Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113015060/fn3138sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113015060/fn3138Isup2.hkl |
CCDC reference: 957039
For related literature, see: Allan et al. (2006); Allen (2002); Aullón & Alvarez (1996); Groot et al. (1991); Sheldrick (2013).
All starting materials were obtained from the Aldrich Chemical Company and used without further purification. The 3,6,9-trithiabicyclo[9.3.1]pentadecane ligand was prepared in four steps (see Scheme 2). Analyses were performed by Canadian Microanalytical Service Ltd.
(i) Step 1. Conversion of 1, 3-cyclohexanedicarboxylic acid to its dimethyl ester, (1). (±)-1, 3-Cyclohexanedicarboxylic acid (5.20 g, 30.2 mmol) was dissolved in methanol (150 ml) to which concentrated H2SO4 (1 ml) was then added. The solution was stirred under reflux for 24 h then cooled to room temperature and neutralized with aqueous NaOH (2 M), and the solvent was removed under reduced pressure. Water (100 ml) was added to the residue and the mixture extracted with ether (4 × 50 ml). The extract was dried over MgSO4 and filtered, and the ether was removed under reduced pressure to yield (1) as a pale-yellow oil in 99% yield. 1H NMR (Frequency?, TMS, δ, p.p.m.): 3.68 (6H), 2.20–2.40 (2H), 1.90–2.05 (2H), 1.70–1.80 (2H), 1.50–1.60 (2H), 1.30–1.40 (2H).
(ii) Step 2. Conversion of (1) to the corresponding diol, (2). Under an atmosphere of dry nitrogen, LiAlH4 (9.5 g, 0.25 mmol) was suspended in dry diethyl ether (250 ml). The temperature of the suspension was maintained with an ice bath and a solution of (1) (14.5 g, 72.5 mmol) in dry diethyl ether (150 ml) was added dropwise over a period of 4 h. The mixture was then stirred overnight and allowed to warm to room temperature. Ethyl acetate (150 ml) was added to quench the remaining LiAlH4, followed by dilute (10%) aqueous H2SO4 (~150 ml) to dissolve sodium and aluminium salts. The two-layered mixture was separated, the aqueous layer washed with diethyl ether (2 × 100 ml), and the washings and original organic layer combined and dried over MgSO4. After filtration, the solvent was removed under reduced pressure to yield (2) as a nearly colourless oil in 85% yield. 1H NMR (Frequency?, TMS, δ, p.p.m.): 3.89 (2H), 0.8–2.7 (14H).
(iii) Step 3. Conversion of (2) to the corresponding dibromide, (3). This procedure was carried out in dry solvents under a dry nitrogen atmosphere. PBr3 (6.0 ml, 63.8 mmol) was dissolved in dry benzene (15 ml). Pyridine (1.5 ml) was added dropwise over a period of 15 min. A mixture of (2) (7.2 g, 50 mmol) and pyridine (1.0 ml) was added dropwise over a period of 4 h while maintaining a temperature of 278 K with a cold-water bath. The reaction was allowed to warm slowly to room temperature while stirring overnight. Water (250 ml) was added slowly to quench the remaining PBr3. The mixture was extracted with CHCl3 (3 × 200 ml) and the combined extracts dried over CaCl2. The solution was filtered and volatiles removed under reduced pressure to give (3) as a pale-yellow oil in 70% yield. 1H NMR (Frequency?, TMS, δ, p.p.m.): 3.25–3.40 (two doublets; 4H), 2.10–2.70 (10H).
(iv) Step 4. Formation of 3,6,9-trithiabicyclo[9.3.1]pentadecane, (4). This procedure was carried out under nitrogen and anhydrous conditions in a three-necked round-bottomed flask fitted with two dropping funnels on top of condensers. Sodium (0.90 g, 40 mmol) was reacted with commercial absolute ethanol (500 ml) in the round-bottomed flask and a solution of bis(2-mercaptoethyl)sulfide (3.08 g, 20.0 mmol) in tetrahydrofuran (THF) (75 ml) was placed in one dropping funnel. In the other funnel was placed (3) (5.40 g, 20.0 mmol) in commercial absolute ethanol (150 ml). A portion (10 ml) of the THF solution was added dropwise over a period of 10 min with stirring under reflux. Both solutions were then admitted dropwise at a rate of 2:1 ethanol:THF over a period of 4 h, and the resulting mixture was refluxed for a further 24 h. Upon cooling to room temperature, the solvent was removed under reduced pressure and the residue suspended in CHCl3 (300 ml). The suspension was washed with water (3 × 200 ml), and the organic layer dried over CaCl2 and filtered. The filtrate was reduced in volume under reduced pressure to approximately 30 ml and hot commercial absolute ethanol (60 ml) added. The solution was filtered and placed in a freezer for 1 d, after which time white crystals of (4) (m.p. 363.45–365.65 K) had formed. These were separated by filtration in 30% yield. 1H NMR (Frequency?, TMS, δ, p.p.m.): 2.60–3.00 (12H), 0.80–2.20 (10H); 13C NMR (Frequency?, TMS, δ, p.p.m.): 21–42. 12 main peaks, some as doublets due to the presence of two diastereomers. Mass spectrum, calculated for (C12H22S3)+: m/z = 262; found: m/z = 262.
(v) Preparation of the title complex, (I). Bis(acetonitrile)dichloropalladium(II) (0.39 g, 1.50 mmol) was dissolved in acetonitrile (80 ml) to give a yellow–orange solution. Likewise, (4) (0.40 g, 1.5 mmol) was dissolved in acetonitrile (80 ml) to give a colourless solution. The solutions were mixed at room temperature and stirred for 4 h, and then the volume was reduced in a rotary evaporator to ~15 ml. The resulting suspension was filtered at room temperature to yield orange crystals of (I) in 95% yield; these were dried in air. Analysis, calculated for C12H22Cl2PdS3.CH3CN: C 34.97, H 5.24, N 2.91, Cl 14.74%; found: C 35.23, H 5.82, N 3.02, Cl 14.15%.
H atoms were introduced into idealized positions and refined using the riding-atom formalism (idealized methyl refined as a rotating group.) The applied constraints were: Cmethine—Hmethine = 0.98 Å, Cmethylene—Hmethylene = 0.97 Å, Cmethyl—Hmethyl = 0.96 Å, and Uiso(Hmethine) = 1.2Ueq(Cmethine), Uiso(Hmethylene) = 1.2Ueq(Cmethylene), Uiso(Hmethyl) = 1.5Ueq(Cmethyl). A partial-occupancy acetonitrile solvent molecule was present. All atoms in this group (N1, C13 and C14) were constrained to have the same occupancy, which was allowed to refine freely (tied to the second free variable) and converged to 0.798 (10). A similarity restraint (the command SIMU within SHELXL-2013; Sheldrick, 2013) was applied to N1—C13—C14. Only reflections between 2θ = 5 and 53° were included (the command SHEL 8.146492 0.796384 within SHELXL-2013) in order to minimize beam-stop effects and weak intensity at higher angles.
Data collection: MSC/AFC Diffractometer Control Software (Rigaku, 1998); cell refinement: MSC/AFC Diffractometer Control Software (Rigaku, 1998); data reduction: MSC/AFC Diffractometer Control Software (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013); molecular graphics: Mercury (Macrae et al., 2008) and ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).
[PdCl2(C12H22S3)]·0.8C2H3N | F(000) = 1917 |
Mr = 472.62 | Dx = 1.668 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 16 reflections |
a = 24.906 (4) Å | θ = 10.1–13.1° |
b = 18.144 (2) Å | µ = 1.59 mm−1 |
c = 8.328 (2) Å | T = 299 K |
V = 3763.4 (12) Å3 | Irregular, yellow |
Z = 8 | 0.30 × 0.20 × 0.10 mm |
Rigaku AFC6S diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 26.4°, θmin = 2.8° |
ω–2θ scans | h = 0→32 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→23 |
Tmin = 0.715, Tmax = 0.853 | l = −10→0 |
4892 measured reflections | 3 standard reflections every 150 reflections |
3850 independent reflections | intensity decay: −5.8% |
2488 reflections with I > 2σ(I) |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0435P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
3850 reflections | Δρmax = 0.46 e Å−3 |
192 parameters | Δρmin = −0.58 e Å−3 |
12 restraints |
[PdCl2(C12H22S3)]·0.8C2H3N | V = 3763.4 (12) Å3 |
Mr = 472.62 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 24.906 (4) Å | µ = 1.59 mm−1 |
b = 18.144 (2) Å | T = 299 K |
c = 8.328 (2) Å | 0.30 × 0.20 × 0.10 mm |
Rigaku AFC6S diffractometer | 2488 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
Tmin = 0.715, Tmax = 0.853 | 3 standard reflections every 150 reflections |
4892 measured reflections | intensity decay: −5.8% |
3850 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 12 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.46 e Å−3 |
3850 reflections | Δρmin = −0.58 e Å−3 |
192 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pd1 | 0.07275 (2) | 0.03067 (2) | 0.45790 (4) | 0.03345 (12) | |
Cl1 | 0.06611 (6) | 0.12759 (7) | 0.27642 (17) | 0.0558 (4) | |
Cl2 | 0.08395 (5) | −0.05430 (7) | 0.25322 (16) | 0.0495 (3) | |
S1 | 0.05690 (5) | 0.11118 (7) | 0.66059 (16) | 0.0417 (3) | |
S2 | 0.25544 (5) | −0.07024 (7) | 0.61307 (15) | 0.0416 (3) | |
S3 | 0.07756 (5) | −0.06267 (7) | 0.63987 (15) | 0.0400 (3) | |
N1 | 0.3855 (4) | 0.2380 (6) | 0.3889 (16) | 0.148 (5) | 0.794 (10) |
C13 | 0.4218 (4) | 0.2337 (5) | 0.4601 (17) | 0.095 (4) | 0.794 (10) |
C14 | 0.4692 (4) | 0.2286 (5) | 0.5518 (16) | 0.117 (5) | 0.794 (10) |
H14A | 0.4971 | 0.2066 | 0.4881 | 0.176* | 0.794 (10) |
H14B | 0.4627 | 0.1987 | 0.6449 | 0.176* | 0.794 (10) |
H14C | 0.4802 | 0.2770 | 0.5849 | 0.176* | 0.794 (10) |
C1 | 0.1071 (2) | 0.1845 (3) | 0.6590 (7) | 0.0461 (13) | |
H1A | 0.1067 | 0.2066 | 0.5529 | 0.055* | |
H1B | 0.0953 | 0.2221 | 0.7339 | 0.055* | |
C2 | 0.16499 (18) | 0.1666 (2) | 0.6989 (6) | 0.0371 (10) | |
H2 | 0.1666 | 0.1510 | 0.8114 | 0.045* | |
C3 | 0.1987 (2) | 0.2373 (3) | 0.6809 (7) | 0.0464 (13) | |
H3A | 0.1964 | 0.2550 | 0.5712 | 0.056* | |
H3B | 0.1846 | 0.2753 | 0.7511 | 0.056* | |
C4 | 0.2573 (2) | 0.2223 (3) | 0.7233 (7) | 0.0509 (13) | |
H4A | 0.2783 | 0.2662 | 0.7010 | 0.061* | |
H4B | 0.2599 | 0.2123 | 0.8375 | 0.061* | |
C5 | 0.2810 (2) | 0.1579 (3) | 0.6312 (7) | 0.0477 (12) | |
H5A | 0.3170 | 0.1481 | 0.6701 | 0.057* | |
H5B | 0.2835 | 0.1706 | 0.5183 | 0.057* | |
C6 | 0.24677 (18) | 0.0882 (2) | 0.6497 (6) | 0.0356 (10) | |
H6 | 0.2457 | 0.0753 | 0.7640 | 0.043* | |
C7 | 0.18938 (18) | 0.1054 (2) | 0.5957 (6) | 0.0378 (11) | |
H7A | 0.1675 | 0.0613 | 0.6044 | 0.045* | |
H7B | 0.1896 | 0.1206 | 0.4840 | 0.045* | |
C8 | 0.27251 (19) | 0.0237 (3) | 0.5589 (6) | 0.0394 (11) | |
H8A | 0.3111 | 0.0288 | 0.5693 | 0.047* | |
H8B | 0.2640 | 0.0299 | 0.4461 | 0.047* | |
C9 | 0.18580 (18) | −0.0813 (3) | 0.5521 (6) | 0.0398 (11) | |
H9A | 0.1771 | −0.0450 | 0.4705 | 0.048* | |
H9B | 0.1808 | −0.1299 | 0.5059 | 0.048* | |
C10 | 0.14825 (19) | −0.0717 (3) | 0.6949 (6) | 0.0471 (12) | |
H10A | 0.1590 | −0.0282 | 0.7544 | 0.057* | |
H10B | 0.1522 | −0.1139 | 0.7655 | 0.057* | |
C11 | 0.0531 (2) | −0.0193 (3) | 0.8234 (6) | 0.0442 (12) | |
H11A | 0.0141 | −0.0198 | 0.8229 | 0.053* | |
H11B | 0.0651 | −0.0479 | 0.9151 | 0.053* | |
C12 | 0.0723 (2) | 0.0593 (3) | 0.8418 (6) | 0.0476 (13) | |
H12A | 0.1108 | 0.0598 | 0.8606 | 0.057* | |
H12B | 0.0548 | 0.0820 | 0.9334 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.03253 (19) | 0.0364 (2) | 0.03140 (19) | −0.00201 (14) | −0.00319 (16) | 0.00041 (16) |
Cl1 | 0.0715 (9) | 0.0464 (7) | 0.0494 (8) | −0.0079 (6) | −0.0103 (7) | 0.0135 (6) |
Cl2 | 0.0517 (7) | 0.0559 (7) | 0.0408 (6) | 0.0035 (6) | −0.0045 (6) | −0.0131 (6) |
S1 | 0.0364 (6) | 0.0443 (7) | 0.0443 (7) | 0.0013 (5) | 0.0016 (5) | −0.0072 (6) |
S2 | 0.0415 (7) | 0.0424 (7) | 0.0409 (6) | 0.0107 (5) | −0.0042 (6) | −0.0022 (6) |
S3 | 0.0401 (6) | 0.0411 (6) | 0.0389 (6) | −0.0051 (5) | −0.0020 (5) | 0.0051 (5) |
N1 | 0.103 (7) | 0.145 (10) | 0.196 (12) | −0.018 (7) | −0.039 (9) | 0.036 (9) |
C13 | 0.071 (6) | 0.064 (6) | 0.151 (11) | −0.006 (5) | −0.016 (7) | −0.005 (6) |
C14 | 0.109 (9) | 0.078 (7) | 0.165 (13) | −0.011 (6) | −0.002 (9) | 0.005 (8) |
C1 | 0.048 (3) | 0.031 (2) | 0.060 (3) | 0.006 (2) | −0.001 (3) | −0.012 (2) |
C2 | 0.038 (2) | 0.030 (2) | 0.044 (3) | −0.0032 (19) | −0.002 (2) | −0.005 (2) |
C3 | 0.052 (3) | 0.029 (2) | 0.057 (3) | −0.007 (2) | −0.004 (3) | 0.003 (2) |
C4 | 0.049 (3) | 0.040 (3) | 0.064 (3) | −0.014 (2) | −0.013 (3) | 0.004 (3) |
C5 | 0.041 (3) | 0.049 (3) | 0.054 (3) | −0.005 (2) | −0.003 (3) | 0.007 (3) |
C6 | 0.038 (2) | 0.036 (2) | 0.033 (2) | −0.0014 (19) | 0.000 (2) | 0.003 (2) |
C7 | 0.036 (2) | 0.036 (2) | 0.042 (3) | −0.002 (2) | −0.004 (2) | −0.009 (2) |
C8 | 0.036 (2) | 0.048 (3) | 0.034 (2) | 0.004 (2) | 0.001 (2) | −0.002 (2) |
C9 | 0.044 (3) | 0.038 (2) | 0.037 (3) | 0.003 (2) | −0.002 (2) | −0.001 (2) |
C10 | 0.044 (3) | 0.054 (3) | 0.044 (3) | 0.008 (2) | −0.002 (2) | 0.011 (2) |
C11 | 0.041 (3) | 0.061 (3) | 0.031 (2) | −0.010 (2) | 0.003 (2) | 0.002 (2) |
C12 | 0.049 (3) | 0.064 (3) | 0.029 (2) | −0.001 (3) | 0.006 (2) | −0.008 (2) |
Pd1—Cl1 | 2.3246 (13) | C4—H4A | 0.9700 |
Pd1—Cl2 | 2.3154 (13) | C4—H4B | 0.9700 |
Pd1—S1 | 2.2669 (13) | C4—C5 | 1.518 (7) |
Pd1—S3 | 2.2759 (13) | C5—H5A | 0.9700 |
S1—C1 | 1.827 (5) | C5—H5B | 0.9700 |
S1—C12 | 1.820 (5) | C5—C6 | 1.532 (6) |
S2—C8 | 1.814 (5) | C6—H6 | 0.9800 |
S2—C9 | 1.818 (5) | C6—C7 | 1.531 (6) |
S3—C10 | 1.827 (5) | C6—C8 | 1.533 (6) |
S3—C11 | 1.824 (5) | C7—H7A | 0.9700 |
N1—C13 | 1.085 (13) | C7—H7B | 0.9700 |
C13—C14 | 1.410 (15) | C8—H8A | 0.9700 |
C14—H14A | 0.9600 | C8—H8B | 0.9700 |
C14—H14B | 0.9600 | C9—H9A | 0.9700 |
C14—H14C | 0.9600 | C9—H9B | 0.9700 |
C1—H1A | 0.9700 | C9—C10 | 1.523 (6) |
C1—H1B | 0.9700 | C10—H10A | 0.9700 |
C1—C2 | 1.514 (6) | C10—H10B | 0.9700 |
C2—H2 | 0.9800 | C11—H11A | 0.9700 |
C2—C3 | 1.540 (6) | C11—H11B | 0.9700 |
C2—C7 | 1.531 (6) | C11—C12 | 1.512 (7) |
C3—H3A | 0.9700 | C12—H12A | 0.9700 |
C3—H3B | 0.9700 | C12—H12B | 0.9700 |
C3—C4 | 1.525 (7) | ||
Cl2—Pd1—Cl1 | 91.92 (5) | C4—C5—C6 | 111.6 (4) |
S1—Pd1—Cl1 | 89.11 (5) | H5A—C5—H5B | 108.0 |
S1—Pd1—Cl2 | 176.65 (5) | C6—C5—H5A | 109.3 |
S1—Pd1—S3 | 89.59 (5) | C6—C5—H5B | 109.3 |
S3—Pd1—Cl1 | 178.45 (5) | C5—C6—H6 | 108.0 |
S3—Pd1—Cl2 | 89.33 (5) | C5—C6—C8 | 110.3 (4) |
C1—S1—Pd1 | 110.16 (18) | C7—C6—C5 | 108.8 (4) |
C12—S1—Pd1 | 104.33 (17) | C7—C6—H6 | 108.0 |
C12—S1—C1 | 103.8 (3) | C7—C6—C8 | 113.6 (4) |
C8—S2—C9 | 104.9 (2) | C8—C6—H6 | 108.0 |
C10—S3—Pd1 | 106.55 (17) | C2—C7—H7A | 109.5 |
C11—S3—Pd1 | 102.68 (17) | C2—C7—H7B | 109.5 |
C11—S3—C10 | 98.7 (2) | C6—C7—C2 | 110.7 (4) |
N1—C13—C14 | 179.6 (16) | C6—C7—H7A | 109.5 |
C13—C14—H14A | 109.5 | C6—C7—H7B | 109.5 |
C13—C14—H14B | 109.5 | H7A—C7—H7B | 108.1 |
C13—C14—H14C | 109.5 | S2—C8—H8A | 107.4 |
H14A—C14—H14B | 109.5 | S2—C8—H8B | 107.4 |
H14A—C14—H14C | 109.5 | C6—C8—S2 | 119.8 (3) |
H14B—C14—H14C | 109.5 | C6—C8—H8A | 107.4 |
S1—C1—H1A | 107.4 | C6—C8—H8B | 107.4 |
S1—C1—H1B | 107.4 | H8A—C8—H8B | 106.9 |
H1A—C1—H1B | 106.9 | S2—C9—H9A | 109.5 |
C2—C1—S1 | 119.6 (3) | S2—C9—H9B | 109.5 |
C2—C1—H1A | 107.4 | H9A—C9—H9B | 108.1 |
C2—C1—H1B | 107.4 | C10—C9—S2 | 110.8 (3) |
C1—C2—H2 | 108.1 | C10—C9—H9A | 109.5 |
C1—C2—C3 | 108.6 (4) | C10—C9—H9B | 109.5 |
C1—C2—C7 | 114.2 (4) | S3—C10—H10A | 108.8 |
C3—C2—H2 | 108.1 | S3—C10—H10B | 108.8 |
C7—C2—H2 | 108.1 | C9—C10—S3 | 114.0 (3) |
C7—C2—C3 | 109.5 (4) | C9—C10—H10A | 108.8 |
C2—C3—H3A | 109.5 | C9—C10—H10B | 108.8 |
C2—C3—H3B | 109.5 | H10A—C10—H10B | 107.7 |
H3A—C3—H3B | 108.1 | S3—C11—H11A | 109.1 |
C4—C3—C2 | 110.5 (4) | S3—C11—H11B | 109.1 |
C4—C3—H3A | 109.5 | H11A—C11—H11B | 107.8 |
C4—C3—H3B | 109.5 | C12—C11—S3 | 112.7 (3) |
C3—C4—H4A | 109.0 | C12—C11—H11A | 109.1 |
C3—C4—H4B | 109.0 | C12—C11—H11B | 109.1 |
H4A—C4—H4B | 107.8 | S1—C12—H12A | 109.7 |
C5—C4—C3 | 113.1 (4) | S1—C12—H12B | 109.7 |
C5—C4—H4A | 109.0 | C11—C12—S1 | 109.7 (3) |
C5—C4—H4B | 109.0 | C11—C12—H12A | 109.7 |
C4—C5—H5A | 109.3 | C11—C12—H12B | 109.7 |
C4—C5—H5B | 109.3 | H12A—C12—H12B | 108.2 |
Pd1—S1—C1—C2 | −67.6 (5) | C3—C4—C5—C6 | −53.7 (6) |
Pd1—S1—C12—C11 | −38.8 (4) | C4—C5—C6—C7 | 56.2 (6) |
Pd1—S3—C10—C9 | −53.7 (4) | C4—C5—C6—C8 | −178.6 (4) |
Pd1—S3—C11—C12 | −38.7 (4) | C5—C6—C7—C2 | −60.5 (5) |
S1—C1—C2—C3 | 177.4 (4) | C5—C6—C8—S2 | 158.7 (4) |
S1—C1—C2—C7 | 54.9 (6) | C7—C2—C3—C4 | −55.8 (6) |
S2—C9—C10—S3 | 167.9 (3) | C7—C6—C8—S2 | −78.9 (5) |
S3—C11—C12—S1 | 52.3 (5) | C8—S2—C9—C10 | −98.9 (4) |
C1—S1—C12—C11 | −154.2 (3) | C8—C6—C7—C2 | 176.2 (4) |
C1—C2—C3—C4 | 178.8 (5) | C9—S2—C8—C6 | 68.7 (4) |
C1—C2—C7—C6 | −177.1 (4) | C10—S3—C11—C12 | 70.5 (4) |
C2—C3—C4—C5 | 53.1 (6) | C11—S3—C10—C9 | −159.7 (4) |
C3—C2—C7—C6 | 60.9 (5) | C12—S1—C1—C2 | 43.6 (5) |
Experimental details
Crystal data | |
Chemical formula | [PdCl2(C12H22S3)]·0.8C2H3N |
Mr | 472.62 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 299 |
a, b, c (Å) | 24.906 (4), 18.144 (2), 8.328 (2) |
V (Å3) | 3763.4 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.59 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Rigaku AFC6S diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.715, 0.853 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4892, 3850, 2488 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.109, 0.99 |
No. of reflections | 3850 |
No. of parameters | 192 |
No. of restraints | 12 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.58 |
Computer programs: MSC/AFC Diffractometer Control Software (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2013), Mercury (Macrae et al., 2008) and ORTEP-3 (Farrugia, 2012), OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).
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Group 10 transition metal complexes, in the +2 oxidation state (d8), normally exhibit stable square-planar geometries, in compliance with the 16-electron rule. However, the presence of two non-bonding orbitals perpendicular to the coordination plane, i.e. the occupied dz2 and the empty pz, means that higher coordination numbers can be achieved, with the cation possessing the ability to act as either a Lewis base or Lewis acid, or in some reported cases, both (Aullón & Alvarez, 1996). Further, Allan et al. (2006) have reported the high-pressure (46 kbar; 1 bar = 100000 Pa) conversion of cis-dichloro-(1,4,7-trithiacyclononane-S,S')palladium from a square-planar mononuclear complex to a six-coordinate chain polymer via apical coordination to both the third S atom in the ligand and a meridionally coordinated S atom in another nominal monomeric Pd complex. The authors present their work as a route to novel metal stereochemistries.
In the title complex, (I), the thioether ligand has the potential for up to three metal binding sites, but it coordinates in a cis-bidentate manner via two adjacent S atoms to the Pd centre, yielding a five-membered chelate ring (Fig. 1). The overall coordination geometry at the metal is square planar, with the remaining coordination sites occupied by chloride ligands. Atom Pd1 deviates from the Cl2S2 mean plane by 0.0406 (7) Å. A survey of the Cambridge Structural Database (CSD, Version 5.34 with February 2013 update; Allen, 2002) for all cis-PdCl2S2-containing structures was performed, yielding 115 unique observations of Pd—Cl and Pd—S bond lengths, and Cl—Pd—Cl and S—Pd—S angles. Average distances of 2.32 (3) and 2.31 (14) Å were found for Pd—Cl and Pd—S, respectively, while for Cl—Pd—Cl and S—Pd—S average angles of 92 (4) and 89 (5)° were found. The results reported here for (I) are in agreement with these previous values.
The overall structure of (I) is similar to that reported by de Groot et al. (1991) using the 2,5,8-trithia(9)-m-benzeneophane ligand, but stands in contrast with the coordination mode exhibited by Pd with the 2,5,8-trithia(9)-o-benzeneophane ligand. In that complex, a cis-PdCl2S2 coordination motif was also reported (de Groot et al., 1991), but the third S atom was present at a distance of 3.076 (3) Å, indicating apical coordination to Pd. In the title complex, the intramolecular distance from Pd to the third S atom is 5.0721 (14) Å, while the closest intermolecular approach of a third S atom to Pd1 is 5.2031 (14) Å [for atom S2, generated by the symmetry operation (1/2 - x, -y, z - 1/2)], which far exceeds the sum of the van der Waals radii for Pd and S (3.43 Å; Standard reference?). Of note in (I) is that the square-planar PdCl2S2 surfaces, oriented away from the uncoordinated macrocyclic atoms, pack in a face-to-face manner across the inversion centres at Wyckoff position 4b (Fig. 2). Plane-to-plane separations for the PdCl2S2 pairs are 3.6225 (12) Å off-set by 1.1263 (19) Å, with Pd···Pd separations of 3.8551 (8) Å.