complex dichlorido{1,2-bis[(2-methoxyethyl)sulfanyl]benzene}palladium(II) [2.258 (1) and 2.242 (1) Å], but the Pd1—S2 bond in (II) is quite similar to the values found for the dithioether. Relatively few complexes with PdII coordinated by a sulfinyl group are described in the literature. The Pd—S bond lengths of most of them are somewhat longer than in (II), e.g. 2.252 and 2.257 Å in cis-dichlorido[3,4-bis(p-tolylsulfinyl)hexane]palladium(II) (Pettinari et al., 1999). Only in dichlorido[(S-methyl-L-cysteine)sulfoxide]palladium(II) monohydrate (Allain et al., 1980) was a similarly short Pd—S bond found (2.200 Å). The C1—S1 [1.777 (2) Å] and C2—S2 [1.781 (3) Å] bond lengths are nearly the same as in dichlorido{1,2-bis[(2-methoxyethyl)sulfanyl]benzene}palladium(II) [1.778 (4) and 1.781 (3) Å]. The same applies for the aromatic C1≐C2 bond, which is 1.384 (4) Å in (II) and 1.385 (5) Å in the reference compound dichlorido{1,2-bis[(2-methoxyethyl)sulfanyl]benzene}palladium(II). Comparing the bond lengths of the S1—C1≐C2—S2 unit in complex (II) with those in ligand (I), it becomes obvious that the thioether sulfoxide is very well preorganized for coordination to PdII. The changes observed in the geometry upon coordination are minimal. Only the C1—S1 bond is shortened by about 0.02 Å, resulting in a further closing of the distance between the two S atoms [ 3.2137 (7) Å in (I) and 3.1566 (9) Å in (II)].